Interface Vol. 28, No. 2, Summer by The Electrochemical Society

VOL. 28, NO. 2 Summer 2019

IN THIS ISSUE 3 From the Editor:

Not All Who Wander Are Lost, But Some Are

7 From the President:

One Year of Presidency— Just a Blink Given Our Society’s Long History

13 235th ECS Meeting Highlights

39 Looking at Patent Law 45 Tech Highlights 47 Current Trends in Electrolytes

49 Electrolyte Development for High-Performance Li-Ion Cells: Additives, Solvents, and Agreement with a Generalized Molecular Model

55 Lithium Metal Polymer Electrolyte Batteries: Opportunities and Challenges

63 Controlling Ionic Transport through the PEO-LiTFSI/ LLZTO Interface

Current Trends in

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71 Electrolyte Solutions for

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The Electrochemical Society Interface • Summer 2019 • www.electrochem.org

FROM THE EDITOR

Not All Who Wander Are Lost, But Some Are

s the (likely several) devoted readers of this column no doubt recall, in the last issue I made a plea to all of you to reach out and renew some old friendships. The suggested selection criterion was for someone whose memory makes you automatically smile. Through my contacts at the federal level, I have determined that many of you have actually done that which will help balance some of the bad karma you have created (you know who you are). I suspect that as your mind wandered through all of the people who have been important in your life, you found you would describe more than a few of them as mentors. The three entries in the Merriam-Webster dictionary defining “mentor” include: “capitalized: a friend of Odysseus entrusted with the education of his son Telemachus;” “(geographical name) city in northeastern Ohio northeast of Cleveland, population 47,159;” and “a trusted counselor or guide.” For purposes of this essay, let’s select the third definition, which—while succinct—does not capture the true essence of a mentor. Mentoring can be described in many ways, but I think that the title of an essay by Kirk Martini, a colleague of mine at Virginia, captures it: “Usually Nice, Always Helpful.”* He points out that many of us who serve as mentors, formally or informally, are more concerned with being pleasant than being valuable. The best mentor-mentee relationships are founded on a deep trust in which both people have an unshakable faith in the good intentions of the other. It is not a mutual admiration society where we only tell each other how wonderful we are. In a variant of a quote attributed to Harry Truman (apparently incorrectly), Carl Icahn, and the fictitious Gordon Gekko, among others: “You want a friend, get a dog.” As a side note, as the owner of two whippets, I know this to be true. Other than small children, no one greets you with more unbounded enthusiasm when you get home (or come back from getting the mail). Of course, mentors and mentees should celebrate victories large and small; but those victories are often the fruit of difficult conversations where truth is spoken, often in the form of questions from the mentor to the mentee about goals and the methods to reach those goals. I have had more than my fair share of fabulous mentors (to those who have not, please excuse my good fortune). For each one, I can remember an instance (okay, more than one) in which my mentor sat me down and said, in effect, “Rob, you are being a bonehead.” Of course, they were far more articulate, but equally direct. I was not always the most willing recipient at the time (a belated apology to them), but in retrospect I can see that it was those conversations as much as any others that changed the vector of my career and life. They cared enough to do the uncomfortable job of telling me what I needed to hear, rather than what I wanted to hear, for which I am forever in their debt. Obviously (hopefully), there are a lot of ways to tell someone something that they don’t want to hear. Some are efficient, some are effective, but few are both. It may sound like mentoring is a job only for those who are the perfect combination of Plato, Mother Teresa, and an army drill sergeant. I beg to differ. The simple key to being a good mentor is having the best interest of the mentee as the number one, number two, and number three priorities of the relationship. A rule of thumb is that, to the mentor, the mentee’s success should be more important than the mentor’s success. Sharing one’s own battle scars can be helpful in showing that mistakes or missteps are usually not fatal, although they may seem so at the time, and that true good is often the offspring of challenges and the grit to respond to them. So here is another call to arms: be a mentor—you probably are already and may not know it. More importantly, be a good mentor. It will be a small, but important, way to honor those who served (and may still be serving) you. Until next time, be safe and happy.

Rob Kelly Editor rgk6y@virginia.edu https://orcid.org/0000-0002-7354-0978

*www.people.virginia.edu/~km6e/Papers/pausch-mentor-essay.pdf The Electrochemical Society Interface • Summer 2019 • www.electrochem.org

Published by: The Electrochemical Society (ECS) 65 South Main Street Pennington, NJ 08534-2839, USA Tel 609.737.1902, Fax 609.737.2743 www.electrochem.org Editor: Rob Kelly, rgk6y@virginia.edu Guest Editors: Bryan D. McCloskey, bmcclosk@ berkeley.edu; Kang Xu, conrad.k.xu.civ@mail.mil Contributing Editors: Donald Pile, Donald.Pile@gmail. com; Alice Suroviec, asuroviec@berry.edu Managing Editor: Annie Goedkoop, Annie.Goedkoop@electrochem.org Print Production Manager: Dinia Agrawala, interface@electrochem.org Staff Contributors: Beth Craanen, Annie Goedkoop, Mary Hojlo, Ngoc Le, John Lewis, Jennifer Ortiz, Shannon Reed, Andrew Ryan. Advisory Board: Brett Lucht (Battery), Dev Chidambaram (Corrosion), Durga Misra (Dielectric Science and Technology), Philippe Vereecken (Electrodeposition), Jennifer Hite (Electronics and Photonics), A. Manivannan (Energy Technology), Sean Bishop (High-Temperature Energy, Materials, & Processes), John Weidner (Industrial Electrochemistry and Electrochemical Engineering), Uwe Happek (Luminescence and Display Materials), Slava Rotkin (Nanocarbons), Jim Burgess (Organic and Biological Electrochemistry), Andrew Hillier (Physical and Analytical Electrochemistry), Ajit Khosla (Sensor) Director of Publications: Beth Craanen, Beth.Craanen@electrochem.org Publications Subcommittee Chair: Eric Wachsman Society Officers: Christina Bock, President; Stefan De Gendt, Senior Vice President; Eric Wachsman, 2nd Vice President; Turgut Gür, 3rd Vice President; James Fenton, Secretary; Gessie Brisard, Treasurer; Christopher J. Jannuzzi, Executive Director & CEO Statements and opinions given in The Electrochemical Society Interface are those of the contributors, and ECS assumes no responsibility for them. Authorization to photocopy any article for internal or personal use beyond the fair use provisions of the Copyright Act of 1976 is granted by The Electrochemical Society to libraries and other users registered with the Copyright Clearance Center (CCC). Copying for other than internal or personal use without express permission of ECS is prohibited. The CCC Code for The Electrochemical Society Interface is 1064-8208/92. Canada Post: Publications Mail Agreement #40612608 Canada Returns to be sent to: Pitney Bowes International, P.O. Box 25542, London, ON N6C 6B2 ISSN : Print: 1064-8208

Online: 1944-8783

The Electrochemical Society Interface is published quarterly by The Electrochemical Society (ECS), at 65 South Main Street, Pennington, NJ 08534-2839 USA. Subscription to members as part of membership service; subscription to nonmembers is available; see the ECS website. Single copies $10.00 to members; $19.00 to nonmembers. © Copyright 2019 by The Electrochemical Society. Periodicals postage paid at Pennington, New Jersey, and at additional mailing offices. POSTMASTER: Send address changes to The Electrochemical Society, 65 South Main Street, Pennington, NJ 08534-2839. The Electrochemical Society is an educational, nonprofit 501(c)(3) organization with more than 8,500 scientists and engineers in over 75 countries worldwide who hold individual membership. Founded in 1902, the Society has a long tradition in advancing the theory and practice of electrochemical and solid state science by dissemination of information through its publications and international meetings. 3 All recycled paper. Printed in USA.

The Electrochemical Society Interface • Summer 2019 • www.electrochem.org

Vol. 28, No. 2 Summer 2019

Current Trends in Electrolytes by Bryan D. McCloskey and Kang Xu

Electrolyte Development for High-Performance Li-Ion Cells: Additives, Solvents, and Agreement with a Generalized Molecular Model by Eric R. Logan, Kevin L. Gering, Xiaowei Ma, and Jeff R. Dahn

the Editor: 3 From Not All Who Wander

Are Lost, But Some Are

the President: 7 From One Year of Presidency— Just a Blink Given Our Society’s Long History

and 8 Diversification Inclusion at ECS

Lithium Metal Polymer Electrolyte Batteries: Opportunities and Challenges by Jijeesh Ravi Nair, Laura Imholt, Gunther Brunklaus, and Martin Winter

ECS Meeting 13 235th Highlights

Controlling Ionic Transport through the PEO-LiTFSI/LLZTO Interface by Arushi Gupta and Jeff Sakamoto

Electrolyte Solutions for “Beyond Li-Ion Batteries”: Li-S, Li-O2, and Mg Batteries by Daniel Sharon, Michael Salama, Ran Attias, and Doron Aurbach

39 Looking at Patent Law 45 Tech Highlights 78 Section News 79 Awards Program 81 New Members 86 Student News ECS Meeting 90 237th Call for Papers

20 Society News 35 People News S: 36 Plan What You Need to Know

On the Cover: Li-ion solvation structure dictates its deposition at Li metal surface. The Electrochemical Society Interface • Summer 2019 • www.electrochem.org

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The Electrochemical Society Interface • Summer 2019 • www.electrochem.org

FROM T HE PRESIDENT

One Year of Presidency— Just a Blink Given Our Society’s Long History

However, scientific publishing has become a multibillion y year as ECS president dollar business. Its sheer size allows it to exercise an influence starts as our Society moves from which we cannot hide. ECS is one of the few not-forinto its 117th year of profit publishers left, and as a society, we have made a existence. Looking back on ECS’s decision to stay true to our values and to continue to publish history, I recognize the longstanding relevance and impact of peer-reviewed articles. Furthermore, we launched the Free the our Society, yet I’m also cognizant of our continuous need to Science campaign, which has the goal of not only letting us evolve. continue to publish according to our standards but allowing The Society was formed 117 years ago to advance authors to publish at an affordable cost, thus allowing the electrochemical and solid state science and technology. This research dollars to flow into is what we, for example, the research for which they are practice at our meetings, actually intended. which are places for sharing This year also marks 40 our research and engaging in years since ECS elected its discussions with the experts. Given the long existence of first female president, Joan But our Society has more than Berkowitz, an occasion we a long history; we also have our Society, my year as president will celebrate in Atlanta technical interest areas that with the Z03: 40 Years After offer technological solutions will be no more than a blink, yet symposium—looking back, to societal needs. Hence we of course, but also forward. I should not be surprised that what we are going to do together take pride in the fact that ECS we are facing competition; elected a female president success is accompanied by will influence its future. in a time when women in competition. The key is to such positions were few and understand this and to keep far between. Nevertheless, I evolving, just as we move our realize that much more work research forward. We do not needs to be done in this area. stand still and reinvent. To that end, the ECS Board of Directors recently approved a Of course, we are facing challenges, and as we all know, Diversity and Inclusion Statement (see page 10 of this issue). changes in the publishing world present such a challenge. I Also, on page 8 of this issue, former ECS executive director reflect upon the times when I attended my first ECS meeting, Roque Calvo examines the history of diversity and inclusion became a member, and first published in the Journal of The at ECS. Electrochemical Society. It had been a different world, a world Given the long existence of our Society, my year as where the focus was to produce the best quality publication— president will be no more than a blink, yet what we are going an article that was relevant, would stand the test of time, and to do together will influence its future. It is a daunting task, would be read and used long after it was written. Articles but I know that I can count on the vision of our Society, the published in our journal stood—and in fact, still stand—for volunteer members, and the ECS staff to facilitate our next this. We did not talk about the impact factor. We actually read evolution. the article, made judgements based on the technical content, and learned from it.

“

”

Christina Bock ECS President president@electrochem.org https://orcid.org/0000-0001-9737-8701

The Electrochemical Society Interface • Summer 2019 • www.electrochem.org

Diversification and Inclusion at ECS by Roque Calvo Female ECS Presidents

Joan Berkowitz (1979–1980)

Kathryn Bullock (1995–1996)

Jan Talbot (2001–2002)

uring the Society’s long and successful lifetime, there have been profound changes marked by milestones, and at the 2019 fall meeting in Atlanta, Georgia, ECS will hold a symposium to celebrate a seldom recognized but extremely significant milestone in its history. In the Z03: 40 Years After symposium, ECS will recognize the 40th anniversary of the Society’s first female president, Joan Berkowitz, examining diversity and the impact it has had on ECS. While the focus of the symposium will be on the impact of gender in leadership, the diversity of cultures, generations, institutions, and the scope of technical interests have all contributed to the inclusiveness and diversity that have impacted the long-term success of ECS. The most important dynamic, and perhaps the key to the Society’s long-term growth and success, has been its commitment to a powerful purpose and diversification of the ECS community. Progress and breakthroughs in science are typically the result of contributions and input from a multitude of researchers, so it has been natural and intentional for ECS to have facilitated diverse participation in its activities. This has attracted a great number of contributors to the ECS mission, which is simply to disseminate research to advance the science. Through its core activities, ECS has maintained a laser focus on the mission and enabled diverse participation, but there are other important characteristics about its leadership and conduct that have supported diversity and inclusion. These characteristics are truth and passion, which are fundamental to the ECS community and its activities.

International Diversity Since its founding, the Society has supported a diverse community of scientists and engineers who have participated in the meetings, have published in the journals, and have been recognized for their achievements through ECS’s awards program. Since the first ECS meeting, held in April 1902, the ECS community has included global participation from scientists and engineers with common interests in electrochemistry. ECS may have been the first professional society to formally recognize international diversity. In 1930, ECS, which was then called the American Electrochemical Society, dropped “American” from its name because of the robust international participation in its membership and meetings. ECS further welcomed international diversity through its international partnerships. In 1987, ECS held its first joint international meeting in the Pacific Rim (PRiME) in partnership with the Electrochemical Society of Japan. Later, partnerships were established in Latin America (AiMES), Europe (ECEE), and China (ISTC), driving meeting attendees from outside the U.S. to represent over 52% of the participation since 2016. Now, ECS has members, meeting attendees, and authors residing in more than 80 countries. As with ECS meetings, the growth in ECS publications has been primarily from authors outside the U.S. In 2018, these authors represented over 85% of the manuscripts submitted to ECS journals.

Technical Diversity

Robin Susko (2004–2005)

The globalization of ECS has influenced technical diversity in the Society, which has created a multidisciplinary community unlike many other more monolithic professional societies. The diversity or scope of the Society’s fundamental technical areas of electrochemical and solid state science and technology include research interests involving chemistry, physics, materials

science, and several major engineering disciplines (mechanical, chemical, corrosion, optical, and electrical). And this technical diversity connects a large gamut of organizational affiliations to ECS, leading to participation from a healthy mix of industrial, government, and academic research institutions. The strong academic constituency enables further diversification by enabling student participation and thus providing ECS with contributors ranging from graduate students to world-recognized scientists. Through the development of programs aimed at supporting students, this segment of ECS’s community has been the fastest growing over the past 10 years, with the number of student chapters growing from 15 to 81.

Gender Diversity Finally, after four decades of progress, gender diversity in the ECS community can be observed through a high level of participation by women in the programs and leadership of the organization, and through increasing recognition of their research achievements. The rest of this article is dedicated to pioneering female leaders who influenced ECS. Through their experiences, it was clear to see how they drove further diversity and inclusion in ECS and in the world of science, which has been late to embrace gender diversity. During my career at ECS, I had the opportunity to work with all seven female ECS presidents: Joan Berkowitz (1979–1980), Kathryn Bullock (1995–1996), Jan Talbot (2001–2002), Robin Susko (2004–2005), Esther Takeuchi (2011– 2012), Johna Leddy (2017–2018), and Christina Bock (2019–2020). I also worked with five female leaders who were elected to the office of ECS secretary or treasurer, and during 15 of the 26 years I served as executive director, there was a prominent female officer providing input and direction at the highest level of leadership in ECS. They all left a unique legacy and were friends and mentors whose courage and influence effectively guided me during my service to ECS.

The Electrochemical Society Interface • Summer 2019 • www.electrochem.org

Joan Berkowitz—ECS’s first great stride in gender diversity came with the election of its first female vice president, Joan Berkowitz, in 1976. After her three-year service as vice president, she was elected as the first female president and board chair, leading ECS in that role from 1979 to 1980. She accepted ECS’s nomination at a time when male-dominated corporate research institutions like AT&T, IBM, TI, GE, Intel, and RCA exercised a heavy influence on ECS. This corporate support and the development of wet and dry electrochemistry led to the vibrant growth of ECS publications, meetings, and membership during her presidency. Her character, leadership, and collaboration abilities were the benchmarks of her success and opened opportunities for future women leaders in ECS. Kathryn Bullock—In 1992, Kathryn Bullock was elected as vice president, and like Berkowitz, she came from the corporate world, beginning her career at Johnson Controls and later moving to AT&T Bell Laboratories. Her industry experience, along with her longtime work for ECS divisions and sections, prepared her for the grassroots membership and programming needs of the Society. During her presidency, she was tasked with overseeing the Society’s aggressive entry into the digital world. In 1995, ECS launched its first organizational website and opened a digital abstract submission website for its meetings. This forever changed the way ECS exchanged information and interacted with its community. As president during this change, Bullock provided guidance in future programming decisions and skilled diplomacy in board-related decisions; she piloted the board with the courage necessary to lead a dramatic change in the way ECS did business. Jan Talbot—In 1998, Jan Talbot was elected vice president, which set her up to lead ECS as president in the year of its most significant milestone—the ECS Centennial in 2002. She came from a university background and brought a different skill set than her predecessors, but one that was effective and timely. Talbot worked in hands-on positions in ECS, serving as a section officer, chair of the Education Committee, and Interface editor, all of which provided her with deep understanding of the organization’s mechanics. This experience, coupled with her special ability to collaborate and build consensus, enabled her successful leadership of the Centennial Celebration. The Centennial brought together influential scientists and engineers from ECS’s past and a few dozen representatives from its sister societies—all with strong connections to and opinions about this celebration of ECS history. Talbot was a perfect representative for ECS who complemented past president Bob Frankenthal (a senior ECS member who chaired the Centennial) as a leader of this important celebration. The timing of Talbot’s presidency

also coincided with ECS’s second joint meeting with the International Society of Electrochemistry (ISE) in San Francisco. ISE’s president at the time was Erika Kalman, and the two superbly navigated the challenges of working jointly to organize a highly successful international meeting. Sadly, the San Francisco meeting was immediately followed by 9/11, but Talbot’s positive spirit helped ECS through this tragic time. Robin Susko—Robin Susko followed in Talbot’s footsteps, taking the reins of the fiveyear Centennial Fundraising Campaign (2002– 2007) after being elected to the presidency in 2004. Like Talbot, she presided over two of the most significant meetings in ECS history (the 203rd ECS Meeting, held in Paris, France, and PRiME 2004, held in Honolulu, Hawaii). Coming from the corporate environment at IBM, Susko brought a different type of diplomacy to ECS but was equally effective in building support for and international partnerships with ECS. While ECS experienced great success during her presidency, Susko’s most significant impact came during her term as the first female ECS secretary (1996– 2000). Under her direction, the executive director role was restructured to provide this senior staff officer position with the authority, accountability, and security necessary to direct ECS during the challenging years ahead. As executive director at that time, I gained confidence in my role and clarity in regard to my responsibilities, which enabled my strategic abilities and provided me with opportunities that led to a long and progressive career at ECS. I am thankful for her wisdom, support, and courage. Esther Takeuchi—Esther Takeuchi was elected vice president in 2008 and began her service at the time we were building the ECS Digital Library as we know it today. It was a period of great change in the way that ECS disseminated content because of the powerful new tools for discovery inspired by Google and the challenges being posed to the historical subscription model of content distribution. Journal subscriptions rates were being challenged by government funding agencies that correctly observed that the dissemination of research papers funded by taxpayers was being obstructed by the high cost to subscribe. This was a critical issue for ECS; as early as 2010, ECS published the first information about this challenge, which it eventually addressed with the launch of the Free the Science initiative in 2014. Takeuchi was a key strategist and advocate behind this initiative and brought superb diplomacy and management skills to the presidency, which she acquired from experience in both the academic and industrial worlds. And, as a 2010 U.S. National Medal of Technology winner, she held a position of great stature in the ECS community, which afforded her credibility that was important to drive change and diversity.

Esther Takeuchi (2011–2012)

Johna Leddy (2017–2018)

Christina Bock (2019–2020)

(continued on next page)

The Electrochemical Society Interface • Summer 2019 • www.electrochem.org

(continued from previous page)

Johna Leddy and Christina Bock—The impact of the two most recent female presidents, Johna Leddy and Christina Bock, goes beyond their presidencies because both served in other ECS officer positions; Leddy was secretary (2008–2012) and Bock was treasurer (2010–2014). These offices have historically been male dominated, so these two women started on a pioneering path. Leddy was the second female ECS secretary and was immediately followed by Lili Deligianni (2012–2016), who represented the third female to hold this office out of the last six ECS secretaries. Bock was the first and only female ECS treasurer until Gessie Brissard was elected last year (2018–2022). These four-year offices, combined with the terms of vice president, president, and past president, extended their board service to nine years. The duration of their service and thus the impact that Leddy and Bock have had on ECS cannot be overstated. Their collective influence has led to greater inclusiveness and programmatic success, exemplified by the Leddy/Bock co-creation of the Electrochemical Energy Summit. The summit was first conducted in 2011 and has become one of the most important in ECS’s biannual meeting series. Leddy and Bock’s creative planning was captured on video (https://youtu.be/bpzyj7YCiBU) and epitomizes the power and influence of gender diversification in ECS.

Next Steps The Society’s commitment to accelerating scientific discovery and innovation has been greatly enhanced by its commitment to diversity and inclusion. And to further enhance this commitment, on all levels

and across all the Society’s affairs, ECS is proud to announce that the ECS Board of Directors recently approved a Diversity and Inclusion Statement (see below). From the beginning, the ECS community has placed great importance on inclusiveness and diversity; now, these values are reflected in the objectives, activities, governance, and culture of the organization. They are critical components of the Society’s past and future success in achieving its primary mission— to advance electrochemical and solid state science and technology.

About the Author Roque Calvo is the former ECS executive director and chief executive officer (1991– 2018). During his long tenure with ECS, Calvo spearheaded the Society’s transition to digital platforms and facilitated the vast expansion of its global partnerships, student programs, and awards portfolio. He served a pivotal role in the implementation of many momentous and far-reaching Society enterprises, including the establishment of this magazine and the launch of the Free the Science initiative, which continues to guide the Society’s direction. https://orcid.org/0000-0002-1746-8668

ECS’s Commitment to Diversity and Inclusion ECS is committed to accelerating scientific discovery and innovation, and to leading the community as the advocate, guardian, and facilitator of the Society’s technical domain. A major part of this commitment is to foster diversity and inclusion, on all levels, across all the Society’s affairs. To that end, ECS is proud to announce that the Board of Directors, on the recommendation of ECS’s Ethical Standards Committee, chaired by Johna Leddy, recently approved the following Diversity and Inclusion Statement: The Electrochemical Society strives to be an inclusive organization that promotes and values diversity. We recognize and respect the rights of all, and are committed to building and maintaining a culture that encourages, supports, and celebrates the unique backgrounds and experiences of our members, volunteers, employees, and constituents. Diversity is our strength. It fuels innovation, enhances collaboration, enables our best accomplishments, brings us closer to the communities we serve, and advances our mission to promote electrochemical and solid state science worldwide. Please join the Society in celebrating diversity in all its forms. To learn more, get involved, or share your views on this vital topic, contact ECS Executive Director Christopher Jannuzzi at Chris.Jannuzzi@electrochem.org.

The Electrochemical Society Interface • Summer 2019 • www.electrochem.org

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The Electrochemical Society Interface • Summer 2019 • www.electrochem.org

235th ECS Meeting May 26-30, 2019 Dallas, TX Sheraton Dallas

235th Meeting Highlights

ver 2,200 people from 60 countries attended the 235th ECS Meeting in Dallas, TX, May 26-30, 2019. Attendees could choose from 47 symposia, with over 1,800 oral talks and 432 posters, of which 866 were student presentations.

Opening Reception The opening reception kicked off the meeting. Held in the Dallas Sheraton Convention Center, the well-attended Sunday evening social event featured light snacks and an open bar. ECS division members and ECS Texas Section members worked tables to introduce attendees to their divisions and section and discuss with potential members what each has to offer. The lively event offered attendees ample opportunity to network.

Plenary Session ECS President Yue Kuo welcomed attendees to the meeting during Monday evening’s plenary session, an event that wrapped up the day’s technical sessions, honored award winners, and featured the meeting’s ECS Lecture. Among those award winners, Kuo congratulated distinguished Society award winners Héctor D. Abruña, recipient of the Allen J. Bard Award in Electrochemical Science, and David Lockwood, recipient of the Gordon E. Moore Medal for Outstanding Achievement in Solid State Science and Technology. Abruña was recognized for revolutionizing electrochemists’ understanding of electrochemical interfaces, for the novel modification of electrode surfaces, and for developing fuel cell electrocatalysts, organic materials for batteries, and graphene as an electrochemical platform. Lockwood was recognized for his outstanding original contributions to the elucidation of the role of quantum-confinement effects in the optical and electrochemical properties of semiconductor nanostructures with applications in optoelectronics and photonics. In addition, Kuo presented Rangachary Mukundan with a scroll in honor and appreciation of the seven years he served as a technical

ECS President Yue Kuo presented the opening remarks at the 235th ECS Meeting.

editor for the Journal of The Electrochemical Society and ECS Electrochemistry Letters. “Thank you for your service to the Society. The dissemination of the research in our technical domain is at the heart of ECS’s mission. It is individuals, like you, who make this happen,” said Kuo. He also recognized ECS summer fellowship winners Bilen Akuzum, recipient of the Edward G. Weston Fellowship, and Ritambhara Gond, recipient of the Joseph W. Richards Fellowship. Lastly, Kuo thanked the meeting sponsors and ECS’s institutional members for their continued support and commitment to ECS. Kuo recognized several organizations for their milestone institutional membership anniversaries through ECS’s Leadership Circle Awards, including: Gelest and Los Alamos National Laboratory, which celebrated 10 years with ECS, as well as El-Cell GmbH, Ford Motor Company, Ion Power, SanDisk, and Tianjin Lishen Battery Joint Stock Co., which celebrated five years with ECS. Kuo concluded by recognizing Alvaro Masais, from Ford Motor Company, and Rod Borup, from Los Alamos National Laboratory, on stage with awards for their organizationsʼ continued partnership with ECS.

The ECS Lecture Koen Kas, professor of molecular oncology, healthcare futurist, and entrepreneur, was the meeting’s plenary speaker. His ECS Lecture, “Guardian Angels Turning Sickcare into Healthcare,” presented a view of the future in which wearable sensors (many based on electrochemical principles) will function as guardian angels, watching over indicators of our health and then informing the digital tools that will help us change our behavior on an arc towards, in Kas’s words, “delight.” The goal is to use data to develop information and knowledge about our conditions and to use the Internet of Things to communicate that information and knowledge to a suite of digital tools that will give us the feedback we need in the form most effective for making that change. Kas described one of the roles of technology as being to (continued on next page)

Koen Kas delivered the ECS Lecture during the plenary session.

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(continued from previous page) remove the “friction” that we all naturally feel toward changing our behavior, even when we know it will be to our advantage in allowing us to enjoy life throughout its entirety. As Kas put it: “Our goal should be to die young—as late as possible.” Although much of our health is defined by our genomics, we do have substantial control over the other important factors: environment and lifestyle. In order to achieve “healthcare by default”—that is, the ability to maintain our health with as little external intervention as possible— the skills and inventiveness of the members of the electrochemical community are required to create the range of sensors and analyses needed. The sensors need to be inexpensive, robust, and effective. Through a litany of examples, Kas described how we are moving in this direction already. Wearable biosensors that monitor hydration, heart rhythm, movement, glucose levels, the presence of infection, and migraines often operate on electrochemical principles. Linking these principles to advances in flexible electronics is allowing these sensors to become ubiquitous. In some cases, these sensors are part of a system that is allowing patients to stay in their home longer, even as they near the end of life. Kas addressed the very large issue of privacy directly by making the case that there must be a value proposition for people to allow some of their most personal data to be collected. He gave the example of Disneyland, where customers often give access to their location within the park in exchange for information regarding wait times at rides. While admitting that privacy and the use of personal medical data are, and will remain, major issues, Kas envisions the future as markedly different in the way we will view our health. Rather than wait until we get sick (i.e., our health has failed in some tangible way), we will monitor our wellness, allowing us (and/or our physician) to intervene early when smaller changes can have large, positive effects. Ironically, it will harken back to long ago in China, when doctors were paid as long as their patients stayed well, and lost income when their patients became sick. That approach—the focus on maintaining and enhancing wellness—is enabled by the work that many in our community do.

ECS Data Science Hack Week Building on the success of the first ECS Data Science Hack Day held October 2017, the Society offered an expanded program at its meeting. The ECS Data Science Hack Week kicked off on Sunday and consisted of all-day sessions from Monday through Wednesday, as well as optional software training tutorials offered at the start of the week. Hack Week brought together electrochemical engineers from different backgrounds in order to increase the awareness and impact of data science tools, open source software, and shared datasets in electrochemistry and solid state science and technology by offering

Participants engaged in conversation on the first day of ECS Data Science Hack Week. 14

An ECS Data Science Hack Week participant, Aigerim Omirkhan, from Imperial College London shared a laugh with peers.

participants a space to create, share, use, and improve open source software tools and public datasets to accelerate research progress in the electrochemical field. These activities included “project hacking time,” advanced topics like cloud computing, machine learning, data visualization, and concluded with project presentations. This successful event was guided by Daniel Schwartz, David Beck, and Matthew Murbach of the University of Washington, the organizers of both Hack Day and Hack Week. Daniel Schwartz is the Boeing-Sutter Professor of Chemical Engineering and director of the Clean Energy Institute at the University of Washington. He brings electrochemistry and modeling expertise to the team. David Beck is a senior data scientist with the eSciences Institute at the University of Washington who leads regular hackathons. He is also the associate director of the NSF Data Intensive Research Enabling CleanTech PhD training program. Matthew Murbach is a past president of the ECS University of Washington Student Chapter and an advanced data sciences PhD trainee. He has been leading student section software development sessions on the UW campus and has practical experience coaching electrochemical scientists and engineers in software development.

Annual Society Business Meeting and Luncheon During the Annual Society Business Meeting and Luncheon held on Tuesday, ECS leadership reported on the Society’s 2018 successes with a focus on the organization’s future. “As you all know, Free the Science is the major, long-term initiative of the Society,” said ECS President Yue Kuo. “Since it launched, over a third of the research that has been published in ECS’s journals has been published as open access. Most importantly, of those authors choosing open access, the vast majority—over 90%—have done so at no cost to them or their institutions.” Kuo explained that this was all made possible due to ECS’s commitment to Free the Science, through which the Society has paid over $2.1 million in open access publishing costs on behalf of authors. “That means, now more than ever, ECS needs your support,” said Kuo. “You can support ECS by making a donation, renewing your membership, attending our meetings, and publishing in an ECS journal, ideally open access. These simple contributions allow you to support the next generation of scientists and ECS’s initiative to Free the Science.” Kuo also discussed his time as president. “During my presidency, I traveled extensively throughout Asia, including Russia, introducing communities to the great work and long-standing history of the Society to strengthen our global presence within the electrochemical and solid state communities,” said Kuo. “This is a part of my job, which I took very seriously, and I hope others will carry that mantle forward in the future.” The Electrochemical Society Interface • Summer 2019 • www.electrochem.org

In addition, Kuo also highlighted ECS’s unprecedented growth in 2018 with the founding of student chapters around the world, in Europe, Asia, and Africa, as well as in North and South America. Following the reports, Kuo introduced speaker Carol A. Bessel, the acting division director of the National Science Foundation’s (NSF) Division of Chemistry, who presented a talk titled “Perspectives on the State of Science and Technology: Innovation and the Workforce of the Future.” For much of the last century, NSF has promoted the progress of science—improving national health, serving as a primary driver of the U.S. economy, enhancing the nation’s security, and creating advances in knowledge to maintain global leadership. Its objectives and activities are in line with ECS’s mission to encourage research, discussion, critical assessment, and dissemination of knowledge in electrochemical and solid state fields in order to promote science and technology in the public interest. Bessel said that while NSF’s overarching goals remain the same today, science and technology are constantly innovating. She believes the workforce of the future must change a great deal to keep pace. Her presentation examined the state of science and workforce development, including the outlook for funding, challenges faced by both funders and those seeking funds, and priority technical areas for NSF both today and in the future.

Award Highlights

Carol Bessel presented her talk, “Perspectives on the State of Science and Technology: Innovation and the Workforce of the Future,” during the Annual Society Business Meeting and Luncheon.

Two Society awards were presented during the plenary session. The Allen J. Bard Award in Electrochemical Science was presented to Héctor D. Abruña. Abruña is the Émile M. Chamot Professor of Chemistry and the director of the Center for Alkaline-Based Energy Solutions and the Energy Materials Center at Cornell University. The Allen J. Bard Award in Electrochemical Science was established in 2013 to recognize distinguished contributions to electrochemical science. The award address, “Energy Conversion and Storage: Novel Materials and Operando Methodsbard,” highlighted the development of new materials and operando methods for energy conversion and storage with emphasis on fuel cells and battery materials and technologies. The presentation offered a brief overview of the methods employed—particularly the use of X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), X-ray microscopy, and tomography and transmission electron microscopy (TEM) under active potential control—concluding with an assessment of future directions.

HÉctor D. AbruÑa (left), recipient of the Allen J. Bard Award in Electrochemical Science, shook hands with ECS President Yue Kuo (right).

Abruña is also the recipient of countless other awards, including a Presidential Young Investigator Award, an A. P. Sloan Fellowship, a J. S. Guggenheim Fellowship, and a J. W. Fulbright Senior Fellowship. He is a recipient of the Electrochemistry Award of the American Chemical Society (2008) and the C. N. Reilley Award in Electrochemistry (2007). He was elected Fellow of the American Association for the Advancement of Science in 2007, member of the American Academy of Arts and Sciences in 2007, and Fellow of the International Society of Electrochemistry in 2008. He received the David C. Grahame Award from The Electrochemical Society in 2009, the Faraday Medal of the Royal Society in 2011, and the Brian Conway Prize from the International Society of Electrochemistry in 2013. He was named Fellow of The Electrochemical Society in 2013, and in 2017 was the recipient of the Gold Medal of the International Society of Electrochemistry. Most recently, he was elected member of the National Academy of Sciences. Abruña is the coauthor of over 480 publications (h-index=85) and has given over 600 invited lectures worldwide. He considers his 55 PhD students and 70 postdoctoral associates his most important professional achievement. The Gordon E. Moore Medal for Outstanding Achievement in Solid State Science and Technology was presented to David J. Lockwood. Lockwood is an adjunct professor at the University of Windsor in Windsor, Ontario, and researcher emeritus at the National Research Council of Canada, where his research centers on the optical properties of low-dimensional materials and has focused on Group IV and III-V semiconductor nanostructures. The Gordon E. Moore Medal for Outstanding Achievement in Solid State Science and Technology was established in 1971 as the Solid State Science and Technology Award for distinguished contributions to the field of solid state science and technology. It was renamed in Moore’s honor in 2005. The award address, “Towards SiliconBased Photonic Integrated Circuits: The Quest for Compatible Light Sources,” highlighted the essential role optoelectronics and photonics play in daily life, including information and communication technologies, environmental and green technologies, mechanical and chemical sensing, consumer electronics, and biomedicine. Lockwood believes there is currently an opportunity for optics to move “inside the box” and change the interconnect topology at all levels and that such optical interconnects will help in extend the life of Moore’s law. The presentation reviewed the use of the quantum confinement approach employed to produce efficient light emission in silicon and germanium, as well as nanostructured systems such as porous silicon, silicon quantum wells and wires, super unit cells, and arrays of silicon-germanium quantum dots. (continued on next page)

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• The ECS Energy Technology Division Research Award was presented to Plamen Atanassov of the University of California, Irvine. • The ECS Industrial Electrochemistry and Electrochemical Engineering Division Student Achievement Award was presented to Xinyou Ke of Case Western Reserve University. • The ECS Energy Technology Division Graduate Student Award sponsored by Bio-Logic was presented to Zan Gao of the University of Virginia.

Z01 General Student Poster Session

David Lockwood (left), recipient of the Gordon E. Moore Medal for Outstanding Achievement in Solid State Science and Technology, was presented the award plaque by ECS Executive Director & CEO Chris Jannuzzi (right).

Lockwood obtained his PhD from Canterbury University, New Zealand, in 1969, and was awarded a DSc in 1978 from Edinburgh University, United Kingdom, for his work on the electronic, optical, and magnetic properties of solids. He has published more than 600 scientific articles in journals and books, and has six U.S. patents. He is a fellow of the Royal Society of Canada, The Electrochemical Society, the American Physical Society, and the Institute of Physics, and has served on the editorial boards of six physics journals in addition to being the founding editor of the Nanostructure Science and Technology book series. He has received six major awards from within Canada and abroad. Within ECS, he has co-organized numerous symposia, served on the board of directors, and chaired the Luminescence and Display Materials Division.

Award Winners Ten division awards were presented over the course of the meeting: • The ECS Electronics and Photonics Division Award was presented to Jung Han of Yale University. • The ECS Nanocarbons Division Richard E. Smalley Research Award was presented to Maurizio Prato of the University of Trieste. • The ECS Industrial Electrochemistry and Electrochemical Engineering Division New Electrochemical Technology (NET) Award was awarded to Rami Michel Abouatallah of Hydrogenics Corporation. Abouatallah sadly passed away unexpectedly in his home in 2017. He will be remembered by his family, friends, colleagues, and ECS. • The ECS Energy Technology Division Supramaniam Srinivasan Young Investigator Award was presented to Fikile Brushett of the Massachusetts Institute of Technology. • The ECS Physical and Analytical Electrochemistry Division David C. Grahame Award was presented to Shelley Minteer of the University of Utah. • The ECS Industrial Electrochemistry and Electrochemical Engineering Division H. H. Dow Memorial Student Achievement Award was presented to Pongsarun (Boom) Satjaritanun of the University of South Carolina. • The ECS Dielectric Science and Technology Division Thomas D. Callinan Award was presented to Sean King of Intel Corporation.

There were 866 posters presented in the Z01 General Student Poster Session. The session’s award winners are listed below. • 1st Place: $1,500 cash award: Shirin Mehrazi, University of California, Merced “Rheological Study of Micro Porous Layer and Its Effect on Transport Properties in a PEMFC” • 2nd Place: $1,000 cash award: Billal Zayat, University of Southern California “Efficient and Inexpensive All-Iron Alkaline Water Electrolyzer” • 3rd Place: $500 cash award: Alana Danielle Dunne, Lewis University “Development of a Conductive Biomimetic Nanocomposite Anode for Improved Microbial Fuel Cell Efficiency” The following ECS division members served as student poster judges. • Rohan Akolkar, Case Western Reserve University • Josh Gallaway, Northeastern University • Jeffrey Halpern, University of New Hampshire • Sadagopan Krishnan, Oklahoma State University • Juan Matos, University of Concepcion • Julie Renner, Case Western Reserve University • Brian Skinn, Faraday Technology, Inc. • John Staser, Ohio University • Eiji Tada, Tokyo Institute of Technology • Jianhua Tong, Clemson University • Hiroaki Tsuchiya, Osaka University • Petr Vanýsek, Northern Illinois University • Gabriel Veith, Oak Ridge National Laboratory • Wenzhou Wu, Purdue University ECS thanks the faculty advisors and the division members who served as judges for their support of the symposium.

Two of the three General Student Poster Session winners (left to right): BillAl Zayat and Shirin Mehrazi. Not pictured: Alana Danielle Dunne. 16

The Electrochemical Society Interface • Summer 2019 • www.electrochem.org

Sponsors and Exhibitors Special thanks to the meeting’s sponsors and exhibitors, whose support and participation directly contributed to the success of the meeting. Thank you for developing the tools and equipment driving scientific advancement and for sharing your innovations with the ECS community.

Meeting Sponsors Gold

Silver

Bronze

The Electrochemical Society Interface • Summer 2019 • www.electrochem.org

Scenes from the Meeting

The Electrochemical Society Interface â&#x20AC;˘ Summer 2019 â&#x20AC;˘ www.electrochem.org

Bio-Logic EIS Quality Indicators

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EIS doesn’t need to be painful Video tutorial at www.bio-logic.net The Electrochemical Society Interface • Summer 2019 • www.electrochem.org

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Highlights from IBA 2019 We often ascribe the genius of groundbreaking discoveries to the prowess of several key individuals; however, scientific pursuits tend to reflect a different and more humbling reality. Behind the honors and awards, scientific accomplishments have always entailed the accumulated knowledge and collaborative efforts of an entire community. At the International Battery Association (IBA), we seek to recognize that fact by celebrating our combined devotion toward the future of electrochemical energy storage. Along the warm beaches of La Jolla, San Diego, leading battery scientists gathered for a common goal: to bring together top scientists and engineers from all parts of the country and around the world, providing a cordial, sincere, and personal atmosphere, in order to foster connections amongst young scientists. Chaired by Ying Shirley Meng, the organizing committee worked tirelessly to welcome over 300 professionals from 20 countries to an event composed of 88 oral presentations and over 180 poster presentations that addressed today’s most pressing questions facing energy storage materials and systems. The IBA meeting’s unique tradition and close-knit style allowed leaders of public institutions, industry, and academia to engage in

stimulating discussions on the current state of the art, providing opportunities to access resources and tools that are accelerating research and development in the field. The meeting featured poster sessions where students and junior researchers alike shared their work. While the oral presentation speakers covered established findings from recent years of work, the poster presenters shared unpublished work, representing some of the most exciting findings in the field to date. These sessions gave rise to several interesting debates amongst the participants from which several new ideas and potential collaborations were formulated. The poster sessions also provided a means for enthusiastic young talents to engage with those more senior within the community. On the last night of the meeting, a celebration banquet, along with an award ceremony, was held to recognize outstanding research achievements, as well as individuals who contributed tremendously to the field. At dinner, participants enjoyed La Jolla’s finest cuisines while singing along to stunning musical performances by the talented students of UC San Diego. It was a marvelous demonstration of creativity in both the arts and sciences.

Attendees of the 2019 International Battery Association meeting in La Jolla, CA. 20

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SOCIE T Y NE WS The IBA meeting concluded on International Women’s Day (March 8, 2019). The committee is proud to host a diverse group of female scientists who continue to play an important role in promoting female representation in STEM. The organizing committee would like to thank all participants, as well as the members of the IBA local and advisory committees. We would like to express our gratitude toward all the sponsors for their generous support and donations. Finally, the IBA meeting was a resounding success thanks in part to the dedication and hard work of all the volunteers, who demonstrated careful planning and unwavering commitment in the months leading up to the event. We look forward to the next IBA meeting, which will take place in March 2020 in Slovenia. This article was written by Darren Tan and Shuang Bai. Outstanding achievements in research, technology development, and engagement were recognized with awards during the celebration banquet. From left to right: Martin Winter, Christopher Johnson, and Michael Thackery, winner of the IBA Medal of Excellence.

IBA 2019 was honored to promote female representation in STEM fields.

The IBA 2019 organizing committee thanks the meeting’s volunteers, pictured here with Ying Shirley Meng, committee chair, (front row, center).

Results of the 2019 Election of Officers and Slate of Officers for 2020

Christina Bock President

The Electrochemical Society has announced the results of the 2019 Society election with the following persons elected: president—Christina Bock, National Research Council of Canada; and vice president—Turgut Gür, Stanford University. The terms of Stefan De Gendt (vice president), Eric Wachsman (vice president), James Fenton (secretary), and Gessie Brisard (treasurer) were unaffected by this election. At the Board of Directors meeting in Dallas, Texas, on May 30, 2019, members voted to approve the slate of candidates recommended by the ECS Nominating Committee. The slate of candidates for the next election of ECS officers, to be held from January to March 2020, include: for president—Stefan De Gendt, for vice president (one to be elected)—Gerri Botte and Adam Weber, and for secretary (one to be elected)—Marca Doeff and Sanna Virtanen. Full biographies and candidate statements will appear in the winter 2019 issue of Interface.

The Electrochemical Society Interface • Summer 2019 • www.electrochem.org

Turgut Gür Vice President

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2019–2020 ECS Committees Executive Committee of the Board of Directors

Christina Bock, Chair........................................................................................President, Spring 2020 Stefan De Gendt.............................................................................Senior Vice President, Spring 2021 Eric Wachsman............................................................................ Second Vice President, Spring 2022 Turgut Gür........................................................................................Third Vice President, Spring 2023 James Fenton.................................................................................................... Secretary, Spring 2020 Gessie Brisard................................................................................................... Treasurer, Spring 2022 Christopher Jannuzzi.............................................................................Executive Director, Term as ED

Board of Directors, Nonprofit Financial Professional

Robb Micek........................................................................................................................Spring 2022

Audit Committee

Yue Kuo, Chair.........................................................................Immediate Past President, Spring 2020 Christina Bock..................................................................................................President, Spring 2020 Stefan De Gendt.............................................................................Senior Vice President, Spring 2020 Gessie Brisard................................................................................................... Treasurer, Spring 2022 Robb Micek................................................................... Nonprofit Financial Professional, Spring 2022

Education Committee

James Noël, Chair..............................................................................................................Spring 2021 Kalpathy Sundaram............................................................................................................Spring 2020 Alice Suroviec....................................................................................................................Spring 2020 Keryn Lian..........................................................................................................................Spring 2021 David Hall..........................................................................................................................Spring 2021 Vimal Chaitanya.................................................................................................................Spring 2022 Takayuki Homma................................................................................................................Spring 2022 Walter Van Schalkwijk........................................................................................................Spring 2023 Tobias Glossmann..............................................................................................................Spring 2023 Margaret Calhoun..................................................................................Student Member, Spring 2020 Feng Zen................................................................................................Student Member, Spring 2021 James Fenton.................................................................................................... Secretary, Spring 2020 William Mustain.............................................. Chair, Individual Membership Committee, Spring 2020

Ethical Standards Committee

Yue Kuo, Chair.........................................................................Immediate Past President, Spring 2020 D. Noel Buckley.............................................................................................Past Officer, Spring 2020 Paul Natishan.................................................................................................Past Officer, Spring 2021 James Fenton.................................................................................................... Secretary, Spring 2020 Gessie Brisard................................................................................................... Treasurer, Spring 2022

Finance Committee

Gessie Brisard, Chair........................................................................................ Treasurer, Spring 2022 Mark Verbrugge.................................................................................................................Spring 2020 Boryann Liaw.....................................................................................................................Spring 2020 Robert Kostecki..................................................................................................................Spring 2021 Peter Foller........................................................................................................................Spring 2022 Robb Micek................................................................... Nonprofit Financial Professional, Spring 2022 James Fenton.................................................................................................... Secretary, Spring 2020 Tim Gamberzky...........................................................................Chief Operating Officer, Term as COO

Honors and Awards Committee

Shelley Minteer, Chair.............................................................................................PAED, Spring 2023 Vimal Chaitanya........................................................................................................ DST, Spring 2020 Thomas Moffat.........................................................................................................ELDP, Spring 2020 Jean St-Pierre........................................................................................................... ETD, Spring 2020 Viola Birss..............................................................................................................PAED, Spring 2021 Francis D’Souza.....................................................................................................NANO, Spring 2021 Scott Calabrese Barton.............................................................................................. ETD, Spring 2021 Junichi Murota..........................................................................................................EPD, Spring 2022 Dev Chidambaram................................................................................................. CORR, Spring 2022 Wei Tong..................................................................................................................BATT, Spring 2022 Nianqiang Wu.........................................................................................................SENS, Spring 2023 John Flake................................................................................................................IEEE, Spring 2023 Fernando Garzon.................................................................................................. HTEMP, Spring 2023 Christina Bock......................................................................................... ETD, President, Spring 2020

Individual Membership Committee

William Mustain, Chair......................................................................................................Spring 2020 R. Bruce Weisman..............................................................................................................Spring 2020 Timothy Paschkewitz..........................................................................................................Spring 2020 Toshiyuki Nohira................................................................................................................Spring 2021 Chi-Chang Hu....................................................................................................................Spring 2021 James Burgess...................................................................................................................Spring 2022 Luis A. Diaz Aldana............................................................................................................Spring 2022 Jeffrey Henderson..................................................................................Student Member, Spring 2020 Seyyedamirhossein Hosseini.................................................................Student Member, Spring 2021 Marion Jones...................................................................Chair, Sponsorship Committee, Spring 2022 James Fenton.................................................................................................... Secretary, Spring 2020

Nominating Committee

Yue Kuo, Chair.........................................................................Immediate Past President, Spring 2020 D. Noel Buckely.................................................................................................................Spring 2020 Chris Johnson...................................................................................................................Spring 2020 Lili Deligianni....................................................................................................................Spring 2020 Turgut Gür........................................................................................Third Vice President, Spring 2020

Sponsorship Committee

Marion Jones, Chair..........................................................................................................Spring 2022 22

Chuck Hussey....................................................................................................................Spring 2020 Peter Fedkiw......................................................................................................................Spring 2020 Xiaoping Jiang...................................................................................................................Spring 2020 Jie Xiao..............................................................................................................................Spring 2021 Christopher Beasley...........................................................................................................Spring 2021 Mark Glick.........................................................................................................................Spring 2021 Alex Peroff.........................................................................................................................Spring 2022 Alok Srivastava..................................................................................................................Spring 2022 Craig Owen........................................................................................................................Spring 2022 William Mustain.............................................. Chair, Individual Membership Committee, Spring 2020 Gessie Brisard................................................................................................... Treasurer, Spring 2022

Technical Affairs Committee

Stefan De Gendt, Chair...................................................................Senior Vice President, Spring 2020 Christina Bock..................................................................................................President, Spring 2020 Yue Kuo...................................................................................Immediate Past President, Spring 2020 Johna Leddy............................................................... Second Immediate Past President, Spring 2020 Turgut Gür........................................................................Chair, Meetings Subcommittee, Spring 2020 Eric Wachsman...........................................................Chair, Publications Subcommittee, Spring 2020 E. J. Taylor.............................................................Chair, Interdis. Sci. & Tech. Subcom., Spring 2022 Christopher Jannuzzi.............................................................................Executive Director, Term as ED

Publications Subcommittee of the Technical Affairs Committee

Eric Wachsman, Chair.................................................................. Second Vice President, Spring 2020 Turgut Gür, Vice Chair......................................................................Third Vice President, Spring 2020 Robert Savinell................................................................................................... JES Editor, 5/17/2020 Jeffrey Fergus............................................................................. ECS Transactions Editor, 12/31/2020 Krishnan Rajeshwar......................................................................................... JSS Editor, 12/31/2021 Robert Kelly................................................................................................ Interface Editor, 5/31/2022 Scott Calabrese Barton.......................................................................................................Spring 2020 Elizabeth Biddinger............................................................................................................Spring 2020 Christina Roth....................................................................................................................Spring 2021 Hui Xu................................................................................................................................Spring 2021

Meetings Subcommittee of the Technical Affairs Committee

Turgut Gür, Chair..............................................................................Third Vice President, Spring 2020 Eric Wachsman, Vice Chair.......................................................... Second Vice President, Spring 2020 Thomas Moffat...................................................................................................................Spring 2020 Thomas Schmidt................................................................................................................Spring 2021 Paul Trulove.......................................................................................................................Spring 2022

Interdisciplinary Science and Technology Subcommittee of the Technical Affairs Committee

E. J. Taylor, Chair......................................................................................................IEEE, Spring 2022 Shelley Minteer.......................................................................................................PAED, Spring 2020 Peter Mascher........................................................................................................... DST, Spring 2020 Andrew Hoff..............................................................................................................EPD, Spring 2020 Katherine Ayers......................................................................................................... ETD, Spring 2020 Alok Srivastava........................................................................................................LDM, Spring 2021 Diane Smith..............................................................................................................OBE, Spring 2021 Jessica Koehne.......................................................................................................SENS, Spring 2021 Juan Peralta Hernandez.............................................................................................IEEE, Spring 2021 John Vaughey..........................................................................................................BATT, Spring 2022 Nick Birbilis........................................................................................................... CORR, Spring 2022 Sean Bishop......................................................................................................... HTEMP, Spring 2022 Jeff L. Blackburn....................................................................................................NANO, Spring 2022 Natasa Vasiljevic......................................................................................................ELDP, Spring 2022

Symposium Planning Advisory Board of the Technical Affairs Committee

Turgut Gür, Chair..............................................................................Third Vice President, Spring 2020 Stanko Brankovic................................................................................. ELDP Division Chair, Fall 2019 Greg Jackson....................................................................................HTEMP Division Chair, Fall 2019 Mikhail Brik.......................................................................................... LDM Division Chair, Fall 2019 Vimal Chaitanya................................................................................ DST Division Chair, Spring 2020 Slava Rotkin................................................................................... NANO Division Chair, Spring 2020 John Staser....................................................................................... IEEE Division Chair, Spring 2020 Marca Doeff..........................................................................................BATT Division Chair, Fall 2020 Masayuki Itagaki................................................................................. CORR Division Chair, Fall 2020 Ajit Khosla...........................................................................................SENS Division Chair, Fall 2020 Junichi Murota.................................................................................. EPD Division Chair, Spring 2021 Vaidyanathan Subramanian................................................................ETD Division Chair, Spring 2021 Diane Smith...................................................................................... OBE Division Chair, Spring 2021 Petr Vanýsek................................................................................... PAED Division Chair, Spring 2021 E. J. Taylor..............................................................Chair, Interdis. Sci. & Tech. Subcom, Spring 2022

Other Representatives

Society Historian Zoltan Nagy...................................................................................................................Spring 2020 American Association for the Advancement of Science Christopher Jannuzzi.........................................................................Executive Director, Term as ED Science History Institute Yury Gogotsi.................................................................................. Heritage Councilor, Spring 2020 National Inventors Hall of Fame Shelley Minteer...................................................Chair, Honors & Awards Committee, Spring 2023 External Relations Representative Mark Orazem.................................................................................................................Spring 2020 The Electrochemical Society Interface • Summer 2019 • www.electrochem.org

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Focus on Focus Issues ECS publishes focus issues of the Journal of The Electrochemical Society (JES) and the ECS Journal of Solid State Science and Technology (JSS) that highlight scientific and technological areas of current interest and future promise. These issues are handled by a prestigious group of ECS technical editors and guest editors, and all submissions undergo the same rigorous peer review as papers in the regular issues. All focus issue papers are now published open access at no cost to the authors. ECS covers the article processing charge for all authors of focus issue papers as part of the Society’s ongoing Free the Science initiative.

The following focus issues have been completed recently: •

•

JES Focus Issue on Advances in Modern Polymer Electrolyte Fuel Cells in Honor of Shimshon Gottesfeld. [JES 166(7) 2019] Thomas Fuller, JES technical editor; Hui Xu, Bryan Pivovar, Yushan Yan, and Piotr Zelenay, guest editors. The advances in polymer electrolyte fuel cell (PEFC) technologies over the past few decades and particularly over the past few years, have been very impressive. The eventual commercial introduction of fuel cell electric vehicles (FCEVs) in 2015 was enabled by the impressive accomplishments of scientists, engineers, and policymakers over that period of time. Among those responsible for the fuel cell community’s success, few, if any, have had the impact that Shimshon Gottesfeld has had. He is a distinguished fuel cell educator, a passionate fuel cell and alternative fuel advocate, and a pioneering fuel cell innovator, responsible for several critical contributions that helped demonstrate the commercial viability of polymer electrolyte fuel cells. The topics covered in this issue include fuel cell catalysts and electrodes; ionomers, ionomeric membrane and water management; fuel cell transport processes; modeling and diagnostics; and fuel cell systems. The authors include not only long-term collaborators and colleagues of Gottesfeld, but also the new generation of fuel cell scientists and electrochemists. JES Focus Issue on 4D Materials and Systems. [JES 166(9) 2019] Rangachary Mukundan, JES technical editor; Ajit Khosla, Hidemitsu Furukawa, Jessica Koehne, Peter Hesketh, Giuseppe Milano, Hiroyuki Matsui, Tsukasa Yoshida, Kafil Razeeb, Luca Magagnin, Sathish Sukumaran, and Johan Moulin, guest editors. This focus issue places particular emphasis on the latest advancements in fundamental science and technological development, challenges, and innovations in electrochemical, chemical, and physical principles related to micro and nano electromechanical systems, lab on a chip, microfluidics, sensors, materials, integrated devices, micronano-fabrication technologies, gels, polymer gels and network materials and their applications, 3D and 4D printing, smart engineering materials, nanocomposites, robotics, soft-smart robotics, wearable devices, implants, material processing theoretical and experimental approach, and printed and flexible electronics and energy solutions for the same.

•

JSS Focus Issue on Chemical Mechanical Planarization for Sub10 nm Technologies. [JSS 8(5) 2019] Jennifer Bardwell, JSS technical editor; Yu-Lin Wang, Ara Philipossian, and Jin-Goo Park, guest editors. Chemical mechanical planarization (CMP) will continue to enable miniaturization in integrated circuit manufacturing in the years to come. However, for sub-10 nm technologies, fundamental understanding of the underlying mechanisms involved has far lagged current industrial practices. Development of superior multi-scale models and new classes of polishers that are capable of collecting in-line data that can be correlated to polish outcomes or used to predict excursions can be of great use. This focus issue brings attention to the recent advances in these areas and the emerging challenges. Semiconductor CMP advances can also affect other electronic materials processes such as packaging and flexible displays where CMP technology can be adapted.

The following focus issues are currently in production with many papers already published: • JES Focus Issue on Advanced Techniques in Corrosion Science in Memory of Hugh Isaacs. [JES 166(11) 2019] Gerald Frankel, JES technical editor; James Noël, Sanna Virtanen, and Masayuki Itagaki, guest editors. • JSS Focus Issue on Gallium Oxide Based Materials and Devices. [JSS 8(7) 2019] Fan Ren, JSS technical editor; Steve Pearton, Jihyun Kim, Alexander Polyakov, Steven Ringel, Rajendra Singh, and Renxu Jia, guest editors. Calls for papers have gone out recently for the following focus issues: • JSS Focus Issue on Recent Advances in Wide Bandgap III-Nitride Devices and Solid State Lighting: A Tribute to Isamu Akasaki. [JSS 9(1) 2020] Kailash Mishra, JSS technical editor; Hiroshi Amano, John Collins, Jung Han, Won Bin Im, Michael Kneissl, Tae-Yeon Seong, Anant Setlur, Tadek Suski, and Eugeniusz Zych, guest editors. • JES Focus Issue on Mathematical Modeling of Electrochemical Systems at Multiple Scales in Honor of Richard Alkire. [JES 167(1) 2020] Venkat Subramanian, JES technical editor; John Harb and John Weidner, guest editors. For recent calls for papers, links to the published issues, titles of upcoming issues, and general information about focus issues, visit

www.electrochem.org/focusissues.

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Scott Donne Appointed JES Associate Editor Scott Donne has recently been appointed as an associate editor of the Journal of The Electrochemical Society. Donne handles manuscripts submitted to the batteries and energy storage topical interest area. Donne is a professor of chemistry in the School of Environmental and Life Sciences at the University of Newcastle, where he also functions in a number of discipline-specific and university-wide administrative capacities.

Donne’s research interests span various areas of electrochemistry, but focus particularly on energy storage materials such as batteries, supercapacitors, and fuel cells. He also has significant experience in electrodeposition, the application of various electroanalytical methods, the study of corrosion, and industrial chemistry. This year, Donne was awarded a Fulbright Future Scholarship, funded by the Kinghorn Foundation.

Free the Science Week 2019 In celebration of its third annual Free the Science Week (April 1-7, 2019), the Society once again took down the paywall to the entire ECS Digital Library. For the duration of the week, readers had unrestricted access to more than 151,000 scientific articles and abstracts. This successful weeklong event produced swells in ECS page visits and content usage that attest to the enduring relevance and value of the Free the Science initiative. ECS was especially pleased to learn that Free the Science Week 2019 drew more new visitors to the digital library than the week’s previous installments. During this year’s Free the Science Week, over 62% of those who visited the digital library during the week were new visitors; that is, more than 39,380 new visitors were exposed to ECS content. A blog series ECS published during the week, intended to educate readers about the Free the Science initiative and the Society’s open access offerings, also gained considerable attention over the course of the week, amassing a combined total of 14,370 unique page views. In terms of publications usage, this year’s Free the Science Week proved the best yet. Over 365,000 full-text articles were downloaded during April 2019, exceeding the download totals for both April 2017 and April 2018, when previous installments of Free the Science Week were held. Additionally, during the month of April, the total usage across all ECS publications increased by 30% over the first-quarter monthly average for 2019.

Moreover, ECS’s subscription-based publications—the Journal of The Electrochemical Society, the ECS Journal of Solid State Science and Technology, and ECS Transactions—collectively received more downloads in April 2019 than they did during nearly every other month in the history of the ECS Digital Library (the one exception being October 2018). Although the download totals for these publications did not exceed the totals received last October, when ECS celebrated International Open Access Week 2018, they surpassed the totals received in October 2015, October 2016, and October 2017—the months during which ECS previously participated in Open Access Week. The fact that Free the Science Week—an event designed and conducted by ECS alone—is eliciting a response from the community comparable to that of Open Access Week—an internationally recognized event—gives ECS great hope for the future of its push toward open science. Taken together, these statistics are encouraging because they demonstrate deep and sustained interest from the electrochemical and solid state communities—not just in ECS’s technical content but also in the Society’s mission and commitment to one day making scientific research free to read and free to publish all year round. ECS thanks everyone who participated in Free the Science Week 2019 by downloading and sharing free research. Your support brings the Society one step closer to making its vision for open science a reality.

Research is meant to be shared.

Visit freethescience.org 24

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Join ECS in ATLANTA, GEORGIA for the

236th ECS Meeting October 13-17, 2019

Featured events include: • Plenary/ECS Lecture‑Valerie Browning, DARPA’s Defense Sciences Office • 40 Years After: A symposium in honor of Joan Berkowitz, ECS’s first female President

Valerie Browning

• The Electrochemical Energy Summit-E2S: Electrochemistry in Space

Upcoming ECS Sponsored Meetings In addition to the ECS biannual meetings and ECS satellite conferences, ECS, its divisions, and its sections sponsor meetings and symposia of interest to the technical audience ECS serves. The following is a partial list of upcoming sponsored meetings. Please visit the ECS website (www.electrochem.org/upcoming-meetings) for a list of all sponsored meetings.

2019 • The 26th International Workshop on Active-Matrix Flatpanel Displays and Devices (AM-FPD19); July 2-5, 2019; Kyoto, Japan; www.amfpd.jp • 70th Annual Meeting of the International Society of Electrochemistry (ISE); August 4-9, 2019; Durban, South Africa; https://annual70.ise-online.org/index.php • 2019 Workshop on Electrochemical Measurements; August 12-16, 2019; Cleveland, Ohio; https://chemistry.case.edu/research/yces • Euroanalysis XX 2019; September 1-5, 2019; Istanbul, Turkey; http://euroanalysis2019.com/ • 6th International Conference on Advanced Capacitors (ICAC 2019); September 8-12, 2019; Ueda, Japan; www.icac2019.org • 15th International Conference on Electrified Interfaces (ICEI2019); November 3-8, 2019; Valdivia, Chile; www.deq.cl/icei2019 To learn more about what an ECS sponsorship could do for your meeting, including information on publishing proceedings volumes for sponsored meetings, or to request an ECS sponsorship of your technical event, please contact ecs@electrochem.org.

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New Division Officers New officers for the spring 2019–spring 2021 term have been elected for the following divisions.

Electronics and Photonics Division

Chair Junichi Murota, Tohoku University Vice Chair Yu-Lin Wang, National Tsing Hua University 2nd Vice Chair Jennifer Hite, Naval Research Laboratory Secretary Qiliang Li, George Mason University Treasurer Robert Lynch, University of Limerick Members-at-Large Travis Anderson, Naval Research Laboratory Albert Baca, Sandia National Labs Helmut Baumgart, Old Dominion University D. Noel Buckley, University of Limerick Yu-Lun Chueh, National Tsing Hua University M. Jamal Deen, McMaster University Stefan De Gendt, IMEC/K U Leuven Erica Douglas, Sandia National Laboratories Takeshi Hattori, Hattori Consulting International Andrew Hoff, University of South Florida Hemanth Jagannathan, IBM Jr-Hua He, King Abdullah University of Science and Technology Hiroshi Iwai, Tokyo Institute of Technology Soohwan Jang, Dankook University Zia Karim, Yield Engineering Systems Yue Kuo, Texas A&M University Mark Overberg, Sandia National Laboratories Fred Roozeboom, Eindhoven University of Technology Tadatomo Suga, University of Tokyo

Energy Technology Division

Chair Vaidyanathan Subramanian, University of Nevada Reno Vice Chair William Mustain, University of South Carolina Secretary Katherine Ayers, Proton Energy Systems, Inc. Treasurer Minhua Shao, Hong Kong University of Science and Technology Members-at-Large To be announced at a future date.

Organic and Biological Electrochemistry Division

Chair Diane Smith, San Diego State University Vice Chair Sadagopan Krishnan, Oklahoma State University Secretary/Treasurer Song Lin, Cornell University Members-at-Large Mekki Bayachou, Cleveland State University James Burgess, Augusta University David Cliffel, Vanderbilt University Toshio Fuchigami, Tokyo Institute of Technology Jeffrey Halpern, University of New Hampshire Flavio Maran, Universita degli Studi di Padova Shelley Minteer, University of Utah Kevin Moeller, Washington University in St. Louis Dennis Peters, Indiana University James Rusling, University of Connecticut

Physical and Analytical Electrochemistry Division

Chair Petr Vanýsek, Northern Illinois University Vice Chair Andrew Hillier, Iowa State University Secretary Stephen Paddison, University of Tennessee Treasurer Anne Co, Ohio State University Members-at-Large Plamen Atanassov, University of New Mexico David Cliffel, Vanderbilt University Hugh De Long, United States Army Research Alanah Fitch, Loyola University Pawel Kulesza, Uniwersytet Warszawski Shelley Minteer, University of Utah Robert Mantz, United States Army Research Paul Trulove, United States Naval Academy Iwona Rutkowska, Uniwersytet Warszawski Brian Skinn, Faraday Technology, Inc.

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The Electrochemical Society Interface • Summer 2019 • www.electrochem.org

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ECS Division Contacts High-Temperature Energy, Materials, & Processes

Battery

Marca Doeff, Chair Lawrence Berkeley National Laboratory mmdoeff@lbl.gov • 510.486.5821 (US) Y. Shirley Ming, Vice Chair Brett Lucht, Secretary Jie Xiao, Treasurer Doron Aurbach, Journals Editorial Board Representative Corrosion

Masayuki Itagaki, Chair Tokyo University of Science itagaki@rs.noda.tus.ac.jp • 471229492 (JP) James Noël, Vice Chair Dev Chidambaram, Secretary/Treasurer Gerald Frankel, Journals Editorial Board Representative Dielectric Science and Technology

Vimal Chaitanya, Chair New Mexico State University vimalc@nmsu.edu • 575.635.1406 (US) Peter Mascher, Vice Chair Uros Cvelbar, Secretary Zhi David Chen, Treasurer Peter Mascher, Journals Editorial Board Representative Electrodeposition

Stanko Brankovic, Chair University of Houston srbrankovic@uh.edu • 713.743.4409 (US) Philippe Vereecken, Vice Chair Natasa Vasiljevic, Secretary Luca Magagnin, Treasurer Takayuki Homma, Journals Editorial Board Representative Electronics and Photonics

Junichi Murota, Chair Tohoku University murota@riec.tohoku.ac.jp • + 81.227522208 (JP) Yu-Lin Wang, Vice Chair Qiliang Li, Secretary Robert Lynch, Treasurer Fan Ren, Journals Editorial Board Representative Energy Technology

Vaidyanathan Subramanian, Chair University of Nevada Reno ravisv@unr.edu • 775.784.4686 (US) William Mustain, Vice Chair Katherine Ayers, Secretary Minhua Shao, Treasurer Thomas Fuller, Journals Editorial Board Representative

Greg Jackson, Chair Colorado School of Mines gsjackso@mines.edu • 303.273.3609 (US) Paul Gannon, Sr. Vice Chair Sean Bishop, Jr. Vice Chair Cortney Kreller, Secretary/Treasurer Raymond Gorte, Journals Editorial Board Representative

Industrial Electrochemistry and Electrochemical Engineering

John Staser, Chair Ohio University staser@ohio.edu • 740.593.1443 (US) Shrisudersan Jayaraman, Vice Chair Maria Inman, Secretary/Treasurer John Harb, Journals Editorial Board Representative Luminescence and Display Materials

Mikhail Brik, Chair University of Tartu brik@fi.tartu.ee • + 372 737.4751 (EE) Jakoah Brgoch, Vice Chair Rong-Jun Xie, Secretary/Treasurer Kailash Mishra, Journals Editorial Board Representative Nanocarbons

Slava Rotkin Pennsylvania State University rotkin@psu.edu • 814.863.3087 (US) Hiroshi Imahori, Vice Chair Olga Boltalina, Secretary R. Bruce Weisman, Treasurer Francis D’Souza, Journals Editorial Board Representative Organic and Biological Electrochemistry

Diane Smith, Chair San Diego State University dksmith@mail.sdsu.edu • 619.594.4839 (US) Sadagopan Krishnan, Vice Chair Song Lin, Secretary/Treasurer Janine Mauzeroll, Journals Editorial Board Representative Physical and Analytical Electrochemistry

Petr Vanýsek, Chair Northern Illinois University pvanysek@gmail.com • 815.753.1131 (US) Andrew Hillier, Vice Chair Stephen Paddison, Secretary Anne Co, Treasurer David Cliffel, Journals Editorial Board Representative Sensor

Ajit Khosla, Chair Yamagata University khosla@gmail.com • 080.907.44765 (JP) Jessica Koehne, Vice Chair Larry Nagahara, Secretary Praveen Sekhar, Treasurer Ajit Khosla, Journals Editorial Board Representative 28

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ECS MArkET rESEArCh SurvEy rESulTS SOCIE T Y NE WS

Last year, ECS conducted a large-scale market research survey to better assess the needs of the community it stewards. The survey was international in scope, covering a wide breadth of demographics. The Society’s principal goal in carrying out the survey was to evaluate, enhance, and determine the future of ECS programs, particularly those related to individual and institutional membership, Interface, and open access. In total, almost 1,870 responses were collected from a diverse pool of respondents all around the world. Their feedback revealed key, actionable insights into the value propositions of various ECS services and offerings. Moreover, the results attest to the enduring importance of the role the Society serves for its vast community of researchers. ECS thanks everyone who took the time to respond to the survey. Your input will be invaluable in charting the Society’s course for the years to come.

MEMbErShip

2/3

iNTErfACE

global, relevant, credible, established, prestigious

opEN ACCESS

72.5%

of members feel engaged

individuals join for professional recognition, colleague recommendations, and to support the community

ECS’S Top ATTribuTES

recommend subscribing to ECS plus

93.4%

satisfied with quality of interface

iNSTiTuTioNAl MEMbErShip Almost

90%

PUBLISHING

91.6%

agree that the most important goal of free the Science is to accelerate scientific advancement

indicate that institutional membership helps support the ECS community

DEMogrAphiC

WorkplACE

1,869

55%

from North America

survey responses

68.5%

44% of survey responses were

of survey respondents were from academia

34% from ages 36-55

from industry/ government

from those 35 or younger

gEogrAphiC

20%

The Electrochemical Society Interface • Summer 2019 • www.electrochem.org

16% from Asia 22% from

European union

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Redcat Blog Highlights There’s a lot going on within The Electrochemical Society and around the world in the solid state, electrochemical, and technology field. The ECS Redcat Blog lets you keep up with the latest events and news in both, all in one place! Here, you can stay up-to-date on the latest breakthroughs in the field, ECS’s biannual meetings, abstract deadlines, grant deadlines, award winners (your favorite), most-read articles in the Journal of The Electrochemical Society and the ECS Journal of Solid State Science and Technology, and more. That’s a lot of content! We’ve highlighted the top five most-visited blogs of 2019 as a preview of what the ECS Redcat Blog has to offer. Because ECS believes in sharing and distributing information, each year the Society hosts its very own Free the Science Week as a preview of what ECS one day hopes to accomplish—complete open access publishing. Free the Science Week offers unrestricted access to all of the research ever published in the ECS Digital Library, meaning access to over 151,000 articles and abstracts. Free the Science Week is so popular the blog article “Make the Most of Free the Science Week” brought in over 35,000 page views and nearly 15,000 unique page views, making it the most-visited blog post this year! But, as we mentioned, we cover more than ECS. Did you know? A man with no science background or financial support decided to take it upon himself to stop global warming; for more than a decade, he worked alone out of a garage at a storage

60 Minutes correspondent Lesley Stahl (right) took a tour of Marshall Medoff’s (left) lab. (Photo Credit: 60 Minutes)

facility, which eventually led him to the idea of turning plant life into environmentally friendly transportation fuels. Read the second most popular Redcat Blog: “Marshall Medoff: Amateur Scientist, Reputable Results.” And just as there are breakthroughs, there are setbacks that call for the attention of the science community; specifically, the sensors field in this case. After two Boeing 737 Max 8 aircrafts crashed less than four months apart from each other, officials were forced to take a closer look at suspected faulty sensors on the aircraft model. Learn what went wrong in the third most-read Redcat Blog: “Faulty Sensors on Boeing 737 Max 8 Aircrafts?” Coming in as the fourth most-read Redcat Blog is again a reflection of ECS’s unique initiative to Free the Science. The blog article “All ECS Research Free during Free the Science Week” dives into what Free the Science is, how it works, its impact, traction, and future. Christopher Jannuzzi, ECS executive director and chief executive officer, says, “Our hope is that the glimpse into the future that Free the Science Week provides will rally the entire ECS community to support this vital initiative so we can make all of ECS’s outstanding content truly open access to all.” Luckily, the Society is not alone in its support of open access publishing. Earlier this year, the “University of California cut ties with Elsevier,” a decision fueled by Elsevier’s refusal to “strike a package deal that would provide a break on subscription fees and make all articles published by UC authors immediately free for readers worldwide,” according to the online magazine Science. The move was a big statement for the 10-campus system which accounts for nearly 10% of all U.S. publishing output, reflecting their strong support for an open access model and also making it the fifth most-read story on the Redcat Blog. If you enjoyed our top Redcat Blog stories, be sure to visit electrochem.org/redcat-blog for updates like these and more!

ECS Redcat Blog The blog was established to keep members and nonmembers alike informed on the latest scientific research and innovations pertaining to electrochemistry and solid state science and technology. With a constant flow of information, blog visitors are able to stay on the cutting-edge of science and interface with a like-minded community.

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2019 Leadership Circle Awards This year we would like to award the following organizations the 2019 Leadership Circle Award to show gratitude for their continued partnership commitment to ECS.

Silver Level – 10 Years of Membership • Gelest, Inc. www.gelest.com Gelest, Inc., headquartered in Morrisville, PA, USA, was founded in 1991 to serve the advanced technology applications markets and is recognized worldwide as an innovator, manufacturer, and supplier of Organo-Silicon and Metal-Organic materials for commercial production and R&D support. • Los Alamos National Laboratory www.lanl.gov Los Alamos National Laboratory was established in 1943 as site Y of the Manhattan Project. The primary responsibility of the laboratory is assuring the safety and reliability of the nation’s nuclear deterrent. Though the world is rapidly changing, this essential responsibility remains the core mission. The people of Los Alamos continually work on advanced technologies to provide the United States with the best scientific and engineering solutions to many of the nation’s most crucial challenges.

Bronze Level – 5 Years of Membership • El-Cell GmbH https://el-cell.com EL-Cell GmbH offers electrochemical test equipment and services to academics and professionals who conduct highquality battery research at the leading edge of knowledge. ElCell GmbH’s combination of mechanical and electrochemical expertise has created a unique environment for producing electrochemical test equipment of the highest quality.

• Ford Motor Company https://corporate.ford.com Ford Motor Company was incorporated in 1903. Ford believes that the freedom of movement drives human progress; and, the organization aspires to become the world’s most trusted company, designing smart vehicles for a smart world. • Ion Power, Inc. www.nafionstore.com Ion Power Inc. was founded in 1999 to promote the use of NafionTM. They develop, manufacture, and distribute value-added products containing NafionTM PFSA materials by The Chemours Company. Their products are used in fuel cells and for water electrolysis in industry and research. • Tianjin Lishen Battery Joint-Stock Co., Ltd. http://en.lishen.com.cn Tianjin Lishen Battery Joint-Stock Co., Ltd. (Lishen Battery) was established in 1997 and is a leader in lithium-ion battery manufacturing. Lishen Battery has China’s first Battery Industry UL Witnessed Test Data Program Lab and the National Postdoctoral Research Workstation. The organization is dedicated to providing customers with total energy solutions whose applications cover a wide range of customer electronics, new energy transportation, and energy storage systems. • SanDisk www.sandisk.com A brand of Western Digital, SanDisk was founded in 1988. It is one of the top companies for development and production of innovative software and flash memory storage solutions. SanDisk is committed to advancing its technology and satisfying customers’ developing needs.

Creating Powerful Partnerships ECS welcomes its newest institutional member, GE Global Research Center. GE Research is GE’s innovation powerhouse where research meets reality. GE Research is a world-class team of 1,000+ scientific, engineering, and marketing minds (600+ PhDs), working at the intersection of physics and markets, physical and digital technologies, and across a broad set of industries to deliver world-changing innovations and differentiated products for GE’s businesses and customers. These innovations and products span the aviation, power, transportation, healthcare sectors, and beyond.

GE continues to build upon a proud heritage of invention that began with the company’s founder, Thomas Edison. GE scientists and engineers have distinguished themselves over time, amassing tens of thousands of patents, two Nobel Prizes in chemistry and physics, and a list of inventions that helped establish GE’s large industrial footprint. Today, GE’s products generate one-third of the world’s electricity, power flights that take off every two seconds, and produce 16,000 imaging scans of patients per minute in health care. To learn more, visit GE’s website at www.ge.com/research.

The Electrochemical Society Interface • Summer 2019 • www.electrochem.org

SOCIE T Y NE WS Institutional Membership Program Institutional membership provides organizations the opportunity to support and advance the dissemination of electrochemical and solid state science research. Member organizations save 15-20% in spending through discounts on ECS subscriptions, meeting

registrations, marketing opportunities, and are able to provide ECS membership benefits to their employees. Contact Shannon.Reed@electrochem.org to learn more about institutional membership benefits.

websites of note by Alice H. Suroviec

CytoFluidix • The aim for the CytoFluidix is to provide a platform to share the up-to-date information and resources of Lab-on-a-chip, microfluidic/nanofluidic instruments or systems. The scope of this website includes but is not limited to microfluidics and nanofluidics, life science applications, analysis and synthesis applications, imaging and detection technologies, as well as MEMS and nanotechnologies. This website has many useful articles and tutorials aimed at both researchers and students. www.cytofluidix.com

Electronics Tutorials • Electronics Tutorials is exactly what the name of the website promises. It is a large collection of tutorials for both the student and the researcher. The topics range from Introduction to AC Circuit Theory to Sequential Logic. Many of the tutorials are also videos that the student can follow along to. www.electronics-tutorials.ws

Science X • Science X is a web-based science and technology news service. The topics covered include physics, medicine, nanotechnology, electronics, chemistry, and engineering. Science X publishes 200 articles a day and if you choose to subscribe you can save favorite articles and receive a daily newsletter. This website provides a broad spectrum of articles and an easy way to share them through social media. https://sciencex.com/news

About the Author

Alice Suroviec is a professor of bioanalytical chemistry and chair of the Department of Chemistry and Biochemistry at Berry College. She earned a BS in chemistry from Allegheny College in 2000. She received her PhD from Virginia Tech in 2005 under the direction of Mark R. Anderson. Her research focuses on enzymatically modified electrodes for use as biosensors. She is an associate editor for the physical and analytical electrochemistry, electrocatalysis, and photoelectrochemistry topical interest area of the Journal of The Electrochemical Society. She may be reached at asuroviec@berry.edu. https://orcid.org/0000-0002-9252-2468

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In the

issue of

• The fall 2019 issue of Interface will be a special issue on Sensors. Guest edited by Peter Hesketh (Georgia Institute of Technology) and Joseph Stetter (KWJ Engineering Inc.). • Tech Highlights, brought to you by Donald Pile and his team of experts, will pique your interest in recently published noteworthy articles from the ECS journals. (The full text of all articles highlighted in this regularly-occurring column is always free to read in the ECS Digital Library!)

• A preview of the 236th Meeting of The Electrochemical Society taking place in Atlanta, Georgia, October 13-17, 2019 • Recognition of the newest class of ECS fellows and Society, division, and section award winners. • Announcement of ECS journals 2018 impact factors. • The Electrochemical Society and Toyota Research Institute of North America announces 2019-2020 fellowship winners.

6 Ways to Give to ECS

1 23 456 In Person at an ECS meeting

Online at

Mail to 65 S Main St., Bldg. D Pennington, NJ 08534

Planned Giving

Automatic Recurring Gifts

Electrochem.org

Securities/ Stock

Visit www.electrochem.org and click the red DONATE button. Contact development@electrochem.org

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In Memoriam memoriam Andrzej Wieckowski (1945 – 2019)

ndrzej Wieckowski (Polish: Więckowski) passed away on January 31, 2019, in Eugene, Oregon, following a long illness. Wieckowski was an ECS emeritus member and fellow who had been a valued member of the Society for over three decades. During this time, he made momentous contributions as a researcher, a symposium organizer, and a member of multiple Society committees. From 1999 to 2001, Wieckowski served as chair of the division formerly known as the ECS Physical Electrochemistry Division (now known as the ECS Physical and Analytical Electrochemistry Division). He also served on the ECS Technical Affairs Committee (2001–2005) and the ECS Honors and Awards Committee (2006–2010). He was a member of the ECS Chicago Section and the faculty advisor for the ECS Central Illinois Student Chapter. Wieckowski was born on February 22, 1945, in Łódź, Poland. He received his MS, PhD, and DSc degrees from the University of Warsaw in 1968, 1973, and 1981, respectively. As a young researcher in Poland, Wieckowski stepped forward to take a highly visible leadership role in the Solidarity Movement while at Warsaw University. He left Poland for North America just two weeks before the imposition of martial law in Poland in 1981, first to Laval University in Quebec City, Canada, then to the University of California, Santa Barbara, to work with Art Hubbard, and finally to the University of Illinois at Urbana-Champaign in 1985. He was an assistant/associate professor of chemistry there from 1985 to 1996 and a full professor from 1996 to 2012. Once at the University of Illinois and, indeed, even before he moved from Santa Barbara to Urbana, Wieckowski had a unique ability to attract students to his group due to his infectious enthusiasm, boundless energy, and excitement for science and cutting-edge experimental approaches. Wieckowski was known for his fundamental spectroscopic and radiochemical research on the solid-liquid electrochemical interface and electrode surface structure, and for molecular-level studies of surface oxidation and reduction processes applicable to electrocatalytic systems, such as fuel cells. He is particularly known for the development of electrochemical NMR, in collaboration with Eric Oldfield, and for the many applications of this pioneering technique to interfacial electrochemical systems. He also developed and utilized broadband-sum frequency generation, cathodoluminescence-electron energy loss spectroscopy, and electrochemical X-ray photoelectron spectroscopy. He is recognized as the coinventor of the direct formic acid fuel cell. During his long, distinguished career at the University of Illinois, he published over 300 journal articles, which have been cited over 13,000 times.

Wieckowski was a longtime member of both ECS and the International Society of Electrochemistry (ISE). He was also a recipient of many prestigious awards over the course of his career. In 1992, Wieckowski was awarded the U.S. Department of Energy Prize for Outstanding Scientific Accomplishment in Materials Chemistry. He received the ISE Jacques Tacussel Prize in 1998 and the ECS Physical and Analytical Electrochemistry Division David C. Graham Award in 2003. He was appointed an ECS fellow in 2006 and an ISE fellow in 2009. Also in 2006, Wieckowski was awarded the Gold Medal of the ISE. He served for 12 years as a North American editor of Electrochimica Acta. In 2013, ECS member and University of Arkansas professor Ingrid Fritsch gave a talk in honor of Wieckowski during his surprise retirement party at the University of Illinois. “Andrzej served on my PhD graduate committee from 1985 to 1989,” Fritsch began. “I want to thank him for making a positive impact on many levels.” Fritsch then explained how Wieckowski had provided her encouragement and support throughout her career. “I can’t say enough how important it has been to me to see Andrzej’s smiling face at The Electrochemical Society conferences that I’ve attended,” Fritsch said. “Actually, I don’t ever remember not seeing him at those conferences. … Andrzej has always advocated that people ‘get out there’ and be active—help to define what is at the cutting edge of the science and disseminate science to others. This is of course what Andrzej, himself, has done.” She went on to describe Wieckowski’s exceptional gift for communicating scientific research. “Andrzej is a fine scientist, not only in doing research, but also in communicating it to others in a comprehensible and convincing fashion,” Fritsch said. “Thus, the science can transcend both the discipline and time; it takes on a kind of immortality.” In 2014, at the 225th ECS Meeting in Orlando, Florida, a symposium was held in Wieckowski’s honor. There, former ECS president Larry Faulkner, who had first brought Wieckowski to the University of Illinois in 1985, gave a speech celebrating Wieckowski’s illustrious career. “With his whole life Andrzej has shown commitment to freedom, truth, and professional integrity,” said Faulkner. “These are the fundamental values of science. Andrzej has lived them wonderfully successfully, because he is also a focused man of extraordinary courage.” Wieckowski is survived by his wife, Teresa; his daughter, Zuzanna; his son-in-law, Taylor; and his granddaughters, Maia, Nicole, and Rachel. Information for this notice was contributed, in part, by Debbie Myers and Piotr Zelenay.

The Electrochemical Society Interface • Summer 2019 • www.electrochem.org

Plan S:

What You Need to Know

ast fall, the international consortium of research funders known as cOAlition S cast much of the scholarly publishing community into disarray with the announcement of its ambitious and divisive open access initiative, Plan S. More recently, cOAlition S released revisions to the plan’s principles and implementation guidance based on feedback received from the wider community.1 In addition to providing greater clarity regarding the terms of the initiative, the revisions extended the plan’s implementation date by one year—to January 1, 2021—in order to provide more preparation time for researchers and publishers. Regardless of your station in the scholarly publishing ecosystem—and whether or not you support Plan S—it’s important to have a general understanding of the initiative, which has the potential to dramatically alter the scholarly publishing industry on a global scale.

What Is Plan S?

Plan S is an open access initiative that aims to accelerate the transition to a system of scholarly publishing defined by full and immediate open access to scientific publications. The plan was initiated by Robert-Jan Smits, the former open access envoy of the European Commission. It was further developed by Marc Schiltz, president of Science Europe, along with the heads of the participating research-funding organizations. Plan S also drew input from the Scientific Council of the European Research Council (ERC). The launch of Plan S was announced on September 4, 2018. Revisions to the plan’s principles and implementation guidance were released on May 31, 2019.

Funders and Supporters

The group of national research-funding organizations that have committed to implement Plan S is known as cOAlition S. This international consortium currently consists of 16 national researchfunding organizations and three charitable foundations. The group invites research funders from around the world, both public and private, to join the coalition. A number of other organizations have issued statements of support for Plan S. Full lists of the initiative’s funders and supporters may be found on the cOAlition S website.2 The research funders that comprise cOAlition S have agreed to implement the 10 principles of Plan S in a coordinated manner.

Principles of Plan S

Plan S consists of one key principle and 10 additional principles (reproduced below).3

With effect from 2021, all scholarly publications on the results from research funded by public or private grants provided by national, regional and international research councils and funding bodies, must be published in Open Access Journals, on Open Access Platforms, or made immediately available through Open Access Repositories without embargo.”

Plan S Making full and immediate Open Access a reality

Key Principle: With effect from 2021, all scholarly publications on the results from research funded by public or private grants provided by national, regional and international research councils and funding bodies, must be published in Open Access Journals, on Open Access Platforms, or made immediately available through Open Access Repositories without embargo.

10 Principles

1. Authors or their institutions retain copyright to their publications. All publications must be published under an open license, preferably the Creative Commons Attribution license (CC BY), in order to fulfill the requirements defined by the Berlin Declaration. 2. The Funders will develop robust criteria and requirements for the services that high-quality Open Access journals, Open Access platforms, and Open Access repositories must provide. 3. In cases where high-quality Open Access journals or platforms do not yet exist, the Funders will, in a coordinated way, provide incentives to establish and support them when appropriate; support will also be provided for Open Access infrastructures where necessary. 4. Where applicable, Open Access publication fees are covered by the Funders or research institutions, not by individual researchers; it is acknowledged that all researchers should be able to publish their work Open Access. The Electrochemical Society Interface • Summer 2019 • www.electrochem.org

5. The Funders support the diversity of business models for Open Access journals and platforms. When Open Access publication fees are applied, they must be commensurate with the publication services delivered and the structure of such fees must be transparent to inform the market and funders potential standardisation and capping of payments of fees. 6. The Funders encourage governments, universities, research organisations, libraries, academies, and learned societies to align their strategies, policies, and practices, notably to ensure transparency. 7. The above principles shall apply to all types of scholarly publications, but it is understood that the timeline to achieve Open Access for monographs and book chapters will be longer and requires a separate and due process. 8. The Funders do not support the ‘hybrid’ model of publishing. However, as a transitional pathway towards full Open Access within a clearly defined timeframe, and only as part of transformative arrangements, Funders may contribute to financially supporting such arrangements. 9. The Funders will monitor compliance and sanction noncompliant beneficiaries/grantees. 10. The Funders commit that when assessing research outputs during funding decisions they will value the intrinsic merit of the work and not consider the publication channel, its impact factor (or other journal metrics), or the publisher.

How Will Plan S Affect Authors?

Once Plan S goes into effect, authors whose funders are members of cOAlition S will be required to publish in Plan S-compliant journals or on Plan S-compliant platforms. cOAlition S has delineated the specific requirements for Plan S compliance for individual publications, journals, platforms, repositories, and transformative agreements. Detailed accounts of these requirements may be found in the principles and implementation guidance of Plan S. All scholarly articles resulting from research funded by members of cOAlition S will need to be openly available immediately upon publication without any embargo period. These articles will also need to be permanently accessible under an open license that allows reuse for any purpose, subject to proper attribution of authorship. For scholarly articles, cOAlition S will require the Creative Commons Attribution (CC BY) 4.0 license4 by default, unless an exception has been agreed by the funder. Under specific conditions, during a transition period, cOAlition S will allow authors to publish open access in subscription journals, provided that the journals are covered by transformative agreements for transitioning to open access. Transformative agreements will only be supported until 2024. www.coalition-s.org/rationale-for-the-revisions www.coalition-s.org/funders 3 www.coalition-s.org/principles-and-implementation 4 https://creativecommons.org/licenses/by/4.0 1 2

Free the Science, and our demonstrated commitment to open access and open science, puts us in an excellent position to not only comply with Plan S, but also to grow our publications’ reach because of it.” Moreover, authors funded by cOAlition S members will need to publish in Plan S-compliant venues in order to ensure the compliance of their scholarly articles.

Where Does ECS Stand on Plan S?

Like the founders of cOAlition S, ECS believes that open access is of paramount importance to the scientific enterprise. It was this staunch belief that led the Society to launch the Free the Science initiative in 2015. Free the Science is ECS’s initiative to move toward a future that embraces open science to further advance research in the Society’s fields. It is a long-term vision for transformative change in the traditional models of communicating scholarly research based on the tenet that research should be free to read and free to publish. The initiative is supported by ECS’s Author Choice Open Access program, as well as ECS Plus, the Society’s transformative agreementbased subscription option, both of which have seen substantial growth since their inception. (Last year, over 42% of ECS’s journal articles were published open access; through ECS Plus, authors at more than 1,000 subscribing institutions currently have the opportunity to publish open access at no cost.) In this sense, ECS has already been working toward the same goal that cOAlition S seeks to accomplish through Plan S. In his Pennington Corner article in the spring 2019 issue of Interface, ECS Executive Director and CEO Christopher Jannuzzi highlighted the connection between Free the Science and Plan S. “Fortunately for ECS,” Jannuzzi said, “Free the Science, and our demonstrated commitment to open access and open science, puts us in an excellent position to not only comply with Plan S, but also to grow our publications’ reach because of it.”

Looking Ahead

At present, ECS aims to ensure its journals’ compliance with Plan S by the revised implementation date of January 1, 2021. As the implementation date approaches, ECS’s foremost allegiance will remain, as ever, with the community of researchers it stewards. The needs of the ECS community will ultimately inform any actions taken in response to Plan S. More information on ECS and Plan S will be included in subsequent issues of Interface.

Ways for Authors to Comply with Plan S

FUNDING

ROUTE

Open Access publishing venues (journals or platforms)

Subscription venues (repository route)

Transition of subscription venues (transformative arrangements)

Authors publish in an Open Access journal or on an Open Access platform.

Authors publish in a subscription journal and make either the final published version (Version of Record (VoR)) or the Author’s Accepted Manuscript (AAM) openly available in a repository.

Authors publish Open Access in a subscription journal under a transformative arrangement.

cOAlition S funders will financially support publication fees.

cOAlition S funders will not financially support ‘hybrid’ Open Access publication fees in subscription venues.

cOAlition S funders can contribute financially to Open Access publishing under transformative arrangements.

Join a Powerful Partnership! SOCIE PEOPLE T Y NE WS

The ECS institutional membership program provides content access, member-related discounts, as well as advertising, exhibit, and sponsorship opportunities. Memberships are available for all types of organizations!

Government

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Standard Package Benefits • Profile on the ECS website featured on the Institutional Members webpage and in the ECS Organizational Member Directory

Academic Institutional Membership Tiers

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• Listing in the quarterly Interface and biannual meeting publications • Eligible for annual Leadership Circle Awards recognition

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Most-valued customizable options: • Up to 50% off Exhibits and General Meeting Sponsorships • 5-30% off ECS Subscriptions • Advertising Discounts • 25-50% discounts on Career Expo packages • Member representatives that receive full member benefits

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Sustaining Institutional membership packages start as low as $1,250 per year!

Contact Shannon.Reed@electrochem.org to customize a package to meet your organization’s needs! 38

Available standard package and customizable options are dependent on the level of institutional membership. The Electrochemical Society Interface • Summer 2019 • www.electrochem.org

Looking at Patent Law:

Patenting Lithium Metal Phosphate Materials for Rechargeable Batteries—A Case Study by E. Jennings Taylor and Maria Inman

n this installment of the “Looking at Patent Law” articles, we present a case study of the lithium metal phosphate cathode material invention. We have chosen this invention to align with the battery focus of this issue of Interface. Recall from our previous article1 that the prosecution history of a patent application is publicly available in the file wrapper on the U.S. Patent & Trademark Office (USPTO) Patent Application Information Retrieval (PAIR) system.2 With the PAIR system as the basis for this case study, we illustrate the prosecution “events” encountered leading to the issuance of the seminal U.S. Patent “Cathode Materials for Secondary (Rechargeable) Lithium Batteries” (U.S. Pat. No. 5,910,382).3 A key figure from the ‘382 patent is presented in Fig. 1. As of March 2019, the ‘382 patent has been cited by over 350 subsequently filed patents/patent applications. In 1997, a manuscript describing the technical aspects of the discovery was published in the Journal of The Electrochemical Society (JES).4 (Note, the paper was published after the filing date of the first patent application and consequently was not prior art.) The 1997 manuscript is the most highly cited publication in JES, with nearly 8,000 citations according to Google Scholar. This journey, shown in Table I, begins with the initial filing of the first provisional patent application, followed by the filing of a utility patent application, through various interactions with the USPTO, to the issue of the first in this family of separate but related patents. After a brief synopsis of the “discovery” of the invention, the events leading to the ‘382 patent will beFig described in chronological order. 1

Fig. 1. Figure from U.S. Patent No. 5,910,382. From U.S. Patent No. 5,910,382

Discovery In 1994, John Goodenough of the University of Texas at Austin directed researchers in his group to initiate research activities exploring various reduction-oxidation couples with polyanions for use in rechargeable batteries. From that research, Goodenough and his colleagues discovered the utility of using the olivine form of various compounds containing lithium, iron, and phosphate as a cathode material in rechargeable lithium-ion batteries. Goodenough and his colleagues recognized the significance of their discovery and began synthesizing larger quantities of lithium iron phosphate (LiFePO4) and other lithium “metal” phosphate (LiMPO4) compounds with other transition metals to determine their efficacy as cathode materials for rechargeable lithium-ion batteries.5

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Table I.

Date

Event

1996 APR 23

Applicant; Provisional Patent Filed; 60/016,060

1996 DEC 4

Applicant; Provisional Patent Filed; 60/032,346

1997 APR 21

Applicant; Utility Application Filed (08/840,523)

1997 SEP 24

USPTO; Notice To File Missing Parts

1997 NOV 4

Applicant; Filing Fee, Inventor Declaration

1997 NOV 4

Applicant; Inventor Assignment

1997 DEC 24

Applicant; Utility Application Filed (08/998,264)

1998 FEB 5

USPTO; Non-Final Office Action (NFOA)

1998 FEB 23

Applicant; Information Disclosure Statement

1998 AUG 5

Applicant; Response to NFOA

1998 DEC 4

USPTO; Notice of Allowance

1999 JUN 8

USPTO; Patent Issued (5,910,382)

2003 FEB 4

USPTO; Patent Issued (6,514,640)

The Electrochemical Society Interface • Summer 2019 • www.electrochem.org

Taylor and Inman

(continued from previous page)

Provisional Patent Application Based on the encouraging progress of the work related to cathode materials for rechargeable lithium-ion batteries, on April 23, 1996, a provisional patent application was filed by the Board of Regents of the University of Texas System on behalf of the inventors (60/016,060).6 The ‘060 provisional application disclosed LiFePO4 as a cathode material for rechargeable lithium batteries. A provisional patent application establishes a filing date for the invention but is not examined (prosecuted) and has a pendency of 12 months.7 Consequently, a provisional patent application is abandoned after one year and does not mature into a regular utility patent application. If a U.S. regular (nonprovisional) and/or foreign patent application is filed within one year of the filing date of the provisional patent application, the U.S. and foreign patent applications receive the priority date of the provisional patent application’s filing date (Fig. 2). In essence, the provisional patent application is a placeholder for subsequently filed nonprovisional patent applications, provided they are filed within one year of the filing of the provisional patent application. In order to establish a filing date, the provisional patent application must include: 1. Specification8 “… a written description of the invention, and the manner and process for making it … to enable any person skilled in the art … to make and use [the invention].” 2. Drawings9 “… where necessary for understanding the subject matter … to be patented.” In order to maintain the filing date of the provisional patent application, the following material must be submitted within a time period (typically two months) specified by the USPTO in a notice to file missing parts: 1. Filing fee in accordance with the current USPTO schedule,10 2. Cover sheet noting “provisional” patent application and including the names of the inventors. An important caveat regarding the provisional patent application is the requirement that it enable one skilled in the art to make or practice the invention. More specifically, if the claims of the subsequently filed nonprovisional patent application are not enabled by the provisional patent application, then the nonprovisional patent application does not benefit from the filing date of the provisional patent application. Additionally, the provisional application does not require an inventor oath or declaration, Invention Disclosure Statement (IDS), or claims. Although claims are not required, many patent attorneys choose to include claims in the provisional patent application. As previously discussed, the named inventors must be correctly represented on U.S. patent applications, including provisional patent applications.11 Specifically, inclusion of a colleague as a co-inventor who did not participate in the conception of the invention is known as a misjoiner and invalidates an otherwise valid patent. Similarly, exclusion of a co-inventor who participated in the conception is known as a nonjoiner and also invalidates an otherwise valid patent. Fig 3

Non-Provisional Receives Benefit of Earlier Provisional Application Filing Date < 12 months

Provisional Filing Date

Time

US or Foreign NonProvisional Filing Date

If an inventor is erroneously omitted or erroneously included as an inventor, the misjoiner/nonjoiner may be corrected and the patent remains valid.12 On December 4, 1996, a second provisional patent application was filed by the Board of Regents of the University of Texas System on behalf of the inventors (60/032,346).13 The ‘346 provisional patent application more generally disclosed LiMPO4 materials with the ordered olivine structure as a cathode material for rechargeable lithium batteries where M is manganese (Mn), iron (Fe), cobalt (Co), or nickel (Ni), or their combination such as Fe1-xMnx. The only difference between the ‘060 and ‘346 provisional patent applications was the additional disclosure of the additional class of LiMPO4 cathode materials. Both provisional patent applications had the same title, same inventors, and same figures. Both the ‘060 and ‘346 provisional patent applications attributed financial support of the research to the Robert A. Welch Foundation, Houston, Texas. Consequently, the lack of federal funding removed the obligation to acknowledge government “march-in rights” to the subject invention.14

Utility Patent Application On April 21, 1997, the Board of Regents of the University of Texas System filed a utility patent application (08/840,523) claiming priority to the ‘060 and ‘346 provisional patent applications. As required to receive the benefit of the provisional patent application filing date, the ‘523 utility patent application was filed within the 12-month period of the ‘060 and ‘346 provisional patent application filing dates. Although an additional inventor was added to the ‘523 utility patent application, the only requirement to claim priority is that the utility and provisional patent application have at least one common inventor.15 In order to establish a filing date, a utility patent application must include 1. Specification8 “… a written description of the invention, and the manner and process for making it … to enable any person skilled in the art … to make and use [the invention].” 2. A minimum of one claim16 “… particularly pointing out … the subject matter … as the invention.” 3. Drawings9 “… where necessary for understanding the subject matter … to be patented.” The ‘523 utility patent application contained claims directed towards two statutory patent classes, a composition of matter (cathode material) and manufacture (battery).17 Two exemplary independent claims18,19 from the patent application illustrating the two statutory classes are: Claim 1 (as filed). A cathode material [composition of matter] for a rechargeable electrochemical cell, said cell also comprising, an anode and an electrolyte, the cathode comprising a compound having the formula LiMPO4, where M is at least one first-row transition-metal cation. Claim 23 (as filed). A secondary battery [manufacture] comprising an anode, a cathode and an electrolyte, said cathode comprising an ordered olivine compound having the formula LiMPO4, where M is at least one first-row transition-metal cation. On September 24, 1997, correspondence from the USPTO assigned patent application number 08/840,523 to the utility patent application and issued a “Notice to File Missing Parts of Application” with a two-month response date. In order to maintain the filing date, the following additional material must be submitted:

Fig. 2. 40

The Electrochemical Society Interface • Summer 2019 • www.electrochem.org

1. Filing fee in accordance with the current USPTO schedule;10 2. Inventor oath or declaration asserting:20 a. The patent application was authorized by the inventor(s); b. The inventor(s) believe he/she is the original inventor or they are the original joint inventors. There are subtle differences between a U.S. provisional and nonprovisional patent application (Table II). On November 4, 1997, the filing fee and declaration were filed within the two-month time period. The declaration was notarized and per the Code of Federal Regulations (CFR):21 “… false statements are punishable by fine or imprisonment … and may jeopardize the validity of … any patent application issuing thereon.” In addition, on November 4, 1997, the inventors assigned their rights in the subject invention to the Board of Regents, The University of Texas System. The Board of Regents, on behalf of the inventors, appointed a power of attorney to represent them in the prosecution of the patent application. Finally, in the applicant response dated November 4, 1997, the Board of Regents claimed “small entity status” as a not-for-profit entity and was thereby eligible for reduced filing fees.

Non-Final Office Action (NFOA) On February 5, 1998, the USPTO issued a NFOA containing 1. a notice to correct the drawings to be in compliance with USPTO standards, 2. the examiner’s search strategy for the subject patent application, 3. a list of references cited by the examiner, and 4. a non-final rejection of the subject patent application. A guide to patent drawings has been published by NOLO Press.22 The notice to file formal drawings was triggered since the non-final rejection contained allowable subject matter (claims). Of the 37 claims submitted in the patent application, 32 were allowed and 5 were objected to as improper dependent claims. Specifically, these 5 dependent claims failed to further limit the subject matter of the claims to which they referred, specifically:23 “… One or more claims may be presented in dependent form, referring back to and further limiting another claim or claims in the same application. ... Claims in dependent form shall be construed to include all the limitations of the claim incorporated by reference into the dependent claim.” The NFOA indicated a three-month period for response, otherwise the application becomes abandoned:24 “… failure of the applicant to prosecute the application within six months after any [office] action … or within such shorter time, not less than thirty days … the application shall be regarded as abandoned by the parties thereto.”

Table II. Comparison of U.S. Provisional and Utility Patent Applications

Provisional Patent Application

Non-Provisional Utility Patent Application

Claims NOT required.

Claims required.

Not examined – cannot issue as patent.

Examined – can issue as patent.

Cannot claim domestic or foreign priority.

Can claim domestic or foreign priority.

Twenty-one year term if nonprovisional is filed within 12 months.

Twenty year term begins with filing date.

As an indication of the breakthrough nature of the invention, the NFOA did not cite any prior art against the patent application for novelty or obviousness.18,25,26

Submission of an Information Disclosure Statement and Duty of Candor On February 23, 1998, the applicants submitted an “Information Disclosure Statement” (IDS) in accordance with U.S. patent laws. The IDS is the submission of relevant background art or information to the USPTO by the applicant. The “Duty of Candor” requires that the inventor submit an IDS within a reasonable time of submission of the patent application:27 “… disclose to the Office [USPTO] all information known to that individual to be material to patentability.” The “Duty of Candor” is specific to any existing claim and requires that the IDS be continually updated while the claim is pending. The “Duty of Candor” ceases only when the claim is allowed and the issue fee is paid. The “Duty of Candor” extends to any individual associated with the filing of the patent application including 1. inventor(s), 2. patent counsel, or 3. those persons who are substantially involved in the preparation or prosecution of the patent application. Substantial involvement could include technical assistants, collaborators, or colleagues. Substantial involvement would generally not extend to clerical workers. Furthermore, the inclusion of a reference in an IDS:28 “… is not taken as an admission that the reference is prior art against the claims.” If a finding of a violation of the “Duty of Candor” resulting in “inequitable conduct” regarding any claim in a patent application or patent is determined, then all the claims are rendered invalid.29 Finally, in spite of the requirement of the “Duty of Candor,” the applicant is cautioned not to “bury” the examiner with a long list of nonmaterial references in hopes that the examiner will not notice the material references.

Response to NFOA The applicants requested an extension of time of three months for response to the NFOA and paid the applicable fee. On August 5, 1998, the applicants submitted an updated IDS in accordance with the “Duty of Candor.” In response to the objection to the five dependent claims, the applicant added two new independent claims. Both of the newly added independent claims were supported (i.e., enabled) by the as-filed patent specification. Two of the objected-to claims were amended to dependent from one newly added independent claim, and the remaining three objected-to claims were amended to depend from the other newly added independent claim.

Restriction Requirement In addition, the USPTO issued a requirement for “Restriction/ Election” for the patent application in accordance with U.S. patent laws. The “Restriction/Election” basically says that the patent application contains two or more inventions and the applicant must “elect” which invention to prosecute first:30 “If two or more independent and distinct inventions are claimed in one application … [the USPTO] may require the application to be restricted to one of the inventions.”

The Electrochemical Society Interface • Summer 2019 • www.electrochem.org

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Taylor and Inman

(continued from previous page)

As described in the Manual of Patent Examination Practice (MPEP),31 “Where an application includes claims directed to different embodiments or species that could fall within the scope of a generic claim, restriction between the species may be proper if the species are independent or distinct.” The restriction requirement separated those claims directed towards two species of cathode materials into two inventions. Specifically, Invention I: Directed towards a cathode material LiMPO4 where M is at least one first-row transition-metal cation. Invention II: Directed towards a cathode material having an ordered or modified olivine structure with the formula LixM1-(d+t+q+r)DdTtQqRrXO4 where M is a cation of a metal selected from the group consisting of Fe, Mn, Co, Ti, Ni or mixtures thereof; D is a metal having a +2 oxidation state selected from the group consisting of Mg2+, Ni2+, Co2+, Zn2+, Cu2+, and Ti2+; T is a metal having a +3 oxidation state selected from the group consisting of Al3+, Ti3+, Cr3+, Fe3+, Mn3+, Ga3+, Zn3+, and V3+; Q is a metal having a +4 oxidation state selected from the group consisting of Ti4+; Ge4+; Sn4+, and V4+; R is a metal having a +5 oxidation state elected from the group consisting of V5+; Nb5+, and Ta5+; X comprises Si, S, P, V or mixtures thereof; and 0 ≤ x ≤ 1; and 0 ≤ d, t, q, r ≤ 1, where at least one of d, t, q, and r is not 0. The applicants “elected” to prosecute Invention I first.

Allowance of Patent Application On December 4, 1998, the USPTO issued a notice of allowance for the claims associated with Invention I. After payment of the issue fee, the ‘523 patent application issued as U.S. Patent No. 5,910,382 on June 8, 1999. Continuation-in-part patent application No. 08/998,264 was filed on December 24, 1997, directed towards Invention II. The ‘264 patent application claimed priority to the ‘060 and ‘346 provisional patent applications and the ‘382 patent. The ‘264 patent application issued as U.S. Patent No. 6,514,640 on February 4, 2003.

Summary In this installment of our “Looking at Patent Law” series, we presented a case study of the prosecution of the seminal “Cathode Materials for Secondary (Rechargeable) Lithium Batteries” patent. The case study begins with a brief synopsis of the discovery of the LiMPO4 materials followed by (1) filing of provisional patent applications, (2) filing of a utility patent application, (3) filing of a continuation-in-part patent application, and (4) allowance of two patents. The case study illustrates the differences between a provisional and nonprovisional utility patent application and the requirements to establish and maintain a filing date for both types of patent applications. The case illustrates the requirement to submit an “Information Disclosure Statement” and the associated “Duty of Candor” in interacting with the USPTO. The case also illustrates the “Restriction/Election” requirement associated with different species of materials and the resulting continuing patent application. With this case study, we hope to demystify the patent prosecution process and better prepare electrochemical and solid state scientists, engineers, and technologists to interact with their patent counsel regarding their inventions.

About the Authors E. Jennings Taylor is the founder of Faraday Technology, Inc., a small business focused on developing innovative electrochemical processes and technologies based on pulse and pulse reverse electrolytic principles. Taylor leads Faraday’s patent and commercialization strategy and has negotiated numerous via field of use licenses as well as patent sales. In addition to technical publications and presentations, Taylor is an inventor on 40 patents. Taylor is admitted to practice before the United States Patent & Trademark Office (USPTO) in patent cases as a patent agent (Registration No. 53,676) and is a member of the American Intellectual Property Law Association (AIPLA). Taylor has been a member of ECS for 38 years and is a fellow of ECS. He may be reached at jenningstaylor@faradaytechnology.com. https://orcid.org/0000-0002-3410-0267

Maria Inman is the research director of Faraday Technology, Inc., where she serves as principal investigator on numerous project development activities and manages the company’s pulse and pulse reverse research project portfolio. In addition to technical publications and presentations, she is competent in patent drafting and patent drawing preparation and is an inventor on seven patents. Inman is a member of ASTM and has been a member of ECS for 21 years. Inman serves ECS as a member of numerous committees. She may be reached at mariainman@ faradaytechnology.com. https://orcid.org/0000-0003-2560-8410

References 1. E. Jennings Taylor and Maria Inman, “Looking at Patent Law: Opportunity Prospecting by Analysis of Analogous Patent Art,” Electrochem. Soc. Interface, 26 (4), 57 (2017). 2. USPTO Patent Application Information Retrieval (PAIR) https:// portal.uspto.gov/pair/PublicPair. 3. John B. Goodenough, Akshaya K. Padhi, K. S. Nanjundaswamy, and Christian Masqueller, “Cathode Materials for Secondary (Rechargeable) Lithium Batteries,” U.S. Patent No. 5,910,382 issued June 8, 1999. 4. A. K. Padhi, K. S. Nanjundaswamy, and J. B. Goodenough, “Phospho-olivines as Positive-Electrode Materials for Rechargeable Lithium Batteries,” J. Electrochem. Soc., 144, 1188 (1997). 5. The Board of Regents of the University of Texas System and Hydro-Quebec versus A123 Systems, Inc., Black & Decker Corp., Black & Decker (U.S.) Inc., and China BAK Battery, Inc., in the United States District Court for the Northern District of Texas, C.A. No. 3:06-CV-1655-B filed May 18, 2010. 6. John B. Goodenough, Akshaya K. Padhi, and K. S. Nanjundaswamy, “LiFePO4 (Synthetic Triphylite), a New Cathode Material for Secondary (Rechargeable) Lithium Batteries,” U.S. Patent Application No. 60/016,060 filed April 23, 1996. 7. 35 U.S.C. §111(b) Application/Provisional Application. 8. 35 U.S.C. §112(a) Specification/In General. 9. 35 U.S.C. §113 Drawings. 10. https://www.uspto.gov/learning-and-resources/fees-andpayment/uspto-fee-schedule 11. E. Jennings Taylor and Maria Inman, “Looking at Patent Law: Why Is the Word ‘Right’ Mentioned Only Once in the Constitution of the United States?” Electrochem. Soc. Interface, 26 (2), 45 (2017).

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12. Manual of Patent Examination Procedure (MPEP) §1481.02 Correction of Named Inventor. 13. John B. Goodenough, Akshaya K. Padhi, and K. S. Nanjundaswamy, “LiFePO4 (Synthetic Triphylite), a New Cathode Material for Secondary (Rechargeable) Lithium Batteries,” U.S. Patent Application No. 60/032,346 filed December 4, 1996. 14. 35 U.S.C. §203 March-in Rights. 15. 35 U.S.C. §119(e)(1) Benefit of Earlier Filing Date; Right of Priority. 16. 35 U.S.C. §112(b) Specification/Conclusion. 17. 35 U.S.C. §101 Inventions Patentable. 18. E. Jennings Taylor and Maria Inman, “Looking at Patent Law: Patentable Inventions, Conditions for Receiving a Patent, and Claims,” Electrochem. Soc. Interface, 26 (3), 44 (2017). 19. 35 U.S.C. §112(c) Specification/Form. 20. 35 U.S.C. §115(b)(1)(2) Inventor’s Oath or Declaration/ Required Statements. 21. 37 CFR §1.68 Declaration in Lieu of Oath 22. D. Pressman and J. Lo, How to Make Patent Drawings, 7th ed., NOLO Press, Berkeley, California (2015). 23. 37 CFR §1.75(c) Claim(s). 24. 35 U.S.C. §133 Time for Prosecuting Application. 25. 35 U.S.C. §102 Conditions for Patentability; Novelty and Loss of Right to Patent. 26. 35 U.S.C. §103 Conditions for Patentability; Non-Obviousness Subject Matter. 27. 37 CFR §1.56(a)(c) Duty to Disclose Information Material to Patentability.

28. Riverwood Int’l Corp. v. R.A. Jones & Co., 324 F.3d 1346, 135455, 66 USPQ2d 1331, 1337-38 (Fed Cir. 2003). 29. Manual of Patent Examination Procedure (MPEP) §2016 Fraud, Inequitable Conduct, or Violation of Duty of Disclosure Affects All Claims. 30. 35 U.S.C. §121 Divisional Applications. 31. Manual of Patent Examination Procedure (MPEP) §806.04 Genus and/or Species Inventions.

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T ECH HIGHLIGH T S Hollow Carbon Spheres as a Sulfur Host for Li-S Batteries Lithium-sulfur batteries demonstrate great promise as a beyond Li-ion energy storage device, offering a practical specific energy density of 400–600 Wh kg-1 which is more than double that of current stateof-the-art Li-ion cells. However, inherent issues, including the insulating nature of S and the polysulfide shuttle mechanism, have impeded the widespread use of Li-S batteries. The S host materials play an extremely important role in overcoming these issues and consequently porous carbon materials have been the subject of much research. Researchers from the Dong-A University have recently presented a scalable method to synthesize hollow carbon spheres (HCSs) for use as a S host, as well as a novel two-step S loading method which involves a solution impregnation before the traditionally used melt diffusion method. Cathode samples prepared via this twostep process demonstrated a significantly higher initial capacity, implying higher S utilization, as well as increased capacity retention, compared to samples prepared via the standard S melt diffusion method. This report demonstrates that the encapsulation of sulfur in hollow porous carbon spheres is an effective approach for the development of high-performance Li-S batteries. From: Y. Choi, N. Yoon, N. Kim, et al., J. Electrochem. Soc., 166, A5099 (2019).

The Properties of ElectrochemicallyGrown Copper Sulfide Films The long-term reliability, specifically corrosion resistance, of copper canisters for spent nuclear fuel storage is the focus of many recent studies in the literature. A thorough understanding of the Cu2S films (characteristics, passivity, growth, etc.) that form on these canisters in sulfate reducing bacteria, groundwater environments is necessary to understand and predict possible corrosion degradation mechanisms (i.e., localized corrosion). To that end, researchers at Western University have characterized electrochemically grown Cu2S films in sodium chloride solutions with varying sulfide concentrations via voltammetry, electrochemical impedance spectroscopy, and surface analytical techniques. Their findings indicate that growth of the Cu2S films occurred in two distinct stages. Initial growth of a thin porous film at low positive potentials was then followed by increased porosity and deposition of an outer layer at higher potentials. At high [SH–], growth of the film slowed, hypothesized, based on collected EIS data, to be due to the formation of this outer layer, not passivation. Lastly, through this work, the researchers confirmed their previous findings that a passive Cu2S

layer will only form in an environment with a high [SH–] level and flow rate.

From: T. Martino, J. Smith, J. Chen, et al., J. Electrochem. Soc., 166, C9 (2019).

Proton Conduction and Oxygen Diffusion in Ultra-Thin Nafion Films in PEM Fuel Cell Proton exchange membrane fuel cells (PEMFCs) are constructed with a PEM between two porous electrodes. The oxygen reduction reaction (ORR)—consisting of O2, H+, and e- reactants—occurs at Pt particles supported on larger carbon particles in the cathode. Researchers in the USA performed experiments to characterize the oxygen and proton transport resistances in thinner Nafion films. Their electrochemical system consisted of Pt microelectrodes patterned on a SiO2 substrate on which any ionomer film may be spin-coated to desired thickness. Nafion films of different thicknesses (100–1000 nm) were exposed to different relative humidity (0.5–0.9 RH), temperature (40–80°C), and oxygen concentration (0–0.9%) levels. The authors measured oxygen permeability (D H) using limiting current experiments and proton conductivity using electrochemical impedance spectroscopy. While the permeability increased with decreasing thickness, the proton conductivity decreased. Further characterization revealed non-ideality of the experimental set-up, wherein the thin film exhibited buckling between the electrodes, suggesting poor adhesion to the SiO2. The thickness of the ionomer film approaching the dimension of the aqueous domains also leads to film anisotropy. The authors discuss various approaches to continue this ongoing investigation. ●

From: D. Chen, A. Kongkanand and J. Jorne, J. Electrochem. Soc., 166, F24 (2019).

Online Continuous Manufacture of Carbon Nanotubes-Grown Carbon Fibers While imparting improved mechanical properties to structures, the fibers in carbon fiber reinforced epoxy composites suffer low interlaminar shear strength (ILSS). Most efforts for improving ILSS using carbon nanotubes (CNTs) have been smallscale laboratory demonstrations. Addressing the need for large-scale production, a team of researchers in China explored the growth of CNTs directly on a reel of carbon fiber filament. The researchers set up a continuous process—consisting of electrochemical oxidation followed by cleaning and drying, then applying a catalyst by dip coating followed by drying and 450°C reduction, then growing CNTs by chemical vapor deposition (CVD) at 650°C—for the fiber to pass through between reels. The authors used electron microscopy to characterize the produced carbon fiber. CNTs were uniformly

The Electrochemical Society Interface • Summer 2019 • www.electrochem.org

and finely distributed and possessed 20– 50 nm diameters. The tensile strength of these carbon fibers was tested at various stages of production. The fiber after the reduction process suffered a slight decrease (4.3%); however, after growth of CNTs the fiber possessed a subsequent increase (9%) in strength. The CVD scheme was found to repair defects in the electrochemically treated fiber. The authors believe this CNT-modified carbon fiber will improve reinforced epoxy composites. From: J. Qin, C. Wang, Y. Wang, et al., ECS J. Solid State Sci. Technol., 8, M23 (2019).

Improved Adhesion of Metal Electrode Layer on Si3N 4 Substrate through an All-Wet Process With continued electronic device miniaturization, the components from which they are built must decrease in size by an accelerated amount. Degradation of device performance becomes more pronounced at these smaller scales. To alleviate thermal degradation, heat sinks can be incorporated within the individual components. Commonly used heat sinks are composed of a metallic circuit layer with a ceramic substrate. A promising substrate candidate is Silicon Nitride (Si3N4) which has both excellent thermal and mechanical properties. The deposition of well adhered metallic layers onto Si3N4 involves complex and expensive processes which fuel the search for cheaper alternative techniques. A team of researchers based in Korea has developed an all-wet process for the deposition of a Ni electrode layer onto a Si3N4 substrate. The method involves the initial deposition of an interfacial Pd-TiO2 layer on the Si3N4 from which an electroless plated Ni electrode can be grown. To achieve a robust adhesion between the Si3N4 and Ni layers, the surface of the nitride was functionalized prior to the deposition of Pd-TiO2. Through both functionalization and interfacial layering, a cost-effective and integrable heat sink component can be built for miniaturized device components. From: D. Kim, N. S. A Eom, J. Kim, et al., ECS J. Solid State Sci. Technol., 8, P159 (2019).

Tech Highlights was prepared by Colm Glynn of Analog Devices International, Mara Schindelholz of Sandia National Laboratories, David McNulty of Paul Scherrer Institute, and Donald Pile of Rolled-Ribbon Battery Company. Each article highlighted here is available free online. Go to the online version of Tech Highlights in each issue of Interface, and click on the article summary to take you to the full-text version of the article.

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Current Trends in Electrolytes by Bryan D. McCloskey and Kang Xu

e are delighted to present this Interface issue highlighting recent developments in electrolyte research for Li-ion, “beyond Li-ion,” and solid state/polymer batteries. Electrolytes are obviously an essential component of any electrochemical device, serving to facilitate ion current between the anode and cathode while insulating any electronic flow. Highly reducing (negative electrode) and oxidizing (positive electrode) environments are present in all high-energy batteries, posing stringent requirements for electrolyte compositions, which can only stabilize via passivation through sacrificial decomposition of certain electrolyte components. The solid electrolyte interphase (SEI) in Li-ion batteries (LIBs) is the most conspicuous example for such passivation. Such interphasial stabilization along with other properties, including high ion conductivity, low cost, high voltage stability, and safety, constitute the core parameters for a practical electrolyte. Recent research on new electrolyte systems focuses on attaining the best combination of these key properties, which ultimately will enable the development of improved batteries with excellent lifetimes and energy and power densities. Furthermore, as new materials and chemistries are developed to push the limits of battery performance, electrolytes will likewise need to be developed that adapt to the requirements necessary to allow these energy storage systems to operate efficiently. This issue is comprised of four articles from leading battery experts who encompass these research directions. The first article, written by Jeff Dahn, Kevin Gering, and colleagues, provides a systematic account of the importance of additives and solvent composition to optimize the properties of liquid LIB electrolytes. They emphasize the complex and poorly understood nature of additive engineering, where ostensibly innocuous changes in battery operating conditions (e.g., slight temperature fluctuations) can have a dramatic impact on optimal additive selection. Furthermore, by using unconventional solvents such as methyl acetate, they show that electrolyte transport properties can be tuned to benefit rate capabilities without substantially impacting stability. Finally, they emphasize the need to more completely understand the electrolyte composition’s effect on battery performance, and highlight the utility of the Advanced Electrolyte Model, a simulations-based model that predicts electrolyte properties, in helping guide electrolyte design. Although liquid-based electrolytes remain the state of the art for LIBs, they are comprised of volatile and flammable organic solvents that pose hazard risks. Furthermore, despite decades of effort to commercialize Li metal anodes, which would provide a quantum leap in specific energies, no liquid electrolyte has been found to support efficient, uniform, and safe Li plating/striping. Electrolytes that limit or eliminate volatile organic components are being pursued to enable Li anodes while improving safety over conventional electrolytes. Two articles—one by Martin Winter and colleagues, another by Jeff Sakamoto and Arushi Gupta—highlight the development of these electrolytes, based on either polymers or inorganic solid state ion conductors. The former provides a concise perspective on polymer-based electrolytes and their development, particularly in the context of enabling Li metal electrodes. Although polymers offer excellent processability compared to ceramic ion conductors, their limited conductivity at room temperature often constitutes the main obstacle to their widespread implementation in electric vehicles. One strategy to overcome these conductivity limitations is to understand, and ultimately harness, ion conduction in hybrid + organic-inorganic electrolytes. Solid state inorganic Li conductors, such as thiophosphates and related derivatives, garnet phase

oxides, and LISICON-type conductors, have been reported to have ion conductivities that rival, and in some cases surpass, liquid electrolytes. However, their poor processability severely impedes their commercial viability. It is envisioned that by combining polymer and inorganic solid state ion conductors in a composite structure, the best properties of both systems—polymer processability plus inorganic conductivity—can be achieved. Gupta and Sakamoto provide a detailed study on understanding transport mechanisms through a polymer-inorganic thin film composite interface, with the goal of guiding rational design for future organic-inorganic electrolyte configurations. In the fourth article, Doron Aurbach and colleagues provide a perspective on electrolytes for the so-called “beyond LIB” chemistries: Mg-ion, Li-S, and Li-air batteries. These chemistries, while all related given their high theoretical energy densities, face daunting challenges primarily associated with reversibility of their active electrochemical processes. For these chemistries to someday supplant LIBs in the rechargeable battery hierarchy, new electrolytes will have to be developed that help mitigate these reversibility challenges. In each case, the understanding of optimal electrolyte design is evolving, with stability towards products, suppression of electrode-electrolyte interfacial impedance, and selective ion transport (when a product is itself ionic) all being important considerations in the various systems. Aurbach and colleagues provide an excellent summary of these important design considerations for each battery chemistry. While efforts pursuing new and aggressive battery chemistries intensify, novel electrolyte formulations are increasingly recognized as essential to overcome outstanding challenges that limit battery performance and safety. Numerous research directions are necessary to push beyond limitations of current electrolytes; this issue provides an excellent overview on these research trends. © The Electrochemical Society. DOI: 10.1149/2.F03192if.

About the Guest Editors Bryan D. McCloskey is an assistant professor in the Department of Chemical and Biomolecular Engineering at the University of California, Berkeley, and holds a joint appointment as faculty engineer in the Energy Storage and Distributed Resources Division at Lawrence Berkeley National Laboratory. His laboratory focuses on characterization of fundamental electrochemical processes to provide guidance for the development of energy storage, electrocatalytic, and corrosion-resistant materials. More information can be found at his group’s website: www.mccloskeylab.com. He may be reached at bmcclosk@berkeley.edu. https://orcid.org/0000-0001-6599-2336 Kang Xu is laboratory fellow and team lead at the U.S. Army Research Lab. He has been working on electrolyte materials and interphasial chemistry for over 30 years. He has published over 200 papers in peer-reviewed journals, has written/edited three chapters/books, and currently holds over 25 issued U.S. patents. His publications have received over 20,000 citations in the open literature, with an h-index of 72. He may be reached at conrad.k.xu.civ@mail.mil.

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Electrolyte Development for High-Performance Li-Ion Cells: Additives, Solvents, and Agreement with a Generalized Molecular Model by Eric R. Logan, Kevin L. Gering, Xiaowei Ma, and Jeff R. Dahn

he electrolyte is one of the most important components of a Li-ion cell. In addition to facilitating the flow of ionic current between electrodes during charge and discharge, the electrolyte plays other important roles. The components of the electrolyte are responsible for forming the passivating solid electrolyte interphase (SEI) layers which enable long-term cycling of a Li-ion cell. Further, under abusive conditions such as extremely fast charge and discharge currents, the electrolyte must be able to sustain large ionic currents with little concentration polarization. As such, the main areas of research focus for the electrolyte of a Li-ion cell can be broken down into two main categories: (1) interfacial properties, which are primarily dictated by low weight percent electrolyte additives; and (2) bulk transport properties, which are dominated by choices of solvent and salt blends. In recent years, much advancement has been made in both areas of electrolyte development. New combinations of low wt. % additives have been developed to extend the cycle and calendar life of Li-ion cells to new highs. Low viscosity cosolvents such as methyl acetate (MA) or ethyl acetate (EA) have been shown to improve the rate capability of Li[Ni, Mn, Co]O2 (NMC)/graphite cells,1-5 following the pioneering work of Smart et al.,6 with minor compromises in cell lifetime. This paper will highlight some recent work on additive development, noting that subtle differences in cycling conditions can “make or break” a given additive combination. Additionally, work on mapping the transport properties for a wide variety of electrolyte systems of interest will be shown. Finally, the Advanced Electrolyte Model (AEM), a theoretical model for calculating the properties of electrolytes, will be presented with an emphasis on the AEM’s agreement to experiment and ongoing efforts to validate the model in a wide array of electrolyte systems.

and a charge/discharge rate of C/3.* At these specific conditions, the best additive combination (for this particular cell type) appears to be 2% vinylene carbonate (VC) + 1% ethylene sulfate (DTD), with ~90% original capacity remaining after over 3,000 cycles (about 2.5 years of testing). Comparatively, 2% VC by itself would show much greater capacity fade over 3,000 cycles if the line was extrapolated. Although the additive blend of 2% VC + 1% DTD performs very well at 40°C, C/3:C/3 cycling, the story is different if the cycling conditions are changed. At 20°C and a charge/discharge rate of 1 C, the shape of the capacity vs. cycle curve of the 2% VC + 1% DTD cell changes dramatically around 2,500 cycles. This rapid increase in capacity loss, termed “rollover” due to the nature of the capacity vs. cycle curve, could not have been predicted given only the 40°C cycling data. The cell with 2% FEC + 1% LiPO2F2, which performed slightly worse than the 2% VC + 1% DTD cell at 40°C, does not show this potentially catastrophic rollover failure at 20°C. Again, given only the 40°C cycling data, this could not have been predicted. This type of failure appears to be at least in part due to impedance increases in the cell. Panels (c) and (d) in Fig. 1 show the difference between the average charge and discharge voltages (called ΔV here) versus cycle number for the 40°C and 20°C cycling, respectively. The increase in ΔV in the 2% VC + 1% DTD cell at 20°C corresponds to an increase in cell impedance, which originates at the positive electrode/electrolyte interface7 and mirrors almost exactly with the rollover failure in panel (b). This issue is not seen in 40°C cycling, and correspondingly, massive increases in ΔV are not seen (except for the additive-free cell). The takeaway here is threefold. First, very good electrolyte additive packages have been developed that can extend the cycle lifetime of a Li-ion cell by several orders of magnitude. Second, one must be very (continued on next page)

Additive Development

The importance of the electrode/electrolyte interphases cannot be understated; Li-ion batteries in their current form would not have been possible without the development of key solid electrolyte interphase-forming additives. Figure 1 shows that a Li-ion cell without any additives is orders of magnitude less competitive than cells with only 2% by weight vinylene carbonate (VC) added to the electrolyte. An additive-free Li-ion cell only lasts for ~200 cycles before reaching 80% of its original capacity, while electrolyte blends containing additives can last for thousands of cycles with very little capacity loss. The unfortunate reality is that one additive blend that works well with one positive/negative electrode chemistry may not necessarily work well with another cell chemistry, even if the differences between electrode types are small. Cycling conditions can also impact the effectiveness of an additive blend. Consider the differences in capacity retention for the electrolytes shown in Fig. 1. Panel (a) in Fig. 1 shows cycling at 40°C *A C-rate refers to the rate of battery charge/discharge relative to its total capacity. For example, if a battery has a total rated capacity of 1 Ah, a 1 C discharge rate would be 1 A, and C/3 would be 1/3 A.

Fig. 1. (a) and (b) normalized capacity as a function of cycle number for pouch-type NMC532/graphite cells with different additive systems cycled at 40°C at a rate of C/3, and 20°C at a rate of 1C, respectively. (c) and (d), difference between average charge and discharge voltage (ΔV) as a function of cycle number for cells cycled at 40°C at C/3 and 20°C at 1C, respectively.

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careful when choosing to use a particular additive blend for a given application. Different failure modes may become possible, even for seemingly harmless changes to cycling conditions, such as moving from 40°C to 20°C. Third, even after millions of person-hours of research around the world, the details of the function of electrolyte additives (especially combinations) are not well understood.

Electrolyte Transport Properties The bulk transport properties of the electrolyte are also key parameters in the design of a Li-ion cell. Under high charge and discharge currents, large concentration gradients can be formed across the cell stack if an inadequate electrolyte system is used. Further, detailed information about the electrolyte transport properties is required in physics-based models of Li-ion (and other) cells. Valøen and Reimers showed in 2005 that often-overlooked transport parameters such as the binary diffusion coefficient and the activity of the electrolyte led to noticeable differences in simulated voltage curves when used in a physics-based model.8 Despite this observation, relatively little work has been done since then to measure the complete set of transport properties for a range of Li-ion electrolytes. Even the original paper by Valøen and Reimers considers only a model system of LiPF6 in PC:EC:DMC 10:27:63 by volume. Notable exceptions to this gap in the literature do exist. Ehrl et al. and Landesfeind et al. have developed robust electrochemical methods to measure the diffusion coefficient, transference number, and thermodynamic factor in liquid binary electrolytes.9-11 Krachkovskiy et al. have used NMR methods to measure the diffusivities of various solvent/salt species and transport numbers in common carbonatebased Li electrolytes.12 Even with the development of these techniques, accurate measurements of transport parameters such as transference number and diffusion coefficient are considerably more difficult than the measurement of ionic conductivity. As such, these transport parameters are severely underreported in the literature; this was true in 2005 (as pointed out by Valøen and Reimers),8 and was still true in 2017 (as pointed out by Ehrl et al.).10’

Advanced Electrolyte Model One route that can be taken to provide accurate values for the transport properties of Li+ electrolytes (and beyond) is by using computational methods. In this contribution, we would like to highlight one such computational effort to both accurately map and

better understand the transport properties of electrolyte systems and its underlying physical chemistry. The Advanced Electrolyte Model (AEM), developed by Kevin Gering at Idaho National Laboratory,13,14 has a foundation of important molecular-scale interactions in an electrolyte solution (ion-ion, ion-solvent, solvent-solvent) using a statistical-mechanics framework based on the Nonprimitive, Nonrestricted Associated form of the Mean Spherical Approximation (NPNRAMSA). From this foundation many thermodynamic and transport quantities are derived. The AEM supports multicomponent calculations (up to five solvents and two salts at a time) and includes many of the most popular solvents and salts used today in Li-ion battery research and industry. Calculations in the AEM run relatively quickly, and most systems will run on a regular laptop (i.e., high-performance computers are not required). The AEM outputs up to 14 different reports on a given electrolyte system, giving detailed information on physicochemical properties of the system as functions of both temperature and salt concentration. To highlight just a few of the AEM’s many outputs, the AEM calculates electrolyte transport properties such as conductivity, viscosity, diffusivities of the different species in the solution, transference number, and activity coefficients. The AEM also calculates the fraction of different species in the solution, such as single ions (SI), contact ion pairs (IP), and triple ions (TI), as well as solvation energies for cations and anions in solution. Figure 2 gives a summary of the flow of information in the AEM, from user input to output from the program itself. This figure also shows some of the different pure solvent and salt properties that go into the calculations in the AEM. The AEM is a useful tool for determining detailed properties of various electrolyte systems, especially for properties that are not trivial to measure, such as diffusivity and transference number. It can be used to predict properties of complex blends of solvents and salts which may give gains in charge rate capability, for example. It is especially useful for researchers interested in studying Li-ion cells with physics-based models, which require electrolyte parameters beyond simply the ionic conductivity. Although the AEM can enable the things listed above, the outputs from the AEM need to be trusted, which requires careful validation from experiment. The validation of the AEM has been the subject of an ongoing collaboration between Dalhousie University and Idaho National Laboratory. Basic electrolyte properties (conductivity and viscosity) have now been validated against experiment for a wide variety of electrolyte systems over a range of conditions, and as a result of this collaboration, the AEM has been improved to provide accurate results for a wider range of electrolytes.1,15,16

Fig. 2. Step-wise overview of the Advanced Electrolyte Model from user input to output of electrolyte properties. 50

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Figure 3 summarizes some of the different electrolyte systems that have been studied and used to validate the AEM. The first is carbonate-based electrolytes containing methyl acetate (MA) as a cosolvent. MA has been shown to improve charge rate capability in Li-ion cells by improving the ionic conductivity of the electrolyte. This effect has been shown to be almost entirely due to the reduction in viscosity that is achieved when MA is added as a cosolvent.1 Figures 3a and c show measured conductivity and viscosity, respectively, at 20°C as a function of LiPF6 concentration for electrolytes containing varying amounts of MA. Corresponding calculations from the AEM are shown as solid lines. Immediately, an improvement to electrolyte transport can be seen on the addition of MA. For example, at 1.0 m LiPF6 and 20°C, almost a 50% increase in conductivity is seen going from the control (EC:DMC 30:70) to 30% MA (EC:DMC:MA 30:40:30). The AEM calculations shown here are from the most recent version of the program (version 2.18.5). Looking qualitatively at the agreement between experiment and calculation, it appears that the AEM is able to correctly calculate the conductivity and viscosity for different LiPF6 concentrations, and different solvent compositions in the EC:DMC:MA space. This ability may not be surprising because the overall solvent permittivity in the solution does not change dramatically going from 0% MA to 30% MA, so from a macroscopic “bulk permittivity” perspective, the system does not change significantly as DMC is replaced with MA. The EC:DMC x:(100-x) system is slightly more complicated, at least from a computational perspective. Changing the EC content in the solvent mixture significantly changes the overall permittivity of the solution, which has a large impact on the electrolyte’s transport properties. In recent years, so-called “EC-free” electrolytes have gained considerable attention for use in high-voltage Li-ion cells.17-19 In many cases, Li-ion cells containing EC-free electrolytes show equal or improved performance compared to traditional ~30% EC electrolytes in cells cycled to elevated voltages (i.e., > 4.3 V). Figures 3b and d show the ionic conductivity and viscosity, respectively, at 20°C for the solvent system EC:DMC x:(100-x) for EC contents from 0% to 30%. In this case, the shape of the conductivity curve changes significantly as the EC content is adjusted. In DMC, the conductivity is

nonlinear with respect to LiPF6 concentration in the low concentration range (this effect can be seen better in Fig. 4), and regains the typical linear conductivity increase as more EC is added. This nonlinear behavior has been attributed to the formation of contact ion pairs (CIP). Due to the low-permittivity environment in pure DMC, small amounts of LiPF6 do not easily dissociate into their constituent ions. However as more salt is added, the neutral LiPF6 dipoles increase the permittivity of the solution to the extent that dissociation occurs, and the conductivity of the solution increases.20 This feature of low permittivity solutions presents certain computational challenges, at least in the framework of the AEM. Earlier versions of the AEM were not able to complete calculations for LiPF6 in DMC, and had trouble with low-EC systems such as EC:DMC 10:90. This challenge was overcome by a rigorous reevaluation of theories within the AEM for concentration-dependent permittivity and related ion association to include the impact of CIP dipoles on the overall permittivity of the solution. This overall improvement was seen starting with AEM version 2.18.4, and the AEM can now successfully calculate transport properties of low-EC and EC-free electrolytes with good accuracy. To highlight the importance of the interaction between experiment and computation, Fig. 4 shows conductivity as a function of salt concentration for the LiPF6-DMC system. Experimentally measured points are shown as black circles, and calculations from several different versions of the AEM are shown as different line-types. The LiPF6-DMC system is a good model system to use for this discussion because it highlights the three main areas of difficulty for calculating electrolyte properties: (1) solvent systems with low permittivity (ϵDMC ≈ 2), (2) low salt concentration (< 0.5 mol/kg), especially for the above-mentioned low-permittivity systems, and (3) very high salt concentration (> 2.0 mol/kg). It should also be stressed that versions of the AEM before version 2.17.2 could not successfully run calculations for this system. Subsequent versions of the AEM have solved each of these issues in turn. Looking at the difference between experimental and calculated conductivity shown in Fig. 4, accuracy at both the low and high concentration ranges has been greatly improved from version 2.17.2 to 2.18.4. By adding the CIP dipole considerations as well as additional salt-solvent interactions (continued on next page)

Fig. 3. (a) Ionic conductivity and (c) viscosity as a function of LiPF6 (molal) concentration for EC:DMC-based electrolytes containing different amounts of methyl acetate (MA). (b) Ionic conductivity and (d) viscosity as a function of LiPF6 concentration for electrolytes with varying amounts of EC (i.e., different effective solvent permittivity). Measurements were made at 20°C and calculations are for electrolytes at 20°C.

Fig. 4. Measurements of ionic conductivity for LiPF6 in DMC, at 20°C. Calculations from different versions of the AEM are shown in different dashed lines. The bottom panel shows the difference between experimental conductivity and AEM calculations over multiple versions of the program.

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at high concentration, the AEM is now able to successfully describe this particularly difficult system, thus adding to its overall validity.

Diffusivity Calculations in the AEM The AEM framework provides results for species diffusivities over salt concentration and temperature, including values for cation, anion, total salt, ion pairs, triple ions, and solvent. The ionic diffusivity values predicted by the AEM are akin to Maxwell-Stefan diffusivities, wherein they represent the diffusion coefficients of the electrolyte with respect to the thermodynamic driving force. The AEM values are all functions of concentration and temperature-dependent terms, giving high accuracy over wide ranges of conditions. A modified Nernst-Einstein expression is used for the terms involving ions and ion-associated species, while an Einstein-Stokes expression is used for the solvent diffusivity. The total salt diffusivity is obtained through the Nernst method of stoichiometric averaging from the ionic diffusivities: D D salt (1)  Dsalt D Nernst D   D  Also calculated within the suite of diffusivity terms is the apparent salt diffusivity, a term often found in relation to Newman-type transport modeling of electrochemical cells. Within the AEM this term is of the form (as per Nyman et al.):21 CTotal   ln γ   ˆ Dapp. DNernst 1   1  CsaltVsalt  ln m  Csolvent 





(2)

diffusivity and other transport modeling terms. Some literature sources also include the term (1 – t+) in the right-hand side of Eq. (2) in connection to the thermodynamic factor; however, the exact value of (1 – t+) plays a minor role in the calculated value of Dapp. and early approximations (e.g., 0.6) can be used. There has been some inconsistent treatment of Eq. (2) terms in literature, which often results in underestimation of both the activity coefficients and the apparent diffusivity. In short, there are errors introduced when the Debye-Hűckel (DH) theory is used to derive activity coefficients or the thermodynamic factor at salt concentrations higher than 0.1 M. The AEM is not constrained by the DH theory and can predict activity coefficients at very high salt concentrations, typically up to 4–6 molal salt for battery electrolytes and well over 10 molal for aqueous systems. It is asserted that AEM provides accurate values of ionic diffusivities and activity coefficients and hence would yield accurate thermodynamic factors and values for Dapp.; the AEM Dapp. values can show noteworthy differences to those obtained under the weak DH basis. In general, Dapp. will have larger values than DNernst, as is seen in both experimental methods8,21 and the AEM. In some cases, Dapp. > DNernst by an order of magnitude at higher salt concentrations, which is tied mostly to the behavior of the activity coefficient over salt concentration. Figure 5 (a–c) shows a comparison between experimental and AEM-calculated diffusivities. For several different salt/solvent systems, the AEM shows very good agreement to experimentally determined values. Figure 5d shows a comparison of predicted DSalt and Dapp. for the systems given in Fig. 3, where clear advantages are seen by the addition of MA.

Conclusion

where the terms above have their classical meanings. An important consideration is the origins of activity coefficients and the

Much progress has been made in the understanding of electrolytes for Li-ion batteries, both from practical and theoretical perspectives. referenced to the apparent Combinations of additives have been developed that can allow cells to cycle for thousands of cycles and last many, many years with very little capacity loss. The transport properties of electrolyte System: g -BL + LiBF4 o solutions have been mapped at 295 K (22 C) Li+ Diffusivities for PC + LiTFSI Li+ Diﬀusivi-es for γ-BL + LiBF at 295K 4 5x10 3.5x10 out over several parameters, Symbols: Experimental Data (PFG-NMR) including temperature, salt Blue Curves: AEM predictions (a) K. Hayamizu et al., Solid State 3.0x10 (b) Ionics, Vol. 107, pp1-12 (1998). concentration, and solvent 4x10 Data points: from PFG-NMR, Sethurajan et al. (JPCB, 2015) 2.5x10 AEM Predictions composition for new systems These authors refer to their data as of interest: high conductivity 3x10 303 K "room temperature diffusivities" 2.0x10 electrolytes containing low1.5x10 viscosity cosolvents like 2x10 methyl acetate (MA) for use 10 in high-power applications, 293 K 10 5.0x10 and so-called “EC-free” electrolytes for use in high 0 0 voltage (> 4.3 V) Li-ion 0.0 0.5 1.0 1.5 2.0 2.5 3.0 0.0 0.5 1.0 1.5 2.0 2.5 3.0 Salt Conc., Molar cells. Gering’s Advanced LiBF Concentration, Molar Electrolyte Model (AEM), Salt Diffusivities for EC-EMC (3:7, wt) + LiPF6 has proven to be a useful tool 10 EC-DMC (3:7, mass) + LiPF PF6- Diffusivities for PC + LiTFSI in quickly and accurately 7x10 3.5x10 (d) determining the properties of EC-DMC-MA (3:4:3, mass) + LiPF AEM predictions 6x10 electrolyte systems, including (2008), Figpredictions 12 lower curve (c) BlueNyman Curves: AEM 10 3.0x10 for transport properties 298 K Data points: from PFG-NMR, 5x10 303 K 2.5x10 Sethurajan et al. (JPCB, 2015) such as diffusivity that are Dapp These authors refer to their data as 4x10 not trivial measurements. 10 2.0x10 "room temperature diffusivities" Continued collaboration 3x10 1.5x10 The main difference here between between the theoretical NMR and AEM could be the incomplete accounting of anion solvation by NMR. Dsalt and experimental wings of 2x10 10 10 293 K 293 K electrolyte research will 10 5.0x10 validate models such as the AEM for an ever-expanding 00 10 0.0 0.5 1.0 1.5 2.0 2.5 0.0 0.5 1.0 1.5 2.0 2.5 3.03.0 0 1 2 3 4 5 number of systems. SaltConc., Conc.,Molar Molar Salt Salt conc., molal © The Electrochemical Society. Fig. 5. Diffusivity comparison of model predictions to measured data using (a,b) PFG-NMR22,23 and (c) electrochemical DOI: 10.1149/2.F04192if.   ln γ   “thermodynamic factor” 1   ln m   

-6

Diffusivity, cm /s

Li Diffusivity, cm /s

-6

-7

-4

-6 -6

Dsalt or Dapp. , cm2/s

Diffusivity, cm /s 2 Diffusivity, cm /s

-6 -6

-5

-6

-7

-6 -7

-8

techniques.21 Note that plots (a) and (b) are for Li ions while plot (c) is for the total salt. Comparison of predicted total salt and apparent diffusivities are shown in (d) for the systems EC-DMC (3:7, mass) + LiPF6 and EC-DMC-MA (3:4:3) + LiPF6. 52

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Acknowledgments The Dalhousie authors thank NSERC and Tesla Canada for funding this work under the auspices of the Industrial Chairs Program. EL thanks NSERC for Scholarship support. Work performed at INL is under United States Department of Energy contract DE-AC0705ID14517. The AEM software is available for licensing. Please contact Ryan Bills: Ryan.Bills@inl.gov; Office phone +1 (208) 526-1896.

About the Authors Eric R. Logan has a BSc in physics from Mount Allison University and an MSc in physics from Dalhousie University. He is currently completing his PhD in physics at Dalhousie University under the supervision of Jeff Dahn. His research is focused on understanding the properties of electrolytes, studying both bulk transport properties and reactivity in full Li-ion cells. He may be reached at Eric.Logan@dal.ca.

Jeff R. Dahn obtained his BSc from Dalhousie University (1978) and his PhD from the University of British Columbia in 1982. Dahn then worked at NRC (Canada) (1982-1985) and at Moli Energy (1985-1990) before taking up a faculty position at Simon Fraser University in 1990. He returned to Dalhousie in 1996. At Moli, he performed pioneering work on lithium-ion batteries. Dahn was appointed as the NSERC/3M Canada Industrial Research Chair in Materials for Advanced Batteries at Dalhousie University in 1996, a position he held until 2016. In 2016, Dahn began a research partnership with Tesla as the NSERC/Tesla Canada Industrial Research Chair. With over 650 journal publications, his h-index is 123. Dahn’s research has been recognized by numerous awards, including a Governor General’s Innovation Award (2016) and the Gerhard Herzberg Gold Medal in Science and Engineering (2017), Canada’s top science prize. He has been awarded two ECS Battery Division awards. He may be reached at Jeff.Dahn@dal.ca. https://orcid.org/0000-0002-6997-2436

References

https://orcid.org/0000-0002-3102-0843 Kevin L. Gering is a distinguished staff scientist at Idaho National Laboratory. Gering is an established expert in the field of molecular-based electrolyte modeling for electrochemical systems (creator of the Advanced Electrolyte Model, AEM), and has developed novel performance and lifecycle (aging) models for lithium-ion systems covering mechanistic aspects of kinetic limitations and performance loss over battery life (CellSage). He is well qualified to speak on issues of electrolyte transport, characterization, screening, and optimization for lithium-ion systems, wherein particular areas of expertise are battery performance at high rates and low temperatures. Gering has a diverse background in modeling complex systems such as marine methane hydrate occurrence, biological composting, and most recently developing mass transport models for highly dynamic TAP micro-reactors. He has participated in work for U.S. Department of Energy (DOE) battery programs. He actively collaborates with other DOE labs, universities, and the private sector, and is an advocate of domestic intellectual property, having a number of patents issued and pending, with some currently under license. He may be reached at Kevin.Gering@inl.gov. https://orcid.org/0000-0002-2821-4057 Xiaowei Ma received his PhD in chemistry from Florida State University in 2013. His doctoral research focused on the synthesis of rare earth intermetallics and Zintl phases using flux methods, with an emphasis on the characterization of magnetic and transport properties. He received his ME in power machinery engineering from Tongji University in 2007. He received his BSc in chemistry from Tongji University in 2004. At Dalhousie University, Ma worked on advanced electrolytes for lithium-ion batteries which can delay or prevent rollover failure. One of his recent papers on this topic was selected as an Editors’ Choice article in the Journal of The Electrochemical Society. Ma joined the Research Department of E-One Moli Energy Canada on April 1, 2019, as a research scientist. He may be reached at XiaoweiM@molienergy.com.

1. E. R. Logan, et al., J. Electrochem. Soc., 165, A21 (2018). 2. J. Li, et al., J. Electrochem. Soc., 165, A1027 (2018). 3. M. C. Smart, B. V. Ratnakumar, K. B. Chin, and L. D. Whitcanack, J. Electrochem. Soc., 157, A1361 (2010). 4. X. Ma, et al., J. Electrochem. Soc., 164, A3556 (2017). 5. X. Ma, et al., Electrochim. Acta, 270, 215 (2018). 6. M. C. Smart, J. Electrochem. Soc., 146, 3963 (1999). 7. X. Ma, submitted to J. Electrochem. Soc. (2019). 8. L. O. Valo̸en and J. N. Reimers, J. Electrochem. Soc., 152, A882 (2005). 9. A. Ehrl, J. Landesfeind, W. A. Wall, and H. A. Gasteiger, J. Electrochem. Soc., 164, A2716 (2017). 10. A. Ehrl, J. Landesfeind, W. A. Wall, and H. A. Gasteiger, J. Electrochem. Soc., 164, A826 (2017). 11. J. Landesfeind, A. Ehrl, M. Graf, W. A. Wall, and H. A. Gasteiger, J. Electrochem. Soc., 163, A1254 (2016). 12. S. A. Krachkovskiy, J. D. Bazak, S. Fraser, I. C. Halalay, and G. R. Goward, J. Electrochem. Soc., 164, A912 (2017). 13. K. L. Gering, Electrochim. Acta, 51, 3125 (2006). 14. K. L. Gering, Electrochim. Acta, 225, 175 (2017). 15. E. R. Logan, et al., J. Electrochem. Soc., 165, A705 (2018). 16. E. R. Logan, E. M. Tonita, K. L. Gering, and J. R. Dahn, J. Electrochem. Soc., 165, A3350 (2018). 17. J. Xia, R. Petibon, D. Xiong, L. Ma, and J. R. Dahn, J. Power Sources, 328, 124 (2016). 18. L. Ma, et al., J. Electrochem. Soc., 164, A5008 (2017). 19. Y. Yamada, et al., J. Am. Chem. Soc., 136, 5039 (2014). 20. L. Doucey, M. Revault, A. Lautié, A. Chaussé, and R. Messina, Electrochim. Acta, 44, 2371 (1999). 21. A. Nyman, M. Behm, and G. Lindbergh, Electrochim. Acta, 53, 6356 (2008). 22. A. K. Sethurajan, S. A. Krachkovskiy, I. C. Halalay, G. R. Goward, and B. Protas, J. Phys. Chem. B, 119, 12238 (2015). 23. K. Hayamizu, Y. Aihara, S. Arai, and W. S. Price, Solid State Ionics, 107, 1 (1998).

https://orcid.org/0000-0003-1986-6261

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Lithium Metal Polymer Electrolyte Batteries: Opportunities and Challenges by Jijeesh Ravi Nair, Laura Imholt, Gunther Brunklaus, and Martin Winter

he rapid market expansion of powerful electronics, dates back to the 1870s, employing solid cellulosic materials (e.g., stationary (“grid”) storage, and electric vehicles (EVs) sawdust) or soluble thickeners (e.g., starch or agar paste)30,31 to has been made possible by the development of costsolidify the electrolyte. In some Leclanché cells/dry cells,32 simple effective, consumer-safe, and high-performance lithiumcloth wrapping or starch-coated paper was used as a separator.32 A ion batteries (LIBs, Fig. 1A).1-6 Li+ ion storage compounds version of the “Daniell element” designed by Guerin33 contained such as graphite, Li4Ti5O12, and Li storage metals or their precursors a gel electrolyte made from the biopolymer agar and an aqueous such as Si, Sn, SiOx, and SnO2 have been explored as anodes,7,8 electrolyte. whereas lithiated transition metal oxides (e.g., LiNixMnyCozO2) in Today, solid polymer electrolytes (SPEs) as well as lithium ion various compositions and structures (spinel, layer), and lithiumcontaining inorganic ceramic or glassy materials are explored27,34 containing olivine-type materials (e.g., LiFePO4), have been used as replacements for common liquid electrolytes. Despite the as cathodes.9-11 In addition, porous single- or multilayer polyolefinadvantages inorganic ceramic/glassy solid electrolytes exhibit over based separators and ceramics12-coated polymer-based separators liquid electrolytes (Table I), they pose intrinsic challenges such as soaked in liquid electrolytes (linear and cyclic organic carbonates in processability, comparatively high costs, grain boundary resistance, various ratios in combination with the lithium salt (LiPF6))13 separate (partially) low ionic conductivity, insufficient wettability, and the electrode components. In liquid electrolyte cells,14 the charge side reactions with Li metal anodes.27,28 Indeed, the lithium ion transport is based on solvated Li+ ions and aggregates thereof with concentration can be extremely high for some of the ceramic solid anions, where solvation/de-solvation processes and corresponding electrolytes (Table II), which increases the dependence on the electrochemical reactions govern the charge/transfer/at interfaces and abundance of Li as well as suggests high costs of these materials through interphases, i.e., the solid electrolyte interphase15,16 (SEI), (not only with regard to the Li amount).3 SPE-based solid electrolytes and cathode electrolyte interphase (CEI),17-19 during operation. show densities in the range of 1 g cm−3 and also the typical lithium ion Lithium metal anodes clearly afford new opportunities in terms concentration is in the range of 1 mol l−1. of cell design, energy density, and particularly specific capacities [Li SPEs consist of a polymer matrix in which lithium salt is metal (3860 mAh g−1), lithiated graphite, (339 mAh g−1)],20 including dissolved, preferably employing polymer repeating units with options for utilizing non-lithiated cathode materials (e.g., V2O5, S, O2) suitable donor atoms (O, N) that coordinate cations to form polymerand many other (conversion) cathodes,10 hence fostering substantial salt complexes.35 After early reports of PEO-based alkali metal R&D efforts for a renaissance of rechargeable LMBs21 (Fig. 1B). In (continued on next page) fact, like LIBs, LMBs constitute a whole family of cell chemistries featuring various electrolytes and cathode materials. Notably, lithium metal anodes are used in primary and secondary high energy density metal batteries for electronic devices, medical, military, and industrial systems,23-25 although challenges in terms of operational safety, thermal runaway, inhomogeneous Li plating and stripping, and significant reactivity of continuously evolving high surface area lithium metal (HSAL)21 under cell operation are yet to overcome in the rechargeable mode.4 Solid electrolytes are considered as potential beneficiary replacements for the presently utilized liquid-solvent-based organic liquid electrolytes, in principle affording superior mechanical properties due to which the formation of HSAL26,27 deposits could be suppressed. Ionic conduction in solids was discovered by Faraday in the 1830s.28,29 “Solidification” of Leclanché cells by Carl Gassner Fig. 1. A) Schematic illustration including various exemplary components of a lithium-ion cell, B) a lithium metal cell, to improve portability and where lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt dissolved in PEO is used as SPE, showing exemplary electrolyte leakage resistance cathode materials, and C) requirements on an ideal electrolyte system, highlighting specific requisites of SPEs; for abbreviations refer to Table I.

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salt mixtures in 1971,36,37 various systems have been explored as polymer electrolytes.38 PEO-based SPEs often exhibit insufficient ionic conductivity due to a larger fraction of contact ion pairs, “ion aggregates”39,40 or extensive crystalline domains. Nevertheless, these electrolytes demonstrated ionic conductivity values > 0.1 mS cm−1 at 70°C. LiTFSI is widely applied as the salt in polyether-based or other polymer matrices, because the TFSI anion is a highly chargedelocalized molecule with low lattice energy, so it readily acts as a plasticizer to prevent polymer chain recrystallization.41 Unlike in liquid electrolytes, solid electrolytes could serve as both separator and Li+ ion conductor,42 so that SPEs should ideally possess sufficient mechanical stability and quasi-separator properties.43 The mechanical properties are particularly relevant for LMBs where controlled lithium plating is vital for function. The features of ideal electrolytes are reported in Fig. 1C. In addition, necessary components, advantages, and disadvantages of major electrolyte classes (liquid, polymer, and ceramic) are summarized in Table I. The molecular details of ion conduction mechanisms are different for various solid electrolytes and are not always fully understood, but frequently reported mechanisms are portrayed in Fig. 2A and B. For polyether-based SPEs, the ionic conduction is strongly related to either main chain segmental motion above the melting point (Tm) or inter- and intra-chain Li+ ion hopping at low temperatures or within crystalline phases44 (Fig. 2A).45 In case of inorganic ceramic electrolytes, Li+ ions are migrating/hopping among vacancies as well as interstitial sites (Fig. 2B), eventually requiring higher activation energies than the segmental motions or translational mobility of solvated ions. However, the concept that charge transport via ion hopping occurs in crystalline polymer electrolytes was introduced in 1999.44,46 In 2011, Bolloré (Blue Solutions) commercialized lithium metal polymer batteries to power their electric cars (Bluecar), which were equipped with a battery pack of 30 kWh, providing driving ranges of up to 250 km (www.bluecar.fr). Very recently, there have been announcements of SPEs (https://ionicmaterials.com) with ionic

conductivities > 1 mS cm−1 at 20°C, rendering practical applications of such materials in batteries for long-range EVs highly likely in the near future. Despite benefits related to operational safety, flexibility, more favorable fabrication processes, and established Li metal compatibility, LMBs with SPE currently face notable challenges such as insufficient room temperature ionic conductivities and a delicate balance between conflicting demands of mechanical strength, ionic conductivity, and wide operational potential window for high-voltage applications. Hence, current research activities are intensively focused on overcoming these challenges for the next generation of SPE-based LMBs.

Solid Polymer Electrolytes, Electrode/Electrolyte Interfaces, and Their Interphases Polymers are very versatile and accordingly a large variety of polymer architectures have been explored as SPE host matrices, including homopolymers (linear chain) and copolymers (linear, branched or hyperbranched, and crosslinked)48 (Fig. 3). Copolymers may be sorted into several subclasses. However, for simplicity, the copolymers are classified as random, alternate, block, or graft copolymers. In particular, homopolymers49,50 including PEO, PMMA, PVC, PAN, PVdF,51 or copolymers such as PVdF-HFP,52 PEOPMMA, PEO-PS, have been prepared and characterized with respect to ionic conductivity and electrochemical stability (Table III).53 Despite the fact that a large family of materials was explored in the last 45 years, a systematic organization of materials is rather challenging due to the multidisciplinary nature of the energy storage research field.54 In this article, polymer electrolytes are simply classified as dry polymer electrolytes and gel polymer electrolytes (GPEs)42,55 depending on the presence or absence of a liquid phase (Fig. 4). Dry polymer electrolytes are truly solid in nature, and do not contain plasticizers or liquid counterparts, whereas GPEs are comprised of many components, including liquids.

Table I. Comparison of major classes of electrolytes employed in Li-based batteries highlighting exemplary electrolyte components, as well as an average estimation of advantages and disadvantages.

Organic solvent liquid electrolyte

Polymer solid electrolyte

Inorganic ceramic solid electrolyte

Components Solvent Linear carbonates, LCs: Dimethyl carbonate, DMC; Diethyl carbonate, DEC; Ethyl methyl carbonate, EMC. Cyclic carbonates Ethylene carbonate, EC; Propylene carbonate, PC. Salt Lithium hexafluorophosphate, LiPF6; Lithium bis(fluorosulfonyl)imide, LiFSI. Additive Vinylene carbonate, VC; Fluoroethylene carbonate, FEC.

Polymer matrix Poly(ethylene oxide), PEO; Poly(methyl methacrylate), PMMA; Polyacrylonitrile, PAN; Poly(vinylidene difluoride), PVdF. Salt Lithium bis(oxalatoborate), LiBOB; Lithium bis(fluorosulfonyl)imide, LiFSI; Lithium bis(trifluoromethanesulphonyl)imide, LiTFSI.

Sulfide, Thiophosphate Li2P2S6, Li2Ga2GeS6; thio-LISICON: Li10GeP2S12; Oxide Perovskite: Li3.3La0.56TiO3, LLTO; Garnet: Li7La3Zr2O12, LLZO; LISICON-family: Li14ZnGe4O16. Phosphate NASICON family22: Li1.3Al0.3Ge1.7(PO4)3, LAGP; Li1.3Al0.3Ti1.7(PO4)3, LATP; LiPON: Li2P5O6N5.

Advantages High ionic conductivity; Low costs; High active material utilization; Good ion transport and reaction kinetics; Established manufacturing and processing.

Safety; Flexibility; Physical and chemical stability; Leakage free; Thin cell processing; Thermal stability.

Safety; Thermal stability; Good physical and chemical stability; Leakage free; Thin cell processing; High Li+ ion transference number.

(Present) Disadvantages Electrolyte leakage; Safety hazards; Limited physical and chemical stability; Electrolyte refilling and formation are necessary for battery assembly.

Low ionic conductivity at room temperature; In part low ion diffusion properties and kinetics; Non-conformal interface with electrodes.

In part low ionic conductivity; Grain boundary resistance; Activation energy for ion mobility; Rigid structure; Nonconformal interface with electrodes; In part high-temperature processing.

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Table II. Comparison of lithium concentration (mol L-1) in organic liquid electrolyte, and P(EO)20LiTFSI SPE against commonly used inorganic ceramic solid electrolytes.

Name

Formula

Li concentration, mol L−1

Table III. List of polymer matrices investigated as SPE in lithium metal batteries with their important physical properties, repeating units and transport number at 60°C.34, 35, 41, 42, 55, 65, 67

Polymer host

Repeating unit

Tg / °C

Tm / °C

tLi+

LP57

1M LiPF6 in EC:EMC (3:7)

1.0

Poly(ethylene oxide)

C2H4O

−67

0.10 - 0.20

PEO membrane

P(EO)20LiTFSI

1.1

Polyacrylonitrile

C3H3N

125

319

0.40 - 0.60

LLTO

Li3.3La0.56TiO3

81.3

LATP

Li1.3Al0.3Ti1.7(PO4)3

10.0

Poly(vinylidene difluoride)

C2H2F2

-40

171

−

LISICON

Li14ZnGe4O16

66.7

Polydimethylsiloxane

SiOC2H6

-125

-40

−

Polyphosphazenes

NPRR′

−

0.23 - 0.38

Poly(vinyl alcohol)

C2H4O

200

−

C4H6O2

-15

0.60 - 0.80

C2H5N

-40

0.50 - 0.60

LLZO

Li7La3Zr2O12

41.3

Agyrodite

Li6PS5Br

40.1

Li7P3S11

28.0

LGPS

Li10GeP2S12

34.7

Poly(trimethylene carbonate)

Li2S-P2S5

Li2P2S6

14.9

Poly(ethylene imine)

Briefly, GPEs are sorted into “polymer in solvent,” “solvent in polymer,” and liquid crystal polymer electrolyte systems. In “polymer in solvent” systems, the major role of the polymer is to jellify (in situ) the liquids to avoid leakage, thereby affording reduced cell housing thickness, as commercially introduced by SANYO.56,57 The “solvent in polymer” GPEs are considered as plasticized polymer electrolytes, where the polymer matrix influences the ion conduction process and enhances the overall safety, flexibility, mechanical integrity, and processability.58 In particular, cyclic carbonates, glymes, and room temperature ionic liquids59 have been used as plasticizers that may decrease viscosity and modulus of polymer electrolytes, while improving ionic conductivities, though at expense of mechanical stability.42 In cases where plastic crystals60 are used as additives, the GPEs are called liquid crystal polymer electrolytes61-63 or ionic plastic crystals.64 GPEs afford reasonably high ionic conductivities, good interfacial properties, and acceptable electrochemical stability depending on the auxiliary solvent(s), even + if the dimensional stability and operational safety still Fig. 2. Schematic presentation of predominant Li ion transport mechanisms in A) ether-based polymer solid electrolyte (modified from Ref. 45 and 95), and B) inorganic ceramic solid electrolyte constitute remaining challenges to overcome. in perovskite type Li Sr7/16Hf1/4Ta3/4O3 (from Ref. 47; reproduced with permission from the American Dry polymer electrolytes are classified into Chemical Society © 3/8 2016). polymer composite electrolytes (PCEs),66 solid polymer electrolytes, and crystalline polymer electrolytes. Most research efforts have been focused on the reduction of polymer crystallinity by plasticization, filler addition, or crosslinking, in order to promote ion transport either due to increased polymer chain segmental motions or hindered reorganization of polymer chains. Inert fillers such as β-alumina, γ-LiAlO2, and zeolite were considered as “insoluble phases” of PCEs to strengthen mechanical integrity, interfacial adhesion, electrochemical stability, and ion transport properties based on increased fraction of amorphous phases.67,68 PCEs can be mixed with other Li+ ion conducting inorganic ceramic particles, and such systems are included in the classification.69,70 Ceramic materials such as Li7La3Zr2O12 (LLZO),71 Li1.3Al0.3Ti1.7(PO4)3 (LATP),72 have been blended with different polymer matrices but increased grain boundary resistances and nonhomogeneous particle size distributions remain major challenges to address in future work. Notably, systems such as crosslinked polymer electrolytes, hybrid electrolytes, or reinforced polymer electrolytes broadly reflect properties of the above-mentioned classes, making their assignment to a particular category difficult. Fig. 3. Common polymer chain architectures (modified from Ref. 48) employed as SPE (continued on next page)

component in LMBs.

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A special class of polymer electrolytes comprises singleion conductors (SICs) where anions are covalently linked to the polymer repeating units and Li+ ions are the only mobile species.73 SICs can be prepared as dry polymer electrolytes, GPEs, or another variety. Unlike liquid electrolytes, these materials do not yield salt concentration gradients (polarization) at higher discharge

Fig. 4. Simplified classification of commonly investigated polymer electrolyte systems.

rates74,75 and feature values of 0.8 ≤ t Li ≤ 1,74 even though the ionic conductivity (10−8 – 10−7 S cm−1) is often low at 25°C. Notably, the strategies for anion immobilization include anion receptors, which represent electron pair acceptors (Lewis acids) while the anions act as electron pair donors (Lewis base). Neutral organic boron compounds (Fig. 5A)76 are known as excellent electron acceptors, thus forming a representative class of anion receptors. In addition, covalent linking of the anions to a polymer backbone (Fig. 5B)77 or side chain (pendent chain, Fig. 5C) is feasible, rendering immobilized anions constituents of the macromolecule repeating units.78 Polymer chains bearing anions may be also anchored to inorganic nanoparticles (SiO2 or TiO2, Fig. 5D), affording functionalized (grafted or co-grafted) inorganic particle anions,79 while grafting of anions onto organic molecules such as rotaxanes has also been demonstrated (Fig. 5E).80,81 A technical revolution based on modern LMBs will be only feasible if the electrode/electrolyte interphases are appropriately engineered. More so than graphite-based LIBs, LMBs suffer from constantly evolving anodes, which deform during charge/discharge cycles, and it is difficult to keep conformity with an SPE membrane. To uniformly deposit Li metal at the anode, the corresponding morphology has to be optimized to achieve high Coulombic efficiency, long cycle life, and avoidance of HSAL formation. The scenario similarly affects cathodes, where intimate contact between the polymer electrolyte and the electrode should be established needs adapted processing techniques. In addition to interfaces, interphases like SEI and CEI need to be tailored for optimum LMBs. Designing an SEI layer with requisite characteristics is rather challenging, and the approaches adopted so far include: (i) SEI formation from specific electrolyte components, e.g. additives,82,83 and (ii) tailor-made artificial SEI layers.84-86 Although the first approach is commercially established, the second case is still in the R&D stage. An artificial SEI layer can be prepared in a controlled manner and may be tailor-made to match both the used electrode and the electrolyte system. Organic (polymer) and inorganic layers have been widely employed.87,88 A transformation

Fig. 5. Different single-ion conductors are sequenced depending on the nature and position of the immobilized anion: A) Lewis acid receptor (modified from Ref. 76), B) polymer backbone (modified from Ref. 77), C) pendent polymer side chain (from Ref. 78; reproduced with permission from the American Chemical Society © 2016), D) grafted inorganic particle (MOx: with M = Si, Ti, etc., modified from Ref. 79), and E) functionalized organic molecules (modified from Ref. 76). 58

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Fig. 6. Interface and interphase characteristics of SPEs: A) an ex situ prepared SPE is sandwiched between the electrodes, B) an in situ prepared conformal SPE coating forms close contact with the electrode, C) multilayer cell production using tailor-made components, and D) multilayer cell design. (*single or multicomponent protection layer)

from the graphite-based anode in liquid electrolytes to lithium metalbased solid state systems89 brings in extra challenges, including the design of an ideal SEI layer, which could resist HSAL deposition or even favorably control the deposition morphology. For better compatibility with the SPE, the lithium surface can be modified by suitable protective (artificial SEI) layers to reduce/avoid the impact of impurities and native layers on the pristine lithium surface,90 which may strongly affect the characteristics of lithium deposition from the SPE.90 Even though SEI formation using an electrolyte additive is for the first cycles of the Li anode comparatively successful to control dendrite growth,91 a better long-term solution may be obtained from artificial multicomponent or multilayer protective films and tailormade engineering approaches. CEI forming electrolyte additives such as FEC, MgTFSI,17,18,92 ceramic particles, or phosphates may reduce cell degradation; nevertheless, long-term stability has to be improved. Hence, distinct strategies have been proposed for the preparation of tailor-made artificial CEI layers, e.g., based on Atomic Layer Deposition (ALD) or sputtering. Furthermore, AlF3, Al2O3, or silica were successfully deposited, whereas the coating of electrode particles with inorganic particles constitutes another approach, thereby allowing for reduced production costs. Unlike in LIBs, full utilization of active materials while retaining electronic and ionic conduction throughout the whole charge/ discharge processes is a challenge in LMBs. Active materials utilization can be increased by modified processing techniques where the electrolyte precursors are either directly (ex situ) deposited93,94 on the electrode followed by a polymerization process or simply polymerized inside the cell (in situ), thus liquid-like electrolyte components form intimate contact with the electrode surface. In the case of ex situ prepared membranes, the sandwiching of polymer electrolytes between electrodes might not deliver the required interfacial conformity; a comparison of approaches is illustrated in Fig. 6A and B. Opportunities may also arise from applying multilayer cell designs (Fig. 6C and D), where tailor-made interphase layers, SPEs, and composite electrode layers are judiciously engineered to outperform the present devices, thereby paving the way for commercialization of high performance and safe solid state LMBs.

Conclusion and Future Perspectives The next generation of rechargeable, HSAL-free LMBs targeted at high performance and safety, low costs, and environmental benignity requires significant steps towards the rational design of materials and engineering of interfaces and interphases. From an SPE perspective, the polymer matrices investigated until now are thermoplastics and very often commercially available polymers or their precursors, which are blended with different salts and solvents to produce respective chemistries. Recent years have witnessed substantial progress in materials and process analyses, polymer matrix engineering, the discovery of suitable salts, monomers, and binders with new properties essential for achieving the anticipated targets. Material interactions at the molecular scale, interface and interphase changes, and aging behavior should be thoroughly investigated to understand the fundamental processes, e.g., by applying operando and in situ analysis techniques, and undeniably, new analysis methodologies must be devised for realizing efficient LMBs. Advanced synthesis and processing techniques will play a crucial role in achieving relevant goals. For SPEs, in situ preparation procedures that require minimal changes at the available industrial fabrication lines compared to LIB cell processing should be adopted, in particular to enhance electronic and ionic conductivities of the composite electrodes (including SPEs) at the microscopic level. The development of interface and interphase engineering techniques will be crucial to produce germane artificial SEI and CEI layers that are designed for more durable, costeffective, sustainable, and industrially upscalable cell manufacturing. Depending on the application, there are multiple sophisticated design solutions, hence the research vista is open for multifaceted approaches as well as multicomponent and multilayer systems where SPEs and/or GPEs (in combination with ceramic/glassy electrolyte components or without) will be indispensable for realization of the LMB cells of tomorrow. ÂŠ The Electrochemical Society. DOI: 10.1149/2.F05192if.

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Acknowledgment Support provided by the German Federal Ministry of Education and Research within the (BMBF) project “FestBatt” (13XP0175A) is gratefully acknowledged.

Battery Research, and present speaker of the National Project Alliance Batterie2020. Currently, he holds several president and chairman positions in scientific societies and is the recipient of 50 awards and recognitions. He may be reached at m.winter@fz-juelich.de and Martin.Winter@uni-muenster.de. https://orcid.org/0000-0003-4176-5811

About the Authors

References

Jijeesh Ravi Nair earned his PhD, a European Doctorate degree (2010), in materials science and technology from Politecnico di Torino, Italy. Currently, he is a research associate at the Helmholtz-Institute Münster (HI MS) Ionics in Energy Storage, a division of Forschungszentrum Jülich. His research focuses on the development of crosslinked solid polymer electrolytes for lithium-based batteries. He has published 68 scientific articles in peer-reviewed international journals and coauthored three book chapters. He has been awarded one international patent, and two of his other patent applications are under evaluation. He may be reached at j.nair@fz-juelich.de.

1. M. Li, J. Lu, Z. Chen, and K. Amine, Adv. Mater., e1800561 (2018). 2. A. Manthiram, ACS Cent. Sci., 3(10), 1063 (2017). 3. R. Schmuch, R. Wagner, G. Hörpel, T. Placke, and M. Winter, Nat. Energy, 3(4), 267 (2018). 4. T. Placke, R. Kloepsch, S. Dühnen, and M. Winter, J. Solid State Electrochem., 21(7), 1939 (2017). 5. R. Wagner, N. Preschitschek, S. Passerini, J. Leker, and M. Winter, J. Appl. Electrochem., 43(5), 496 (2013). 6. M. Winter, B. Barnett, and K. Xu, Chem. Rev., 118(23), 11433 (2018). 7. M. N. Obrovac and V. L. Chevrier, Chem. Rev., 114(23), 11444 (2014). 8. M. Winter, J. O. Besenhard, J. H. Albering, J. Yang, and M. Wachtler, Prog. Batteries Battery Mater., 17, 208 (1998). 9. J. Kasnatscheew, M. Evertz, R. Kloepsch, B. Streipert, R. Wagner, I. Cekic Laskovic, and M. Winter, Energy Technol., 5(9), 1670 (2017). 10. F. Wu and G. Yushin, Energy Environ. Sci., 10(2), 435 (2017). 11. M. S. Whittingham, Chem. Rev., 104(10), 4271 (2004). 12. H. Lee, M. Yanilmaz, O. Toprakci, K. Fu, and X. Zhang, Energy Environ. Sci., 7(12), 3857 (2014). 13. I. Cekic-Laskovic, N. von Aspern, L. Imholt, S. Kaymaksiz, K. Oldiges, B. R. Rad, and M. Winter, Top. Curr. Chem., 375(2), 37 (2017). 14. K. Xu, Chem. Rev., 114(23), 11503 (2014). 15. E. Peled, J. Electrochem. Soc., 126(12), 2047 (1979). 16. M. Winter, Z. Phys. Chem., 223(10-11), 1395 (2009). 17. D. R. Gallus, R. Wagner, S. Wiemers-Meyer, M. Winter, and I. Cekic-Laskovic, Electrochim. Acta, 184, 410 (2015). 18. Y. Qian, P. Niehoff, M. Börner, M. Grützke, X. Mönnighoff, P. Behrends, S. Nowak, M. Winter, and F. M. Schappacher, J. Power Sources, 329, 31 (2016). 19. W. Li, A. Dolocan, P. Oh, H. Celio, S. Park, J. Cho, and A. Manthiram, Nat. Commun., 8, 14589 EP - (2017). 20. M. Winter and J. O. Besenhard, in Handbook of Battery Materials, C. Daniel, Editor, p. 433, Wiley-VCH, Weinheim, (2011). 21. M.-H. Ryou, Y. M. Lee, Y. Lee, M. Winter, and P. Bieker, Adv. Funct. Mater., 25(6), 834 (2015). 22. Y. Meesala, A. Jena, H. Chang, and R.-S. Liu, ACS Energy Lett., 2(12), 2734 (2017). 23. T. Placke and M. Winter, Z Herz- Thorax- Gefäßchir, 29(2), 139 (2015). 24. D. Lisbona and T. Snee, Process Saf. Environ. Prot., 89(6), 434 (2011). 25. J. B. Goodenough, Nat. Electronics, 1(3), 204 (2018). 26. R. van Eldik and W. Macyk, Materials for Sustainable Energy, San Diego, Elsevier Science & Technology (2018). 27. J. W. Fergus, J. Power Sources, 195(15), 4554 (2010). 28. A. Manthiram, X. Yu, and S. Wang, Nat. Rev. Mat., 2(4), 16103 (2017). 29. M. Faraday, Phil. Trans. R. Soc. Lon, 123, 23 (1833). 30. C. J. Coleman, Galvanic Battery (495306) (1893). 31. W. L. F. Hellesen, Dry Battery (439151) (1890). 32. C. Hambuechen, Dry Cell and Its Method of Manufacture (1292764) (1919). 33. P. Benjamin, The Voltaic Cell: Its Construction and Its Capacity, J. Wiley & Sons, New York (1893).

https://orcid.org/0000-0002-1670-7647 Laura Imholt received her bachelor’s and master’s degrees in chemistry from the University of Münster, Germany, in 2013 and 2015, respectively. She earned her PhD in physical chemistry in 2019 from the University of Münster under the guidance of Prof. Martin Winter. Her main research interests are the synthesis and structure-reactivity correlations of polymer electrolytes for applications in lithium metal and lithium-ion batteries. Since March 2019, she has worked as a research scientist at the Fraunhofer Institute for Manufacturing Technology and Advanced Materials (IFAM). She may be reached at l.imholt@fz-juelich.de and laura.imholt@ifam. fraunhofer.de. https://orcid.org/0000-0001-6149-5586 Gunther Brunklaus is currently a group leader at the Helmholtz-Institute Münster (HI MS) Ionics in Energy Storage, a division of Forschungszentrum Jülich. His work focuses on the design of functional materials including the preparation of polymer electrolytes and molecular solids. He is also engaged in the development of solid state NMR and MRI-based methods, particularly emphasizing concepts for in situ applications. He received his doctorate from the University of Münster, Germany, and his habilitation from the University of Mainz, Germany. He has published over 82 technical articles and has been awarded two patents. He may be reached at g.brunklaus@fz-juelich.de. https://orcid.org/0000-0003-0030-1383 Martin Winter currently holds a professorship for materials science, energy, and electrochemistry at the Institute of Physical Chemistry at Muenster University, Germany. The full professorship developed from an endowed full professorship funded by the companies Volkswagen, Evonik Industries, and Chemetall (today: Albemarle). He is director of the MEET Battery Research Center at Muenster University and of the Helmholtz-Institute Muenster (HI MS) Ionics in Energy Storage, a branch of Forschungszentrum Jülich. Winter is the spokesperson of German 60

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34. N. J. Dudney, in Lithium Batteries: Science and Technology, Gholam-Abbas Nazri, Gianfranco Pistoia, G. Nazri, and G. Pistoia, Editors, p. 624, Springer, New York (2009). 35. F. M. Gray, Solid Polymer Electrolytes: Fundamentals and Technological Applications, Wiley-VCH, New York (1991). 36. D. E. Fenton, J. M. Parker, and P. V. Wright, Polymer, 14(11), 589 (1973). 37. D. W. Murphy, J. Broadhead, and B. C. H. Steele, Materials for Advanced Batteries, Springer US, Boston, MA (1980). 38. M. Armand, Solid State Ionics, 69(3-4), 309 (1994). 39. M. Smith, Solid State Ionics, 140(3-4), 345 (2001). 40. L. Yue, J. Ma, J. Zhang, J. Zhao, S. Dong, Z. Liu, G. Cui, and L. Chen, Energy Storage Mater., 5, 139 (2016). 41. J. Mindemark, M. J. Lacey, T. Bowden, and D. Brandell, Prog. Polym. Sci., 81, 114 (2018). 42. A. M. Stephan, Eur. Polm. J., 42(1), 21 (2006). 43. S. S. Zhang, J. Power Sources, 164(1), 351 (2007). 44. E. Staunton, Y. G. Andreev, and P. G. Bruce, J. Am. Chem. Soc., 127(35), 12176 (2005). 45. Z. Xue, D. He, and X. Xie, J. Mater. Chem. A, 3(38), 19218 (2015). 46. S. H. Chung, Y. Wang, S. G. Greenbaum, D. Golodnitsky, and E. Peled, Electrochem. Solid-State Lett., 2(11), 553 (1999). 47. B. Huang, B. Xu, Y. Li, W. Zhou, Y. You, S. Zhong, C.-A. Wang, and J. B. Goodenough, ACS Appl. Mat. Interfaces, 8(23), 14552 (2016). 48. J. Huang and S. R. Turner, Polymer, 116, 572 (2017). 49. D. Devaux, D. Glé, T. N. T. Phan, D. Gigmes, E. Giroud, M. Deschamps, R. Denoyel, and R. Bouchet, Chem. Mater., 27(13), 4682 (2015). 50. A. Pelz, T. S. Dörr, P. Zhang, P. W. de Oliveira, M. Winter, H.-D. Wiemhöfer, and T. Kraus, Chem. Mater., 31(1), 277 (2019). 51. T. He, Z. Zhou, W. Xu, F. Ren, H. Ma, and J. Wang, Polymer, 50(13), 3031 (2009). 52. W. Zhai, H.-j. Zhu, L. Wang, X.-m. Liu, and H. Yang, Electrochim. Acta, 133, 623 (2014). 53. P. Isken, M. Winter, S. Passerini, and A. Lex-Balducci, J. Power Sources, 225, 157 (2013). 54. V. Di Noto, S. Lavina, G. A. Giffin, E. Negro, and B. Scrosati, Electrochim. Acta, 57, 4 (2011). 55. L. Long, S. Wang, M. Xiao, and Y. Meng, J. Mater. Chem. A, 4(26), 10038 (2016). 56. R. J. Brodd, Batteries for Sustainability: Selected Entries from the Encyclopedia of Sustainability Science and Technology, Springer New York; Imprint; Springer, New York (2013). 57. G. Pistoia, Batteries for Portable Devices, Elsevier (2005). 58. J. Y. Song, Y. Y. Wang, and C. C. Wan, J. Power Sources, 77, 183 (1999). 59. B. Rupp, M. Schmuck, A. Balducci, M. Winter, and W. Kern, Eur. Polm. J., 44(9), 2986 (2008). 60. H.-J. Ha, Y. H. Kwon, J. Y. Kim, and S.-Y. Lee, Electrochim. Acta, 57, 40 (2011). 61. S. Wang, X. Liu, A. Wang, Z. Wang, J. Chen, Q. Zeng, X. Wang, and L. Zhang, Polym. Chem., 9(37), 4674 (2018). 62. J. Sakuda, E. Hosono, M. Yoshio, T. Ichikawa, T. Matsumoto, H. Ohno, H. Zhou, and T. Kato, Adv. Funct. Mater., 25(8), 1206 (2015). 63. K. A. Bogdanowicz, P. Gancarz, M. Filapek, D. Pociecha, M. Marzec, I. Chojnacka, and A. Iwan, Dalton Trans., 47(44), 15714 (2018). 64. J. M. Pringle, P. C. Howlett, D. R. MacFarlane, and M. Forsyth, J. Mater. Chem., 20(11), 2056 (2010). 65. N. Kaskhedikar, J. Paulsdorf, M. Burjanadze, Y. Karatas, B. Roling, and H.-D. Wiemhofer, Solid State Ionics, 177(26-32), 2699 (2006).

66. W. Wang, E. Yi, A. J. Fici, R. M. Laine, and J. Kieffer, J. Phys. Chem. C, 121(5), 2563 (2017). 67. A. Manuel Stephan and K. S. Nahm, Polymer, 47(16), 5952 (2006). 68. E. Quartarone, Solid State Ionics, 110(1-2), 1 (1998). 69. Z. Li, H-M. Huang, J-K. Zhu, J-F. Wu, H. Yang, and L. Wei, ACS Appl. Mat. Interfaces (11), 784 (2019). 70. S. Bonizzoni, C. Ferrara, V. Berbenni, U. Anselmi-Tamburini, P. Mustarelli, and C. Tealdi, Phys. Chem. Chem. Phys., 21, 6142 (2019). 71. S. Yu, R. D. Schmidt, R. Garcia-Mendez, E. Herbert, N. J. Dudney, J. B. Wolfenstine, J. Sakamoto, and D. J. Siegel, Chem. Mater., 28(1), 197 (2016). 72. M. Monchak, T. Hupfer, A. Senyshyn, H. Boysen, D. Chernyshov, T. Hansen, K. G. Schell, E. C. Bucharsky, M. J. Hoffmann, and H. Ehrenberg, Inorg. Chem., 55(6), 2941 (2016). 73. K. Murata, S. Izuchi, and Y. Yoshihisa, Electrochim. Acta, 45(89), 1501 (2000). 74. M. Doyle, T. F. Fuller, and J. Newman, Electrochim. Acta, 39(13), 2073 (1994). 75. Y. Ma, J. Electrochem. Soc., 142(6), 1859 (1995). 76. H. Zhang, C. Li, M. Piszcz, E. Coya, T. Rojo, L. M. RodriguezMartinez, M. Armand, and Z. Zhou, Chem. Soc. Rev., 46(3), 797 (2017). 77. K. Borzutzki, J. Thienenkamp, M. Diehl, M. Winter, and G. Brunklaus, J. Mater. Chem. A, 7(1), 188 (2019). 78. L. Porcarelli, A. S. Shaplov, M. Salsamendi, J. R. Nair, Y. S. Vygodskii, D. Mecerreyes, and C. Gerbaldi, ACS Appl. Mat. Interfaces, 8(16), 10350 (2016). 79. N. Lago, O. Garcia-Calvo, J. M. Lopez del Amo, T. Rojo, and M. Armand, ChemSusChem, 8(18), 3039 (2015). 80. L. Imholt, D. Dong, D. Bedrov, I. Cekic-Laskovic, M. Winter, and G. Brunklaus, ACS Macro Lett., 7(7), 881 (2018). 81. L. Imholt, T. S. Dörr, P. Zhang, L. Ibing, I. Cekic-Laskovic, M. Winter, and G. Brunklaus, J. Power Sources, 409, 148 (2019). 82. C. Korepp, H. J. Santner, T. Fujii, M. Ue, J. O. Besenhard, K.-C. Möller, and M. Winter, J. Power Sources, 158(1), 578 (2006). 83. A. M. Haregewoin, A. S. Wotango, and B.-J. Hwang, Energy Environ. Sci., 9(6), 1955 (2016). 84. A. Wang, S. Kadam, H. Li, S. Shi, and Y. Qi, npj Comput. Mater., 4(1), 15 (2018). 85. L. Zhang, K. Zhang, Z. Shi, and S. Zhang, Langmuir, 33(42), 11164 (2017). 86. Q. Qian, Y. Yang, and H. Shao, Phys. Chem. Chem. Phys., 19(42), 28772 (2017). 87. Y. Nan, S. Li, B. Li, and S. Yang, Nanoscale, 11(5), 2194 (2019). 88. N.-L. Wu, Y.-T. Weng, F.-S. Li, N.-H. Yang, C.-L. Kuo, and D.S. Li, Prog. Natur. Sci.: Mater. Int., 25(6), 563 (2015). 89. S. Li, M. Jiang, Y. Xie, H. Xu, J. Jia, and J. Li, Adv. Mater., 30(17), e1706375 (2018). 90. J. Becking, A. Gröbmeyer, M. Kolek, U. Rodehorst, S. Schulze, M. Winter, P. Bieker, and M. C. Stan, Adv. Mater. Interfaces, 4(16), 1700166 (2017). 91. J. Heine, P. Hilbig, X. Qi, P. Niehoff, M. Winter, and P. Bieker, J. Electrochem. Soc., 162(6), A1094 (2015). 92. R. Wagner, B. Streipert, V. Kraft, A. Reyes Jiménez, S. Röser, J. Kasnatscheew, D. R. Gallus, M. Börner, C. Mayer, H. F. Arlinghaus, M. Korth, M. Amereller, I. Cekic-Laskovic, and M. Winter, Adv. Mater. Interfaces, 3(15), 1600096 (2016). 93. C. Gerbaldi, M. Destro, J. R. Nair, S. Ferrari, I. Quinzeni, and E. Quartarone, Nano Energy, 2(6), 1279 (2013). 94. J. R. Nair, L. Porcarelli, F. Bella, and C. Gerbaldi, ACS Appl. Mat. Interfaces, 7(23), 12961 (2015). 95. W. H. Meyer, Adv. Mater., 10(6), 439 (1998).

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Controlling Ionic Transport through the PEO-LiTFSI/LLZTO Interface by Arushi Gupta and Jeff Sakamoto

he interest in increasing battery energy density has created (~1 mS/cm) while the incorporation of PEO/LiTFSI will facilitate the impetus to supplant carbon-based anodes in Li-ion membrane fabrication. batteries with metallic Li.1 However, side reactions and While there have been studies of the interface between LLTO and morphological instability which occur during cycling Li in PEO-LiCF3SO3,27 polymer electrolyte and glass,28 and LLZO and liquid electrolyte has impeded progress to this end.2-4 One liquid electrolyte,29 there have been relatively few investigations of approach to enable this transition is to physically stabilize Li using the PEO-LiTFSI/LLZO interface. Langer et al. was the first to study a solid electrolyte.5 The most promising candidates actively being this interface30 and determined the resistance was relatively high. investigated for solid electrolytes are sulfides,6,7 ceramic oxides,8-10 However, their study focused on the effects of surface irregularities and polymers.11,12 rather than the origins of high Rinterface. The objective of this work LLZO, a ceramic oxide consisting of the garnet crystal structure, was to 1) understand the underpinning mechanisms that control ionic has shown great potential as a solid electrolyte owing to its high transport of the PEO-LiTFSI/LLZO interface and 2) integrate the ionic conductivity (1 mS/cm) and stability against lithium; however, fundamental understanding of interface transport to enable composites difficulty in fabricating LLZO membranes has slowed maturation.13 (continued on next page) On the other hand, PEO/lithium bis(triflouromethanesulfonyl)imide (PEO-LiTFSI)14-18 is relatively easy to process, but it has an inherently Table I. The ionic conductivity of CPE with varying LLZO fractions; low ionic conductivity at room temperature. Thus, there is interest in molecular weights of the PEO were excluded since they were in the range combining the complementary properties of the two electrolytes in where ionic conductivity of PEO was independent of molecular weight.23 the form of LLZO-PEO composites (CPE). In the CPE, LLZO with Temperature Conductivity higher ionic conductivity, acts as the primary conductive phase and Solid Electrolyte (°C) (mS/cm) Reference PEO acts as the percolative network connecting LLZO particles and adding benefit of ease of fabrication.19-25. Table I shows the CPE ionic PEO-LiTFSI (8:1)/cubic LLZO 30 0.55 19 conductivity of varying concentration from literature. It was observed (7.5 wt %) that the conductivity of PEO did increase with the addition of LLZO. PEO-LiTFSI (8:1)/cubic LLZO 30 0.18 20 However, contrary to the rule of mixtures, the CPE with lower volume (10 wt %) fraction of LLZO had a higher ionic conductivity than compositions with higher fraction of LLZO. Hence, it was inferred that contribution PEO-LiTFSI (15:1)/cubic 30 0.01 21 from Li-ion conductivity of LLZO to the total conductivity of LLZO (70 wt %) CPE was negligible. The increase in conductivity at lower volume PEO-LiClO4 (8:1)/cubic LLZO 20 0.95 × 10−2 22 fractions was due to LLZO particles disrupting PEO crystallinity. The (15 wt %) goal of this study was to understand the transport mechanism(s) that govern the total conductivity of LLZO-PEO CPE. To investigate this, PEO-LiClO4 (8:1)/cubic LLZO 30 0.44 23 we considered possible ionic pathways in the CPE with high fractions (20 wt %) of LLZO.21 There are three possible ionic pathways illustrated in Fig. PEO-LiClO4 (20:1)/cubic 20 0.7 × 10−5 24 1a: (1) through PEO-LiTFSI, (2) through PEO-LiTFSI and LLZO, LLZO (40 vol %) or/and (3) through LLZO.26 Considering that typical composite studies consist of relatively low volume fractions of LLZO, pathway PEO-LiClO4 (15:1)/tetragonal 35 0.01 25 3 cannot be the lowest resistance path. Next, if pathway 2 was LLZO (52.5 wt %) predominant, the conductivity would increase with increasing fraction of LLZO, but based on the findings in Fig. 1b, this is typically not the case. We believe that the ionic transport across the PEOLiTFSI/LLZO interface was significantly more resistive than the resistance through PEO-LiTFSI and the dominant ionic conduction pathway was pathway 1. Thus, we believe there is a need to understand the factors that control ionic transport across polymerceramic interfaces to enable transport through LLZO (pathway 2). If successful in enabling pathway 2, the conductivity of the composite Fig. 1. (a) Possible ionic pathways in a PEO-LiTFSI/Ta-doped LLZO (LLZTO) composite electrolyte, through (1) will approach that of LLZO PEO-LiTFSI matrix, (2) both the electrolytes, and (3) LLZO; (b) Effect of the volume percentage of LLZO on the ionic conductivity of CPE (this work).

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Gupta and Sakamoto

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that use pathway 2 (Fig. 1). Achievement of these goals could result in ionic conductivity approaching 1 mS/cm while benefiting from the ease of fabrication offered by PEO. To analyze the interfacial kinetics, a trilaminar cell configuration was designed to accurately deconvolute and measure Rinterface. Electrochemical impedance spectroscopy (EIS) was used to determine Rinterface between the two electrolytes. It was shown that the Rinterface between PEO-LiTFSI and as-densified LLZO is too high to

enable pathway 2. We believe the two factors which primarily limit interfacial kinetics are surface impurities on the LLZO and the abrupt change in Li-ion concentration between the electrolytes. Thus, effects of the two factors on Rinterface and methods to control and minimize the impedance were studied. We believe the results of this study could guide future efforts to develop Li-ion conducting CPE that are simple to fabricate and that exhibit ionic conductivity comparable to liquid Li-ion electrolytes.

Experimental Section Materials Synthesis and Processing

Synthesis procedure for hot-pressed LLZTO (Ta-doped LLZO) and PEO-LiTFSI electrolytes4LLZTO powder was synthesized by a solid-state synthesis method. The details of the method are described in the supplemental section S1.* The LLZTO powder received from synthesis was sintered to provide high density pellets using rapid induction hot-pressing at 1225°C for 40 min at 47 MPa.32 Samples were cut using a diamond saw and then wet polished to 0.1 µm surface finish. A solvent-free hot-pressing method was used to fabricate the PEOLiTFSI electrolytes of desired [EO]:[Li] ratio, to ensure that residual solvent does not affect the electrochemical behavior. The details of the method are described in the supplemental section S2.

Solid-State Cell Assembly and Electrochemical Testing Procedure

To decouple the PEO-LiTFSI/LLZTO Rinterface, a trilaminar cell configuration using blocking electrodes was used (Fig. 2). The LLZTO electrolyte was interposed between two PEO-LiTFSI electrolytes. The sandwiched structure was assembled between two 1.27 cm diameter Au-coated Ni pins (current collectors) and heatconditioned at 80°C under a 100 kPa pressure to form the PEOLiTFSI/LLZTO interface. After conditioning, the cells were brought back to RT. Then, using EIS PEO-LiTFSI/LLZTO Rinterface was tracked at the desired temperature. A detailed description of cell assembly has been discussed in supplemental section S3. For the heat-treatment study, LLZTO was heat-treated in argon at temperatures between 100 and 800°C, in 100°C increments, for 3 hours at each temperature. The [EO]:[Li] ratio in PEO was fixed to avoid any variability in the results due to the salt concentration of PEO. A ratio of 27:1 [EO]:[Li] was selected because it was the lowest salt concentration in the concentration range studied for this paper. Thus, the concentration gradient would be the largest, resulting in the highest Rinterface, between PEO and LLZTO for the 27:1 ratio. For the salt concentration study, PEO-LiTFSI with different salt concentrations, were prepared via a solvent-free hot-pressing process. The cells were integrated in a trilaminar configuration and were conditioned as described above. The LLZTO pellets for this study were heat-treated at 400°C. The temperature 400°C was selected based of on previous study where, the lowest Li-LLZTO impedance was observed for 400 HT LLZTO.33

Materials Characterization Techniques

Fig. 2. (a) Impedance plot of an Au/PEO-LiTFSI/LLZTO/PEO-LiTFSI/ Au symmetric cell at 30°C, inset shows the schematic of a trilaminar cell configuration; (b) equivalent circuit for the trilaminar cell consisting of three elements—the bulk impedance, Rbulk (total of PEO-LiTFSI and LLZTO); the interfacial impedance from two PEO-LiTFSI and LLZTO interfaces, Rinterface; and the capacitive behavior from the Au blocking electrode (MAu); (c) impedance parameters obtained by fitting the impedance plot using the equivalent circuit. 64

The purity of LLZTO was confirmed with X-ray diffraction (XRD) (Rigaku Miniflex 600) using Cu Kα radiation (Fig. S1). Raman spectroscopy (Horiba Micro Raman Spectrometer housed in an argonfilled glovebox) was used to confirm the purity of PEO-LITFSI (Fig. S3). Scanning electron microscopy (TESCAN MIRA3) was used to characterize the surface of LLZO. Electrochemical Impedance Spectroscopy (EIS: Biologic VMP-300 galvanostat/potentiostat) was used to track impedance between 30°C to 80°C from 100 mHz to 7 MHz frequency with a perturbation voltage of 100 mV.

*Supplemental material for this article is online: http://interface.ecsdl.org/content/28/2/63/DC1. The Electrochemical Society Interface • Summer 2019 • www.electrochem.org

layer. Sharafi et al. reported that heat-treating the LLZTO at 400°C resulted in lowering of Li-LLZTO Rinterface.33 Li et al. prescribed heat-treatment at 700°C, in the presence of carbon, to eliminate the carbonate layer for pairing liquid electrolyte with LLZTO.29 Building upon previous work, in this study the effect of heat-treatment temperature on PEO-LiTFSI/LLZTO interface was systematically studied. The optimum heattreatment temperature was determined to remove the Li2CO3 while minimizing Li loss from the LLZTO. Essentially, we believe that removal of the impurity layer through heat-treatment reduces the Rinterface Fig. 3. Schematic of a PEO-LiTFSI and LLZTO interface (to atomic scale). (1) LLZTO; (2) Impurity layer for two reasons. First, it eliminates the (Li2CO3); (3) PEO-LiTFSI; (3’) PEO-LiTFSI (higher salt concentration); Step A. removal of the impurity resistive Li2CO3 layer. Second, elimination layer; Step B. increase in the salt concentration of PEO-LiTFSI. of the Li2CO3 reduces the electrostatic repulsion between the LLZTO surface and PEO-LiTFSI, thus decreasing the Li-ion hopping distance between Results and Discussion electrolytes, thereby facilitating transport across the interface. Li-ion concentration disparity between PEO-LiTFSI and Interfacial Impedance Analysis LLZTO4Figure 3 illustrates the large disparity in Li-ion concentration Using a Trilaminar Cell Configuration between PEO-LiTFSI and LLZTO; the Li-ion concentration in To study the PEO-LiTFSI and LLZTO interface, a trilaminar cell LLZTO was much higher than in PEO and hence, LLZTO was was used (Fig. 2). The frequency-dependent transport phenomena referred to as the higher Li-ion concentration phase (HLIC) and PEO were characterized using EIS at 30°C (Fig. 2.a). From Fig. 2a, it can be as the lower Li-ion concentration phase (LLIC). We believe that observed that the EIS data consist of two distinct frequency-dependent charge transfer kinetics are slowed because the direction of Li-ion phenomena represented by the two semicircles and a capacitive transfer in CPE (LLIC to HLIC) is opposite to the chemical gradient. tail representing the blocking behavior of the Au electrodes. An To homogenize the Li-ion concentration at the PEO-LiTFSI/LLZTO equivalent circuit (Fig. 2b) consisting of three elements—Rbulk (total interface, the Li-ion concentration in PEO can be easily modulated by of PEO-LiTFSI and LLZTO), Rinterface, and MAu—was used to analyze increasing the Li salt concentration. Hence, we studied the effect of the impedance plots. The grain boundary impedance of the LLZTO Li-ion concentration in PEO on the Rinterface. was excluded since its contribution to LLZTO bulk impedance was We believe that by carefully studying the effects of interfacial negligible (2.5%). By comparing these values with literature, it was chemistry and electrolyte concentration the PEO-LiTFSI/LLZTO confirmed that the higher frequency semicircle corresponded to the Rinterface can be reduced to 100 Ohms.cm2; or comparable to Li-ion cell bulk impedance (~0.71 × 10−9 F/cm2) from PEO and LLZTO while the impedance. A low Rinterface would allow for facile ionic transfer across lower frequency semi-circle corresponded to the Rinterface (0.55 × 10−6 the interface and hence, (2) (Fig. 1a) enable high ceramic electrolyte F/cm2).34 The magnitude of the average Rinterface from the impedance volume loadings in CPEs. 2 spectra was measured to be 96 kOhms.cm . For facile ionic transport across the PEO-LiTFSI/LLZTO Effect of Heat-Treatment Temperature interface, the Rinterface should be around 100 Ohms.cm2. Hence, it of LLZTO on the Interfacial Impedance was determined that the high Rinterface limits the total ionic transport To study the effect of heat-treatment temperature of LLZTO on of the composite approach. We believe that by understanding the Rinterface, trilaminar cells were used. The heat-treatment temperature underlying mechanisms that govern interface transport, Rinterface could ranged from untreated to a temperature where evidence of Li loss was be controlled and reduced to enable high conductivity CPE. observed. To minimize storage time, thereby minimizing the chance of contamination in the glove box, the trilaminar cells were assembled Factors Affecting the Interfacial Impedance immediately after heat-treatment. The Rinterface was measured as between PEO-LiTFSI and LLZTO a function of heat-treatment temperature. Three trilaminar cells In this study it was hypothesized that two factors which largely were characterized at 30°C for each HT; the average and standard affect the Rinterface are LLZTO surface impurities and the abrupt deviations are shown in Fig. 4a. change in Li-ion concentration between the electrolytes. Other Multiple observations were made from Fig. 4a. First, it was factors such as chemical interactions between the two electrolytes,35 observed that Rinterface was the highest for untreated LLZTO samples. 27 surface roughness of the LLZTO surface, and external factors such The high impedance was likely due to the presence of a Li2CO3 surface as temperature and stack pressure might also influence Rinterface. layer which acts as a barrier for charge transfer between PEO-LiTFSI Surface impurities on the LLZTO surface4Sharafi et al. reported and LLZTO. Also for untreated samples, because the initial thickness that a Li2CO3 surface layer on LLZO exposed to air resulted in a high of the impurity layer cannot be controlled precisely, the variability 36 Li-LLZO Rinterface. Figure 3 depicts the PEO-LiTFSI/LLZTO phase (2.38 kOhms) in Rinterface was highest for these samples. Second, the with three layers representing PEO-LiTFSI, Li2CO3, and LLZTO. We higher the heat-treatment temperature (closer to the decomposition believe there are a few ways in which the Li2CO3 (Fig. 3) layer can temperature of Li2CO3; 730–1270°C), the lower was the Rinterface of impede the interfacial kinetics. First, Li2CO3 is highly resistive and the cell. Thus, with increasing heat-treatment temperature some does not allow for facile charge transfer. The presence of the highly Li2CO3 was removed, leading to a thinner insulating layer, which then resistive Li2CO3 layer on LLZTO would result in a high Rinterface (Fig. resulted in lower Rinterface. Lastly, the Rinterface decreased with increasing 2a). Secondly, it can be observed in Fig. 3 that the presence of Li2CO3 heat-treatment temperature reaching a minimum at 700°C. Above likely increases the oxygen density on LLZTO surface. The increased 700°C the impedance increased for cells with LLZTO heat-treated at oxygen density could increase electrostatic repulsion between the 800°C. It has been further discussed that 800°C was the temperature oxygen in PEO where Li-ion is attached and LLZTO.35 Due to the where LLZTO starts to decompose. repulsion, the Li-ion hopping distance from PEO to LLZTO would (continued on next page) increase, thus, impeding charge transfer kinetics. Heat-treatment of the LLZTO was shown to be successful in removing the Li2CO3 surface The Electrochemical Society Interface • Summer 2019 • www.electrochem.org

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The change in Rinterface with cell temperature for LLZTO heattreated at different temperatures was also studied (Fig. S5). It was observed that the improved interfacial kinetics with increasing cell temperature for each heat-treatment temperature led to a decrease in

Untreated 700 HT

Rinterface 150 Hz

Rinterface 25 Hz

Rinterface 150 Hz

Rinterface 25 Hz

Fig. 4. (a) Effect of LLZTO HT temperature on the interfacial impedance between PEO-LiTFSI and LLZTO at 30°C; (b) Nyquist plots comparing two Au/PEO-LiTFSI/LLZTO/PEO-LiTFSI/Au symmetric cells at 30°C, one with untreated LLZTO and the other with LLZTO heat treated at 700°C; (c) Impedance parameters obtained by fitting the Nyquist plot using the equivalent circuit in Fig. 2b. 66

Rinterface. It was also observed that the temperature-dependent transport was linear for all heat-treatments between 30 and 80°C. This result has an important implication. Typically, PEO-LiTFSI has two temperature-dependent conductivity regimes (low temperature and high temperature) attributed to its melting point. Thus, the absence of two regimes indicates that Rinterface does not have a strong dependence on PEO-LiTFSI ionic conductivity. Figure 4b compares the impedance behavior of trilaminar cells consisting of untreated and 700 HT LLZTO. It was observed that the Rinterface semicircle, clearly visible for the untreated LLZTO, was not c) apparent for 700 HT LLZTO. Removal of the surface impurity layer Rinterface Untreated from LLZTO led to the reduction 150 Hz in Rinterface. Because there was no 700 HT of LLZTO by decomposition the heat-treatment, the bulk impedance did not dramatically change. The average Rinterface at 30°C was 180 Ohms.cm2. This value is the lowest PEO-LiTFSI/LLZTO Rinterface, which has been reported in literature. By carefully studying the effect of heat-treatment temperature of LLZTO on Rinterface we were able to reduce the impedance by a factor of ~250 from our initial results. Because a change in behavior was observed above 700°C, Xray diffraction (XRD) and scanning electron microscopy (SEM) were used to characterize LLZTO. Figure 5a shows XRD data for representative cubic LLZTO, 700 HT and R800 HT LLZTO. The absence of any interface impurity peaks in the XRD pattern 25 Hz for 700 HT LLZTO indicated that there was no apparent chemical decomposition of the sample at that temperature. However, a peak at 2θ = 29 °, corresponding to La2Zr2O7, was observed for the 800 HT LLZTO indicating Li loss from the LLZTO. Although the XRD analysis indicated that Li loss was observed for 800 HT LLZTO, it does not provide information about how that affects the LLZTO surface. SEM was used to analyze the effect of Li loss on the LLZTO surface. For the SEM analysis three polished samples were analyzed—untreated, 700 HT, and 800 HT LLZTO (Fig. S1, Fig. 5b, and Fig. 5c). The untreated sample had a few pores, but overall the surface was smooth and uniform. Compared to the untreated sample, the 700 HT LLZTO showed some evidence of growth on its surface, but no significant change was observed. However, unlike the untreated and 700 HT LLZTO samples, a significant change in morphology was observed for the 800 HT LLZTO (Fig. 5c). We believe the change in morphology was primarily due to Li loss, which is consistent with the formation of La2Zr2O7 as observed in the XRD analysis. The increase in Rinterface with an 800 HT LLZTO was likely caused by the formation of a resistive layer of La2Zr2O7. Thus, the XRD and SEM analysis confirmed that 700°C was the highest temperature at which LLZTO could be heat-treated without any deleterious effect on LLZTO.

Effect of Salt Concentration in PEO ([EO]:[Li] Ratio) on the Interfacial Impedance between LLZTO and PEO-LiTFSI

As discussed earlier, by increasing the Li-salt concentration in PEO, the abrupt change in Li-ion concentration gradient is reduced, which should facilitate transport. To study the effect of Li-ion concentration of PEO-LiTFSI on the PEO-LiTFSI/LLZTO interfacial kinetics, Rinterface was characterized as a function of Li-salt concentration. PEO-LiTFSI with different salt concentrations; [EO]:[Li] 3:1, 6:1, 9:1, 12:1, 18:1, 27:1, were prepared. Three membranes of each composition were tested using the trilaminar cell configuration. Figure 6a shows the variation in Rinterface at 30°C with salt concentration. It was observed that with increasing salt concentration from 27:1 to 3:1, the Rinterface first decreased reaching a minimum value at 15:1 salt concentration and then increasesd again. When the salt concentration increased from 27:1 to 15:1, the Li-ions participating in Li-ion transport in PEO increased and thus the Rinterface decreased. Beyond 15:1 concentration towards higher salt concentration, the Rinterface increased again. Ideally, by increasing the salt concentration the carrier concentration disparity should decrease and thus the Rinterface should decrease, but that was not the case. We believe this could be explained by the precipitation of Li-salt in the PEO. The Li-ions in the precipitated salt do not participate in ionic conduction and instead acts as inactive filler or worse. It is possible that the LLZTO surface The Electrochemical Society Interface • Summer 2019 • www.electrochem.org

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Fig. 5. (a) X-ray diffraction (XRD) on LLZTO heat-treated at different temperatures—cubic-LLZTO, 700°C, and 800°C (unknown impurity peak indicated by the red star); scanning electron microscopy using for polished LLZTO pellets heat-treated at (b) 700°C and (c) 800°C.

promoted heterogeneous nucleation causing the LiTFSI to precipitate and passivate the interface. Subsequent studies could analyze this, but clearly the Rinterface does increase above the 15:1 [EO]:[Li] ratio. Thus 15:1 was the optimum salt concentration for minimizing the Rinterface. Figure 6b shows the decrease in Rinterface achieved by optimizing the salt concentration in PEO. Two impedance plots are shown for PEO with salt concentration of 27:1 (which was used for the heattreatment study) and 15:1. It was observed that the Rinterface was smaller for the cell with 15:1 compared to 27:1 salt concentration. The average PEO-LiTFSI/LLZTO Rinterface at 30°C was 421 Ohms. cm2 for the 15:1 sample (Fig. 6c). Thus, by carefully studying the effect of Li-ion concentration in PEO-LiTFSI on the PEO-LiTFSI/ LLZTO Rinterface we reduced the impedance by a factor of ~4 from the heat-treatment study results for 400 HT LLZTO.

Significance In section 1 it is shown that total composite ionic conductivity decreased with increasing volume fraction LLZO and that most of the ionic current is carried by the PEO matrix. The challenge with this configuration is that the Li-ion conductivity of the CPE will be limited by PEO, i.e., the lower conductivity constituent. Thus, for high Li-ion conductivity composites it is necessary that the major ionic transport is through LLZO and that the majority phase is LLZO. To enable this, facile ionic transport is required through the PEO/ LLZO interface (Rinterface < 100 Ohms.cm2), which however, was not the case. The results of this study show that by addressing the root cause behind the high Rinterface (surface impurities and abrupt change in Li-ion concentration at the interface) the goal of 100 Ohms.cm2 interfacial impedance was nearly achieved (180 Ohms.cm2). Progress to this end would have implications for CPE. A low Rinterface would allow for facile ionic transfer across the interface, making pathway 2 viable, enabling high ceramic electrolyte volume loadings in CPE. The conductivity of the composite with high ceramic loadings can approach that of LLZO (~1 mS/cm) with PEO/LiTFSI facilitating membrane fabrication. Future studies could build upon these findings to develop high room temperature conductivity thin membranes that are relatively easy to process and integrate into solid-state cells.

Conclusion In this study, it was shown that high PEO-LiTFSI/LLZTO Rinterface (~95 kOhm.cm2) limits the total conductivity of CPE. This study focused on understanding transport across the PEO-LiTFSI/LLZTO interface with the goal of enabling high volume fraction ceramic membranes with high ionic conductivity and simple fabrication. The PEO/LLZO interface kinetics was analyzed using a trilaminar cell configuration that accurately measured impedance across each

interface. First, it was shown that LLZTO surface impurities and abrupt change in Li-ion concentration between PEO-LiTFSI and LLZTO were the underlying causes of the high Rinterface between the two electrolytes. The effect of the heat-treatment temperature of the LLZTO on the Rinterface was studied to remove surface impurities. It was observed that Rinterface was inversely proportional to LLZTO heat-treatment temperature up to 800°C at which Li loss occurred causing an increase in Rinterface. By optimizing the LLZTO surface, the Rinterface was reduced to 180 Ohms.cm2 at 30°C (700 HT), which is the lowest reported in literature. Second, the disparity in Li-ion concentration between PEO and LLZTO was reduced by increasing the salt concentration in PEO. By carefully studying the effect of salt concentration on PEO-LiTFSI/LLZTO interface an optimal salt concentration (15:1) was determined. The Rinterface was reduced by a factor of four compared to 27:1 salt concentration. We believe that by combining the results from the heat-treatment and the salt concentration study, we can achieve Rinterface values, which could enable total cell impedance comparable to Li-ion (~10-100 Ohms. cm2). Based on the findings in this study, it may be possible to fabricate polymer-ceramic composite electrolyte (CPE) membranes exhibiting high ceramic loading and are easy to process. © The Electrochemical Society. DOI: 10.1149/2.F06192if.

Acknowledgment The authors would like to acknowledge the support from Robert Bosch LLC, Research and Technology Center, Sunnyvale, California, USA for this project.

About the Authors Arushi Gupta received her BTech in chemical technology with a specialization in plastics technology from Harcourt Butler Technological Institute (HBTI) in Kanpur, India, in 2015. She earned her MS in macromolecular science and engineering in 2017 from the University of Michigan, Ann Arbor. Currently she is a PhD candidate in macromolecular science and engineering at the University of Michigan, Ann Arbor. Her research focuses on solid polymer electrolytes and polymer composites for next-generation Li metal batteries. She may be reached at arushig@umich.edu. https://orcid.org/0000-0002-9788-8274

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Gupta and Sakamoto

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Jeff Sakamoto has 20 years of experience studying and translating ceramic materials for electrochemical materials into energy technologies for terrestrial and space applications. He was a senior researcher at the Caltech Jet Propulsion Laboratory (2000-2007) c) and a professor at Michigan State University (2007-2014). He has been a professor at the University of Michigan since 2014. The Sakamoto Group is routinely involved in ceramic material synthesis and processing, electrochemical and mechanical property characterization of super Li-ion conducting and cathode Rinterface ceramic104 oxides. Hz Sakamoto is a Kavli Frontiers of Science fellow, and Rinterface was a chair, organizer, speaker, and delegate at National Academy of 112 Hz Sciences Frontiers of Science and National Academy of Engineering Frontiers of Engineering symposia. Sakamoto received two Major Space Act Awards from the NASA Inventions and Contributions Board. He is the primary contributor on 24 patents and received the Teacher-Scholar (2013) and Withrow Excellence in Teaching (2009) Awards at Michigan State University. He may be reached at jeffsaka@ umich.edu. https://orcid.org/0000-0002-3099-462X

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Fig. 6. (a) Effect of salt concentration in the PEO-LiTFSI electrolyte on the interfacial impedance between PEO-LiTFSI and LLZTO electrolytes; (b) Nyquist plots comparing two Au/PEO-LiTFSI/LLZTO/PEO-LiTFSI/ Au symmetric cells at 30°C, one with 27:1 salt concentration and the other with 15:1 salt concentration in the PEO-LiTFSI electrolyte; (c) Impedance parameters obtained by fitting the Nyquist plots using the equivalent circuit in Fig. 2b.

References 1. R. Van Noorden, Nature, 507, 26 (2014). 2. B. Dunn, K. Haresh, and J-M. Tarascon, Science, 334, no. 6058 (2011): 928-935. 3. V. Etacheri, R. Marom, R. Elazari, G. Salitra, and D. Aurbach, Energ. Environ. Sci., 4, 3243 (2011). 4. N. J. Dudney, and J. Li, Science, 347, 131 (2015). 5. P. G. Bruce, S. A. Freunberger, L. J. Hardwick, and J-M. Tarascon, Nat. Mater., 11, 19 (2012). 6. P. Bron, S. Johansson, K. Zick, J. Schmedt auf der Günne, S. Dehnen, and B. Roling, J. Am. Chem. Soc., 135, 15694 (2013). 7. N. Kamaya, K. Homma, Y. Yamakawa, M. Hirayama, R. Kanno, M. Yonemura, and T. Kamiyama, Nat. Mater., 10, 682 (2011). 8. H. Aono, E. Sugimoto, Y. Sadaaka, N. Imanaka, and G. Y. Adachi, J. Electrochem. Soc., 136, 590 (1989). 9. R. Murugan, V. Thangadurai, and W. Weppner, Angew.e Chem., Int. Ed., 46, 7778 (2007). 10. C. Ma, Y. Cheng, K. Yin, J. Luo, A. Sharafi, J. Sakamoto, J. Li, K. L. More, N. J. Dudney, and M. Chi, Nano Lett., 16, 7030 (2016). 11. D. T. Hallinan Jr. and N. P. Balsara, Ann. Rev. Mater. Res., 43, 503 (2013). 12. L. Long, S. Wang, M. Xiao, and Y. Meng, J. Mater. Chem. A, 4, 10038 (2016). 13. A. Manthiram, X. Yu, and S. Wang, Nat. Rev. Mater., 2, 16103 (2017). 14. P. P. Prosini and S. Passerini, Solid State Ionics, 146, 65 (2002). 15. G. B. Appetecchi and S. Passerini, J. Electrochem. Soc., 149, A891 (2002). 16. R. Bouchet, S. Lascaud, and M. Rosso, J. Electrochem. Soc., 150, A1385 (2003). 17. G. B. Appetecchi, S. Scaccia, and S. Passerini, J. Electrochem. Soc., 147, 4448 (2000). 18. F. Croce and B. Scrosati, J. Power Sources 43, 9 (1993). 19. F. Chen, D. Yang, W. Zha, B. Zhu, Y. Zhang, J. Li, Y. Gu, Q. Shen, L. Zhang, and D. R. Sadoway, Electrochim. Acta, 258, 1106 (2017):.

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20. L. Chen, Y. Li, S-P. Li, L-Z. Fan, C-W. Nan, and J. B. Goodenough, Nano Energy, 46, 176 (2018). 21. M. Keller, G. B. Appetecchi, G-T. Kim, V. Sharova, M. Schneider, J. Schuhmacher, A. Roters, and S. Passerini, J. Power Sources, 353, 287 (2017). 22. X. Tao, Y. Liu, W. Liu, G. Zhou, J. Zhao, D. Lin, and C. Zu, Nano Lett., 17, 2967 (2017). 23. K. Karthik and R. Murugan, J. Solid State Electrochem., 22, 1 (2018). 24. F. Langer, I. Bardenhagen, J. Glenneberg, and R. Kun, Solid State Ionics, 291, 8 (2016). 25. J-H. Choi, C-H. Lee, J-H. Yu, C-H. Doh, and S-M. Lee, J. Power Sources, 274, 458 (2015). 26. S. Kalnaus, W. E. Tenhaeff, J. Sakamoto, A. S. Sabau, C. Daniel, and N. J. Dudney, J. Power Sources, 241, 178 (2013). 27. T. Abe, M. Ohtsuka, F. Sagane, Y. Iriyama, and Z. Ogumi, J. Electrochem. Soc., 151, A1950 (2004). 28. W. E. Tenhaeff, K. A. Perry, and N. J. Dudney, J. Electrochem. Soc., 159, A2118 (2012).

29. Y. Li, X. Chen, A. Dolocan, Z. Cui, S. Xin, L. Xue, H. Xu, K. Park, and J. B. Goodenough, J. Am. Chem. Soc., 140, 6448 (2018). 30. F. Langer, M. S. Palagonia, I. Bardenhagen, J. Glenneberg, F. La Mantia, and R. Kun, J. Electrochem. Soc., 164, A2298 (2017). 31. K. Timachova, H. Watanabe, and N. P. Balsara, Macromolecules, 48, 7882 (2015). 32. E. Rangasamy, J. Wolfenstine, and J. Sakamoto, Solid State Ionics, 206, 28 (2012). 33. A. Sharafi, E. Kazyak, A. L. Davis, S. Yu, T. Thompson, D. J. Siegel, N. P. Dasgupta, and J. Sakamoto, Chem. Mater., 29, 7961 (2017). 34. J. T. S. Irvine, D. C. Sinclair, and A. R. West, Adv. Mater., 2, 132 (1990). 35. O. Borodin, G. D. Smith, R. Bandyopadhyaya, and O. Byutner, Macromolecules, 36, 7873 (2003). 36. A. Sharafi, S. Yu, M. Naguib, M. Lee, C. Ma, H. M. Meyer, J. Nanda, M. Chi, D. J. Siegel, and J.Sakamoto, J. Mater. Chem. A, 5, 13475 (2017).

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Electrolyte Solutions for “Beyond Li-Ion Batteries”: Li-S, Li-O2, and Mg Batteries by Daniel Sharon, Michael Salama, Ran Attias, and Doron Aurbach in rechargeable batteries. In Li-S and Li-O2 batteries, the cathode’s reduction products migrate to the anode side and worsen the Li anode passivation.10,11 Thereby, it is critically important to avoid any possible cross-talk between the electrodes in these systems. With rechargeable Mg batteries the situations have to be completely different. Because Mg ions are bivalent, they cannot migrate through surface films comprising ionic magnesium compounds.12 Thereby, Mg metal anodes can behave reversibly only in relatively nonreactive electrolyte solutions, in which they are bare, with no surface films.13

Development of New Nonaqueous Battery Families and the Challenge of Electrolyte Systems for Rechargeable Batteries

Voltage / V

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he development and commercialization of rechargeable Li-ion battery technology is the most impressive success of modern electrochemistry.1 Modern life has led to an exponential expansion of the battery market and is driving the development of new families of batteries beyond LiLithium-Sulfur Batteries ion technology. The current and near-future needs for batteries can be categorized as mobile electronics, electro-mobility, large energy Lithium-sulfur batteries are the subject of very intensive research storage (grid and sustainable energy applications), and very high due to the high theoretical specific capacity of sulfur cathodes energy density systems for drones, unmanned vehicles, robotics, (1672 mAh g−1 upon Li2S formation) which is an order of magnitude and military uses. The success and long-term experience with Li-ion higher than that of lithiated transition-metal oxides and phosphates batteries has enabled development of sister technologies based on cathode materials used in commercial Li-ion batteries (140other active metal anodes, such as rechargeable Na2 and Mg3 batteries. 200 mAh g−1).7,14 Li-ion batteries emerged from rechargeable Li metal batteries nearly The most commonly used solutions for Li-S batteries are ethereal 30 years ago, after commercialization of the latter systems failed due electrolyte solutions based on mixtures of 1,3-dioxolane (DOL) to limitation in cycle life and safety issues.4,5 However, after the great and dimethyl ether (DME) lithium bis(trifluoromethanesulfonyl) progress made in recent decades in electrochemical and materials imide (LiTFSI) as the electrolyte. During the discharge process, science, we have seen a renaissance in redeveloping Li metal-based elemental sulfur S8 accepts electrons to give a chain of electroactive rechargeable batteries.6 A major advantage of these systems is the Li-polysulfides (Fig. 1a). The long-chain Li2Sn (4 ≤ n ≤ 8) are soluble capability to reach very high energy density, especially with high (continued on next page) capacity cathodes in which the active species are sulfur or oxygen.7,8 Here we concentrate on Solid-liquid-sold reaction (normal behavior) three systems that can be considered as “beyond Liion batteries”—rechargeable Li-sulfur, Li-oxygen, and magnesium battery systems— a focusing on the highly important aspect of electrolyte 0.2 3 solutions which can be suitable I 0 Sulfur 2 for them. II -0.2 Carbon particle I II In Li batteries there 1 impregnated with -0.4 0 5 10 15 20 1 2 3 is no chance to reach a Micropore sulfur Time / h Voltage / V thermodynamic stability on the Li-electrolyte solution interface. Fortunately, it Quasi-Solid-state reaction of sulfur with Li ions is possible to stabilize Li metal electrodes in many S8 Solid state transformation nonaqueous solutions by Desolvation passivation phenomena due to spontaneous reactions SEI b Li2Sn that form protective surface 3 1 films. These surface films 1 cycle 2 -1 SEI Sulfur comprise ionic Li moieties Carbon particle 1 -3 Li which are electronically Li2S impregnated with 1 cycle 0 -5 isolating (avoiding further side sulfur covered 0 1000 2000 0.5 1.5 2.5 3.5 Micropore with SEI layer reactions), but can transport Li Capacity / mAh g-1 Voltage, V ions under an electrical field, behaving like solid electrolyte interphases (SEI).9 They Fig. 1. Schematic presentation of two reaction paths observed for Li-S cells with typical CV and galvanostatic responses: allow long-term metastable (a) normally observed solid-liquid-solid reaction and (b) quasi-solid state reaction with Li ions desolvation due to the operation of Li metal anodes formation of SEI. Copyright 2015, Wiley-VCH. Adopted with permission from Wiley.14 The Electrochemical Society Interface • Summer 2019 • www.electrochem.org

Sharon et al.

Li-S batteries.23 This type of behavior is associated with the reaction of desolvated Li ions with sulfur inside the pores of the carbon host and is known as quasi-solid state (QSS) reactions.24,25 In most cases this mechanism is observed for composite S/C electrodes with very narrow micropores (less than 1 nm wide),21,22,24,25 but in some cases this type of operation was described for larger pores size.12 For all examples of QSS reactions of sulfur cathodes, the voltage profiles of the cells measured in the first galvanostatic cycle differ substantially from those measured in subsequent cycles. The low voltage plateau in the first discharge corresponds to the formation of protective surface films on the S/C cathodes.18,20-22 The combination of organic carbonate electrolyte solution containing fluoroethylene carbonate (FEC) with sulfur-microporous carbon composite electrodes results in excellent cycling performance of Li-S cells, which remarkably outperform cells with either nonfluorinated carbonates or ethereal solutions.20 An example of the excellent cycling performance of Li-S cells demonstrating thousands of cycles of S/C composite cathodes operating according to the QSS mechanism in FEC-based electrolyte solution is shown in Fig. 2. Note that the same solutions are suitable for the Li side as well. The surface films formed on Li metal electrodes in these solutions provide them with the best passivation due to a unique surface chemistry21,22 (a description of which is beyond the scope of this paper). These cells show voltage profiles typical for a quasi-solid state mechanism of the S-C cathodes, with a single discharge and charge plateaus (Fig. 2b) related to single reduction and oxidation peaks in the CV curves of these electrodes.21 The microporous carbon for these electrodes was prepared by carbonizing polyvinylidene dichloride (PVDCDC). The cumulative pore volume distribution for this carbon is presented in Fig. 2c. It is seen that the pore width of most of the pores is less than 1 nm.

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in ethereal solvents and diffuse freely to the anode side where they are chemically reduced. This phenomenon, known as the shuttle effect, presents one of the main problems in Li-S cells.15 This effect can be mitigated by enhancing the Li metal anode passivation, using LiNO3 as a “magic” additive which strongly affects the Li surface chemistry. However, these solutions do not enable long cycling of Li-S cells. The encapsulation of sulfur within activated carbons is an effective approach to mitigating the detrimental shuttle mechanism and stabilizing composite sulfur cathodes during prolonged cycling.16,17 The typical cyclic voltammetry and galvanostatic charge-discharge curves of Li-S cells with C/S encapsulated cathodes are shown in Fig. 1a.7 The first voltage plateau at ~2.3 V relates to the reduction of the cyclo-S8 to long-chain lithium polysulfides (Li2Sn 4 < x ≤ 8) soluble in the electrolyte solution, and the following plateau at ~2.1 V is associated with the further reduction of these polysulfides to Li2S2 and Li2S.7 This behavior is generally observed in ethereal electrolyte solutions, but it was also observed with other electrolyte solutions in which Li polysulfides are soluble.18 The majority of publications on Li-S batteries relate to Li-S electrodes which behave according to this solid-liquid-solid reaction path.7,14 Another type of behavior, shown in Fig. 1b, is generally observed for some organic carbonate-based electrolyte solutions,18-22 as well as for bis(fluorosulfonyl)imide (FSI) anion-based ionic liquid electrolyte solutions.18,22 As opposed to ethereal electrolyte solutions, the electrophilic organic carbonates have been shown to be reactive toward lithium polysulfides. However, for several types of microporous carbon hosts, sulfur-carbon composite electrodes may be reversibly lithiated in organic carbonate electrolyte solutions, demonstrating a voltage response very similar to that of solid state

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Fig. 2. (a) Charge capacity and cycling efficiency vs. cycle number curves of Li/S-PVDCDC cell (sulfur loading 1mg) cycled at different current densities, as indicated; (b) Voltage profiles of S-PVDCDC/Li cell measured at cycles 10, 1000, 2000, and 3000, as indicated, at a current density of 1.04 A/g; (c) Cumulative pore volume distribution calculated by DFT from N2 adsorption isotherms measured at 77 K of PVDCDC powder (red curve) and PVDCDC impregnated with 40 wt% of sulfur (black curve); (d) SEM images and EDS results measured for composite S-PVDCDC electrode cycled for 320 cycles at 30°C. Copyright 2016, ECS. Reproduced with permission from ECS.21 72

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Fig. 3. Illustration of the growth mechanism of Li2O2 on top of a carbon cathode with different solvents and counter-anion lithium salts. ACN, glymes, DMA, and DMSO are the solvents acetonitrile, polyethers, dimethylacetamide, and dimethyl sulfoxide, respectively. TFSI− and Tf− are the anions bis(trifluoromethane)sulfonimide and trifluoromethanesulfonate, respectively. Donor numbers provide a scale for nucleophilicity of solvents, and the ionic association strength of a salt is determined by the negative charge delocalization, size, and steric effects for a given anion.46

The surface films formed on S/PVDC-derived carbon electrodes cycled in FEC-based solutions are visible in SEM images (Fig. 2d). As clearly seen, all of the PVDCDC particles are uniformly coated by surface films with attached bright spherical droplets of various sizes up to ~300 nm in diameter. The sites marked in red in Fig. 2d obviously originate from the occasional removal of LiF crystals. These traces provide additional evidence of the existence of surface films on the smooth part of the S-C composite particles, which include polymeric matrices in which the LiF crystals are embedded. Thus, SEI-type surface films formed on the surface of the S/C composite electrodes during the initial discharge play a key role in the operation of the S/C electrodes via the QSS mechanism. They prevent the encapsulated sulfur from detrimental direct contact with the liquid electrolyte solution. These studies suggest the possibility to create Li-S batteries with excellent cycle life. However, excellent cycle life means the use of composite electrodes and a penalty in the specific capacity and energy density side. In turn, it is possible to demonstrate very high energy density Li-S batteries containing ethereal electrolyte solutions and simple S cathodes (> 400 Wh/kg practical), on the account of prolonged cycle life.

Rechargeable Lithium-Oxygen Batteries Paring lithium ions with reduced oxygen species can potentially produce one of the most promising electrochemical storage systems in terms of theoretical energy density. Nevertheless, the study of LiO2 electrochemistry in aprotic solvents is fraught with significant challenges. The main proof of the ineffectiveness of existing LiO2 cells is their poor cyclability. One of the reasons for this poor performance is the degradation of the electrolyte solution during battery operation. Unlike Li-ion batteries where the electrode materials dictate the electrochemical mechanism, in Li-O2 batteries the electrolyte solution governs the electrochemical mechanism and the final products.26 Acknowledging that the solvent stability is crucial for the success of Li-O2 batteries, researchers started looking at a variety of aprotic solvent candidates.27 Screening and examination of electrolyte solutions for Li-oxygen batteries had been going on for more than a decade, but no system was shown to be stable enough to enable sufficient cycling performance. Two notable candidate solvents are the polyethers (glymes)28 and dimethyl sulfoxide (DMSO).29 Different solvents from the polyether family such as diglyme and tetraglyme have been shown to form the desirable Li2O2 oxygen reduction reaction (ORR) product in a reversible manner. Nonetheless, it was found that even the theoretically more stable glymes solvents are

also exposed to attack by the nucleophilic and basic reduced oxygen species.30-32 Attempts to modify the glymes structure by protecting the sensitive chemical sites with different chemical groups showed limited improvement.33,34 For example, we have demonstrated that DMDMP (2,4-Dimethoxy-2,4-dimethylpentan-3-one) showed less formation of side products during the ORR.35 However, the stability of the DMDMP during the oxygen evolution reaction (OER) and toward the lithium metal anode was not sufficient to enable prolonged cycling. It was recently found that the specific structure of glyme solvents significantly affects the performance of Li-oxygen cells.35,36 The cycling performance of Li-O2 cells with diglyme (n = 2) based solutions was substantially better compared to similar cells containing other glymes.37 The reason for this discrepancy is still unclear. Another promising solvent candidate is DMSO. It was reported that Li-O2 cells containing DMSO solutions paired with noncarbon cathodes presented reasonable cycling behavior.38,39 However, by using multiple analytical methods we found that reactivity of the DMSO with the Li anode and the superoxide can lead to an irreversible deposition of LiOH on the cathode surface.40 Although DMSO didn’t show overall improvement in the Li-O2 cells’ performance, in situ spectroscopic study showed that during ORR the usually nonstable intermediate superoxide radical lifetime was extended due to the high Guttman donor number of DMSO compared to glymes solvents.41 The metastable soluble superoxide radical (O2−) moieties switch the growth mechanism of the nonsoluble Li2O2 deposits from surface growth to a solution-derived growth mechanism (i.e., from a bottomup to a top-down Li-peroxide deposition mechanism). The change in the growth mechanism and the Li2O2 deposit morphologies with different aprotic solvents are illustrated in Fig. 3.42 The Li2O2 particles deposited from solution phase (top-down) were found to be bigger and were not limited by the nonconductive nature of the Li2O2 as was previously observed with surface (bottom-up) growth mechanism. The growth mechanism of Li2O2 deposits can be affected also by the association strength of the lithium cations with the counter-anions in the Li+ ions solvation shells (Fig. 3).11 We demonstrated that by changing the counter-anion properties such as size and electronic structure, we were able to switch between a surface to a solution Li2O2 formation mechanism, even with low donor number solvents such as diglyme.43 We note that currently there is no “perfect” solvent for Li-O2 batteries. Nevertheless, we suggest that the glymes family and its derivatives might be a reasonable compromise if other obstacles that affect the stability, such as the high overpotential used to reoxidize the ORR products during OER, are resolved. As can be seen from the voltage profiles in Fig. 4a, when a standard solution of diglyme 0.2 M LiTFSI is used in Li-O2 cells, the overall cell potential during OER surpasses 4 V. At these high oxidation potentials, both the electrolyte solution and the carbon cathode are in danger of oxidation. To overcome this challenge, it was suggested to introduce soluble redox mediators (RMs) that can reduce OER overpotential to acceptable values by enhancing the oxidation of the Li2O2 deposits.44 One promising class of RMs are lithium halides salts.45 Figure 4c shows the voltage profile of Li-O2 cell with diglyme 0.2 M LiTFSI and 50 Mm of LiI. As can be seen during the initial cycles, the oxidation curves present a potential plateau around 3.5 V which correlates to the I3−/I− redox couple. However, with further cycling the cell potential gradually increases to 4 V where I3− is oxidized to the highly corrosive I2. We found that the presence of I− anions promotes side reactions of reduced oxygen species with glymes that irreversibly form LiOH on the cathodes in Li-oxygen cells.46 Thereby, we suggest replacing the iodide halide anion with bromide. As can be seen in Fig. 4b, cells containing 0.2 M LiTFSI with 50 mM LiBr in diglyme present a stable oxidation plateau for 40 cycles at 3.5 V where the Br− is oxidized to Br3−. We propose that the redox activity of Br3− is sufficient to oxidize most of the ORR products below 4 V. In a recent study we demonstrated that commonly used RMs in Li-oxygen cells suffer from intrinsic stability problems. Therefore, when selecting a redox mediator it is important to examine its overall chemical behavior and not just measure its effect on the

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overpotentials of the OER.47 In summary, Li-O2 battery research has made enormous progress over the past 10 years. Challenges and new significant data on the mechanisms of ORR and OER have been gleaned by using advanced techniques. These mechanisms may well help in the design of electrodes and solvents that are stable within the unusual conditions required for Li-O2 cells operation.

Rechargeable Mg Batteries Magnesium secondary batteries have the potential to compete with lithium-ion systems if it is possible to develop high specific capacity cathodes for them.48 Magnesium low reduction potential

(−2.37 V vs NHE) and high volumetric capacity (3833 mAh cm−3) result in worldwide efforts to make rechargeable magnesium batteries a practical reality. Furthermore, magnesium tends to form dendritefree deposits in electrolyte solutions in which Mg electrodes behave reversibly. As such, utilization of Mg anodes in rechargeable batteries is very attractive compared to other active metals (e.g., Li, Na).49,50 Reversible magnesium deposition was demonstrated for the first time in 192751 with Grignard reagents (RMgCl) as the electrolyte in ethereal solvents. Ether solvents are stable toward Mg metal and the reductive nature of the Grignard electrolytes makes them stable with magnesium metal as well, enabling reversible Mg deposition/ dissolution processes in these solutions. However, these solutions suffer from low ionic conductivity and very low anodic stability (<1 V vs. Mg), which makes them irrelevant for any practical Mg batteries. Gregory, et al.,52 developed solutions with organometallic complexes such as Mg(BBu2Ph2)2 for reversible Mg anodes, but their anodic stability was too low (<2 V vs. Mg). The first practical electrolyte solutions for rechargeable magnesium batteries were formulated by reactions of RmMgCl2−m (Lewis base) and RnAlCl3−n (Lewis acid) in ether solvents (THF and glymes) could produce a variety of organometallic magnesium-based electrolytes solutions with tunable electrochemical properties and performance.53 The best example was the reaction product of Bu2Mg and EtAlCl2 in 1:2 ratio in THF.54 This solution exhibits a relatively high conductivity of 1.4 mS cm−1, an electrochemical window up to 2.4 V, and full reversibility of Mg deposition dissolution processes. This electrolyte solution was the first used in secondary magnesium battery prototypes that could undergo thousands of cycles.54 Mechanistic investigation of possible oxidation reactions of these organometallic-based electrolyte solutions showed that the main anodic decomposition mechanism of these electrolytes is β-H elimination.55 Therefore, the products of the Lewis acid/base reactions that form the complex electrolytes should not contain any hydrogen atoms in the β position. There are a few electrolytes that implement this approach, but the first one reported is based on the reaction product of PhxMgCl2−x and PhyAlCl3−y to form the electrolyte termed all phenyl complex (APC).56 The APC electrolyte solutions exhibit higher anodic stability (3.3 V vs. Mg) and fully reversible behavior of Mg electrodes. Another example is the development of magnesium hexamethyldisilazide-chloride (HMDSMgCl)57 and reacting it with AlC3 to form highly stable complex electrolyte solution in which Mg electrodes are reversible.58

Nonorganometallic Electrolyte Solutions for Mg Batteries

Fig. 4. (a) Voltage profiles of Li-O2 cells during prolonged galvanostatic cycling with diglyme solutions: (a) 0.2 M LiTFSI; (b) 0.2 M LiTFSI + 50 mM LiBr; and (c) 0.2 M LiTFSI + 50 mM LiI. Current density was fixed at 0.052 mA cm−2. Adopted with permission from RSC.46 74

That first generation of solutions based on organometallic complexes have pyrophoric nature and are expensive, making them unsuitable for commercial energy storage systems. The first simple (conventional) salt-based electrolyte solutions were products of the reactions between AlCl3 and MgCl2 in THF or glymes. These Lewis acid\base reactions result in electrolyte solutions exhibiting a wide electrochemical window (>3 V), enabling reversible behavior of Mg anodes, termed magnesium aluminum chloro complex (MACC).59 To reach 100% cycling efficiency of Mg deposition/dissolution, an activation step is needed, in which all the possible contaminants that can react with Mg deposits to form passivating films are removed.59 MgTFSI2 is probably the only salt that is readily soluble in ethers at high concentrations, forming solutions possessing high anodic stability (>3.2 V vs. Mg). These solutions exhibit very poor electrochemical performance of Mg anodes.60 A comprehensive study of MgTFSI2 solutions in dimethoxyethane (DME) revealed that the salt completely disassociates into free uncoordinated anions and Mg2+ cations solvated by three DME molecules.61 The strong interactions between the DME molecules and the Mg cations lead to a very high overpotential for Mg deposition in these solutions (>1 V). However, adding MgCl2 to MgTFSI2 in glyme solvents dramatically improves the reversibility of Mg deposition processes, because the presence of chlorides in solutions changes the cation structure and weakens The Electrochemical Society Interface • Summer 2019 • www.electrochem.org

Fig. 5. Images a and b emphasize the importance of chloride for Mg electrochemistry. (a) Cyclic voltammogram of MgTFSI2 DME electrolyte solution, WE-Pt, CE-Mg, RE-Mg.62 (b) CV voltammogram of MgTFSI2\MgCl2 1:2 molar ratio in DME electrolyte solution, WE-Pt, CE-Mg, RE-Mg.62 (c) Electroactive specie in MgTFSI2\MgCl2 1:2 molar ratio in DME.56 (d) HRSEM image of magnesium deposits from of MgTFSI2\MgCl2 1:2 molar ratios in DME electrolyte solution. Adopted with permission from ECS62, adopted with permission from ACS.56

the interactions of Mg cations with the ether molecules (Fig. 5).62 The active cations in these solutions are mostly Mg3Cl42+.56 The Mg cations undergo a relatively easy desolvation due to the large cation size and the relatively weaker involvement of the ether molecules in their structure, and thereby Mg deposition can be fully reversible (low overpotential) in them. Like MACC solutions, the MgTFSI2/ MgCl2/DME solutions also need to undergo an activation process that removes Mg surface reactive contaminants to enable fully reversible behavior of the Mg electrodes in them.62 It appears that the presence of chloride ions is very important for the reversible behavior of Mg anodes in ethereal solutions, but leads to interfacial problems with transition metal oxides that can serve as high-voltage high-capacity cathodes for Mg batteries. As such, we see continuous efforts to develop chloride-free electrolyte solutions for rechargeable Mg batteries. A pioneering work was published by Mohtadi, et al., who found that magnesium could be fully reversibly deposited from Mg(BH4)2 / (DME,THF)63 and from Mg(CB11H12)2 in triglyme or tetraglyme solutions that possess high anodic stability.64 Interestingly, even in chloride-free ethereal Mg salt solutions it was impossible to demonstrate reversible Mg intercalation into transition metal oxides. V2O5 electrodes can insert Mg ions reversibly at high capacity in conventional electrolyte solutions such as Mg(ClO4)2 in acetonitrile (ACN) and thereby can serve as a classical model for the study of the solution effect on Mg ions intercalation into transition metal oxide electrodes. In recent studies we discovered unique solvent and salt effects that impede Mg ions intercalation into V2O5 electrodes.65,66 DME, an important solvent for Mg electrochemistry, was found to inhibit electrochemical intercalation of Mg ions into V2O5 due to strong solvation effects, as illustrated in Fig. 6. In

addition, the TFSI anion, which is considered compatible with Mg anode, was found to form impermeable surface film of MgF2 which may completely passivate metal-oxide cathode. These findings demonstrate the great challenge of integrating components for high energy density Mg batteries. Consequently, high energy density, rechargeable Mg batteries are not easy to elaborate, yet they are in early stages of R&D. © The Electrochemical Society. DOI: 10.1149/2.F07192if.

About the Authors Daniel Sharon is currently a postdoctoral fellow at Argonne National Laboratory and the University of Chicago, USA. He received his BSc in chemistry and PhD in electrochemistry from Bar-Ilan University, Ramat-Gan, Israel (2016). His PhD thesis involved studies of intercalation compounds for electrodes in Li-ion batteries and basic nonaqueous oxygen electrochemistry. His current research interests include the development and introduction of new analytical methods for a better characterization of electrochemical systems. Currently, Sharon is working on developing electrochemical platforms by nanofabrication techniques which can help to explain ions transport mechanisms in solid electrolytes with nanoscale morphologies. He may be reached at dssharon27@gmail.com. https://orcid.org/0000-0002-3385-1536

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gmail.com.

Michael Salama is a PhD student in the Chemistry Department of Bar-Ilan University (BIU), Israel. He received his BSc and MSc degrees in chemistry from BIU. He is supposed to complete his PhD thesis and studies this year. He works in the field of magnesium electrochemistry and Mg rechargeable batteries. The focus of his research is the electrolyte solutions/electrodes interface in magnesium batteries. He may be reached at 123salama@

https://orcid.org/0000-0002-3495-2822 Ran Attias is a PhD student in the Chemistry Department of Bar-Ilan University (BIU), Israel. He received his BSc in biotechnology engineering in 2015 from Ben-Gurion University and his MSc in chemistry in 2017 from BIU. The focus of his research is solid state electrochemistry and nonaqueous magnesium electrochemistry. He may be reached at raniatiias@gmail.com. https://orcid.org/0000-0003-0528-7664 Doron Aurbach, is a full professor and leader of the Electrochemistry Group (40 people) in the Chemistry Department of Bar-Ilan University, Israel. His teams study the electrochemistry of active metals and nonaqueous electrochemical systems, develop spectroscopic methods (in situ and ex situ), study electrochemical intercalation processes and electrochemical water desalination, and develop a wide scope of rechargeable batteries and supercapacitors. He has published more than 630 peer-reviewed papers, 25 patents, and 19 chapters in books. He also has given hundreds of invited talks at international conferences. Aurbach is a technical editor of the Journal of The Electrochemical Society, in charge of the batteries and energy storage topical interest area. He is a fellow of ECS, ISE, and MRS. He received the E. B. Yeager Award of the IBA in 2014, the Allen J. Bard Award of The Electrochemical Society in 2017, and the A. Frumkin Medal of the International Society of Electrochemistry in 2018. He

leads the Israel National Research Center for Electrochemical Propulsion (INREP) which includes 23 research groups from six academic institutions. He may be reached at aurbach@mail.biu.ac.il. https://orcid.org/0000-0001-8047-9020

References 1. N. Nitta, F. Wu, J. T. Lee, and G. Yushin, Mater. Today, 18, 252 (2015). 2. H. Kim, H. Kim, Z. Ding, M. H. Lee, K. Lim, G. Yoon, and K. Kang, Adv. Energy Mater., 6, 1600943 (2016). 3. P. Saha, M. K. Datta, O. I. Velikokhatnyi, A. Manivannan, David Alman, and P. N. Kumta, Prog. Mater. Sci., 66, 1 (2014). 4. P. Dan, E. Mengeritski, Y. Geronov, D. Aurbach, and I. Weisman, J. Power Sources, 54, 143 (1995). 5. I. Weissman, A. Zaban, and D. Aurbach, J. Electrochem. Soc., 143, 2110 (1996). 6. X.B. Cheng, R. Zhang, C.Z. Zhao, and Q. Zhang, Chem. Rev., 117, 10403 (2017). 7. A. Manthiram, Y. Fu, S.H. Chung, C. Zu, and Y.S. Su, Chem. Rev., 114, 11751 (2014). 8. M. Balaish, A. Kraytsberg, and Y. EinEli, Phys. Chem. Chem. Phys., 16, 2801 (2014). 9. E. Peled and S. Menkin, J. Electrochem. Soc., 164, A1703 (2017). 10. M. Wild, L. O’Neill, T. Zhang, R. Purkayastha, G. Minton, M. Marinescu, and G. J. Offer, Energy Environ. Sci., 8, 3477 (2015). 11. D. Aurbach, B. D. McCloskey, L. F. Nazar, and P. G. Bruce, Nat. Energy, 1, 16128 (2016). 12. Z. Lu, A. Schechter, M. Moskovich, and D. Aurbach, J. Electroanal. Chem., 466, 203 (1999). 13. D. Aurbach, I. Weissman, Y. Gofer, and E. Levi, Chem. Rec., 3, 61 (2003). 14. A. Rosenman, E. Markevich, G. Salitra, D. Aurbach, A. Garsuch, and F. F. Chesneau, Adv. Energy Mater., 5, 1500212 (2015). 15. Y. V. Mikhaylik and J. R. Akridge, J. Electrochem. Soc., 151, A1969 (2004). 16. J. L. Wang, J. Yang, J. Y. Xie, N. X. Xu, and Y. Li, Electrochem. Commun., 4, 499 (2002). 17. R. Elazari, G. Salitra, A. Garsuch, A. Panchenko, and D. Aurbach, Adv. Mater., 23, 5641 (2011). 18. E. Markevich, G. Salitra, A. Rosenman, Y. Talyosef, F. Chesneau, and D. Aurbach, J. Mater. Chem A, 3, 19873 (2015).

Fig. 6. (a) An illustration describing the effect of DME addition into Mg(ClO4)2/ACN electrolyte solution. The addition of DME into the ACN-based solution result in formation of thermodynamically stable 3DME:Mg2+ solvate structures, slowing down the insertion of Mg ions into the oxide host. (b) Comparative cyclic voltammetry of monolithic V2O5 electrodes in Mg(ClO4)2/ACN-based electrolyte solutions without (black line) and with DME (red). Adopted with permission from ACS.66 76

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19. A. Zhang, X. Qin, G. R. Lia, and X. P. Gao, Energy Environ. Sci., 3, 1531 (2010). 20. E. Markevich, G. Salitra, A. Rosenman, Y. Talyosef, F. Chesneau, and D. Aurbach, Electrochem. Comm., 60, 42 (2015). 21. A. Rosenman, E. Markevich, G. Salitra, Y. Talyosef, F. Chesneau, and D. Aurbach, J. Electrochem. Soc., 163, A1829 (2016). 22. E. Markevich, G. Salitra, Talyosef, F. Chesneau, and D. Aurbach, J. Electrochem. Soc., 164, A6244 (2017). 23. Z. Lin, Z. Liu, W. Fu, N. J. Dudney, and C. Liang, Angew. Chem. Int. Ed., 52, 7460 (2013). 24. D.W. Wang, G. Zhou, F. Li, K.H. Wu, G. Q. (M.) Lu, H.M. Cheng, and I. R. Gentle, Phys. Chem. Chem. Phys., 14, 8703 (2012). 25. D.W. Wang, Q. Zeng, G. Zhou, L. Yin, F. Li, H.M. Cheng, I. R. Gentle, and G. Q. M. Lu, J. Mater. Chem. A, 1, 9382 (2013). 26. S. Freunberger, Y. Chen, Z. Peng, J. M. Griffin, L. J. Hardwick, F. Bardé, P. Novák, and P. G. Bruce, J. Am. Chem. Soc., 133, 8040 (2011). 27. D. Sharon, D. Hirshberg, M. Afri, A. Garsuch, A. A. Frimer, and D. Aurbach, Isr. J. Chem., 55, 508 (2015). 28. J. Read, J. Electrochem. Soc., 153, A96 (2006). 29. M. J. Trahan, S. Mukerjee, E. J. Plichta, M. A. Hendrickson, and K. M. Abraham, J. Electrochem. Soc., 160, A259 (2012). 30. S. A. Freunberger, Y. Chen, N. E. Drewett, L. J. Hardwick, F. Bardé, and P. G. Bruce, Angew. Chem. Int. Ed. Engl., 50, 8609 (2011). 31. J. M. García, H. W. Horn, and J. E. Rice, J. Phys. Chem. Lett., 6, 1795 (2015). 32. D. Sharon, V. Etacheri, A. Garsuch, M. Afri, A. A. Frimer, and D. Aurbach, J. Phys. Chem. Lett., 4, 127 (2013). 33. B. D. Adams, R. Black, Z. Williams, R. Fernandes, M. Cuisinier, E. J. Berg, P. Novak, G. K. Murphy, and L. F. Nazar, Adv. Energy Mater., 5, 1400867 (2015). 34. Z. Zhang, J. Lu, R. S. Assary, P. Du, H.H. Wang, Y.K. Sun, Y. Qin, K. C. Lau, J. Greeley, P. C. Redfern, H. Iddir, L. A. Curtiss, and K. Amine, J. Phys. Chem. C, 115, 25535 (2011). 35. D. Sharon, P. Sharon, D. Hirshberg, M. Salama, M. Afri, L. J. W. Shimon, W.J. Kwak, Y.K. Sun, A. A. Frimer, and D. Aurbach, J. Am. Chem. Soc., 139, 11690 (2017). 36. K. U. Schwenke, S. Meini, X. Wu, H. Gasteiger, and M. Piana, Phys. Chem. Chem. Phys., 15, 11830 (2013). 37. D. Sharon, D. Hirshberg, M. Afri, A. A. Frimer, and D. Aurbach, Chem. Commun., 53, 3269 (2017). 38. Z. Peng, S. A. Freunberger, Y. Chen, and P. G. Bruce, Science, 337, 563 (2012). 39. M. M. Ottakam Thotiyl, S. A. Freunberger, Z. Peng, Y. Chen, Z. Liu, and P. G. Bruce, Nat. Mater., 12, 1050 (2013). 40. D. Sharon, M. Afri, M. Noked, A. Garsuch, A. A. Frimer, and D. Aurbach, J. Phys. Chem. Lett., 4, 3115 (2013). 41. L. Johnson, C. Li, Z. Liu, Y. Chen, S. A. Freunberger, J.M. Tarascon, P. C. Ashok, B. B. Praveen, K. Dholakia, and P. G. Bruce, Nat. Chem., 6, 1091 (2014). 42. C. M. Burke, V. Pande, A. Khetan, V. Viswanathan, and B. D. McCloskey, Proc. Natl. Acad. Sci., 112, 9293 (2015). 43. D. Sharon, D. Hirsberg, M. Salama, M. Afri, A. A. Frimer, M. Noked, W.J. Kwak, Y.K. Sun, and D. Aurbach, ACS Appl. Mater. Interfaces, 8, 5300 (2016).

44. J. B. Park, S. H. Lee, H. G. Jung, D. Aurbach, and Y. K. Sun, Adv. Mater., 30, 1 (2018). 45. H. Lim, H. Song, J. Kim, H. Gwon, Y. Bae, K. Park, J. Hong, H. Kim, T. Kim, Y. H. Kim, X. Lepró, R. OvalleRobles, R. H. Baughman, and K. Kang, Angew. Chem. Int. Ed. Engl., 53, 3926 (2014). 46. W.J. Kwak, D. Hirshberg, D. Sharon, M. Afri, A. A. Frimer, H.G. Jung, D. Aurbach, and Y.K. Sun, Energy Environ. Sci., 9, 2334 (2016). 47. W.J. Kwak, H. Kim, H.G. Jung, D. Aurbach, and Y.K. Sun, J. Electrochem. Soc. 165, A2274 (2018). 48. R. Attias, M. Salama, B. Hirsch, Y. Goffer, and D. Aurbach, Joule, 3, 27 (2019). 49. I. Shterenberg, M. Salama, Y. Gofer, E. Levi, and D. Aurbach, MRS Bull., 39, 453 (2014). 50. H. D. Yoo, I. Shterenberg, Y. Gofer, G. Gershinsky, N. Pour, and D. Aurbach, Energy Environ. Sci., 6, 2265 (2013). 51. L. W. Gaddum and H. E. French, J. Am. Chem. Soc., 49, 1295 (1927). 52. T. D. Gregory, J. Electrochem. Soc., 137, 775 (2006). 53. D. Aurbach, Electrochem. Solid-State Lett., 3, 31 (2002). 54. D. Aurbach, Z. Lu, A. Schechter, Y. Gofer, H. Gizbar, R. Turgeman, Y. Cohen, M. Moshkovich, and E. Levi, Nature, 407, 724 (2000). 55. D. Aurbach, H. Gizbar, V. Marks, H. E. Gottlieb, O. Chusid, Y. Gofer, and Y. Viestfrid, Electrochem. Solid-State Lett., 9, A257 (2006). 56. M. Salama, I. Shterenberg, L. J. W. Shimon, K. KeinanAdamsky, M. Afri, Y. Gofer, and D. Aurbach, J. Phys. Chem. C, 121, 24909 (2017). 57. C. Liebenow, Z. Yang, and P. Lobitz, Electrochem. Commun., 2, 641 (2000). 58. H. S. Kim, T. S. Arthur, G. D. Allred, J. Zajicek, J. G. Newman, A. E. Rodnyansky, A. G. Oliver, W. C. Boggess, and J. Muldoon, Nat. Commun., 2, 427 (2011). 59. R. E. Doe, R. Han, J. Hwang, A. J. Gmitter, I. Shterenberg, H. D. Yoo, N. Pour, and D. Aurbach, Chem. Commun., 50, 243 (2014). 60. S. Y. Ha, Y. W. Lee, S. W. Woo, B. Koo, J. S. Kim, J. Cho, K. T. Lee, and N. S. Choi, ACS Appl. Mater. Interfaces, 6, 4063 (2014). 61. L. J. W. Shimon, H. Gizbar, M. Salama, D. T. Major, M. Afri, I. Shterenberg, D. Aurbach, K. KeinanAdamsky, N. N. Eliaz, H. E. Gottlieb, Y. Gofer, and M. Kosa, J. Phys. Chem. C, 120, 19586 (2016). 62. H. D. Yoo, I. Shterenberg, M. Salama, Y. Gofer, Y.K. Sun, J.B. Park, and D. Aurbach, J. Electrochem. Soc., 162, A7118 (2015). 63. R. Mohtadi, M. Matsui, T. S. Arthur, and S. J. Hwang, Angew. Chemie - Int. Ed., 51, 9780 (2012). 64. S. Shirai, F. Mizuno, R. Mohtadi, T. J. Carter, R. Zhang, J. W. Kampf, and T. S. Arthur, Angew. Chemie Int. Ed., 53, 3173 (2014). 65. Y. Gofer, R. Pant, R. Attias, B. Hirsch, D. Aurbach, and M. Salama, ACS Energy Lett., 4, 209 (2018). 66. R. Attias, M. Salama, B. Hirsch, Y. Gofer, and D. Aurbach, ChemElectroChem, 5, 3514 (2018).

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Awards, Fellowships, Grants ECS distinguishes outstanding technical achievements in electrochemistry, solid state science and technology, and recognizes exceptional service to the Society through the Honors & Awards Program. Recognition opportunities exist in the following categories: Society Awards, Division Awards, Student Awards, and Section Awards. ECS recognizes that today’s emerging scientists are the next generation of leaders in our field and offers competitive Fellowships and Grants to allow students and young professionals to make discoveries and shape our science long into the future.

See highlights below and visit www.electrochem.org for further information.

Society Awards The ECS Edward Goodrich Acheson Award was established in 1928 for distinguished contributions to the advancement of any of the objects, purposes, or activities of The Electrochemical Society. The award consists of a gold medal and a plaque that contains a bronze replica thereof, a $10,000 prize, Society life membership, and complimentary meeting registration. Materials are due by October 1, 2019. The ECS Charles W. Tobias Young Investigator Award was established in 2003 to recognize outstanding scientific and/or engineering work in fundamental or applied electrochemistry or solid state science and technology by a young scientist or engineer. The award consists of a framed certificate, a $5,000 prize, Society life membership, complimentary meeting registration, and travel assistance to the designated meeting. Materials are due by October 1, 2019.

Division Awards The ECS Electronics and Photonics Division Award was established in 1969 to encourage excellence in electronics research and outstanding technical contribution to the field of electronics science. The award consists of a framed certificate, a $1,500 prize, and the option of up to $1,000 to facilitate travel to the designated meeting for recognition or life membership. Materials are due by August 1, 2019. The ECS Energy Technology Division Research Award was established in 1992 to encourage excellence in energy-related research. The award consists of framed certificate, a $2,000 prize, and membership in the Energy Technology Division for as long as the recipient is an ECS member. Materials are due by September 1, 2019.

The ECS Energy Technology Division Supramaniam Srinivasan Young Investigator Award was established in 2011 to recognize and reward an outstanding young researcher in the energy technology field. The award consists of a framed certificate, a $1,000 prize, and complimentary meeting registration. Materials are due by September 1, 2019. The SES Research Young Investigator Award of the ECS Nanocarbons Division was established in 2007 to recognize and reward one outstanding young researcher in the field of fullerenes, carbon nanotubes, and carbon nanostructures. The award consists of a framed certificate, a $500 prize, and complimentary meeting registration. Materials are due by September 1, 2019. The ECS Nanocarbons Division Robert C. Haddon Research Award was established in 2018 to recognize individuals who have made outstanding contributions to the understanding and applications of carbon materials. The award consists of a framed certificate, a $1,000 prize, and a maximum of $1,500 to facilitate attendance of the meeting at which the award is to be presented. Materials are due by September 1, 2019. The ECS Physical and Analytical Electrochemistry Division David C. Grahame Award was created in 1981 to encourage excellence in physical electrochemistry research and to stimulate publication of high-quality research papers in the Journal of The Electrochemical Society. The award consists of a framed certificate and a $1,500 prize. Materials are due by October 1, 2019. The ECS Corrosion Division Herbert H. Uhlig Award was established in 1972 to recognize excellence in corrosion research and outstanding technical contributions to the field of corrosion science and technology. The award consists of a framed certificate, a $1,500 prize, and possible travel assistance. Materials are due by December 15, 2019. (continued on next page)

The Electrochemical Society Interface • Summer 2019 • www.electrochem.org

AWARDS PROGRAM (continued from previous page)

Student Awards The ECS Georgia Section Outstanding Student Achievement Award was established in 2011 to recognize academic accomplishments in any area of science or engineering in which electrochemical and/or solid state science and technology is the central consideration. The award consists of a $500 prize. Materials are due by August 15, 2019. The ECS Energy Technology Division Graduate Student Award sponsored by Bio-Logic was established in 2012 to recognize promising young engineers and scientists in fields pertaining to this division. The award consists of a framed certificate, a $1,000 prize, complimentary student meeting registration, and complimentary admission to the Energy Technology Division business meeting. Materials are due by September 1, 2019. The ECS Industrial Electrochemistry and Electrochemical Engineering Division Student Achievement Award was established in 1989 to recognize promising young engineers and scientists in the field of electrochemical engineering. The award consists of a framed certificate and a $1,000 prize. Materials are due by September 15, 2019. The ECS Industrial Electrochemistry and Electrochemical Engineering Division H. H. Dow Memorial Student Achievement Award was established in 1990 to recognize promising young engineers and

scientists in the field of electrochemical engineering and applied electrochemistry. The award consists of a framed certificate and a $1,000 prize to be used for expenses associated with the recipient’s education or research project. Materials are due by September 15, 2019. The ECS Korea Section Student Award was established in 2005 to recognize academic accomplishments in any area of science or engineering in which electrochemical and/or solid state science and technology is the central consideration. The award consists of a $500 prize. Materials are due by September 30, 2019. The ECS India Section S. K. Rangarajan Graduate Student Award was established in 2017 to assist a deserving student in India to pursue a career in disciplines related to electrochemistry and solid state science and technology. The award consists of a $500 prize. Materials are due by September 30, 2019. The ECS Corrosion Division Morris Cohen Graduate Student Award was established in 1991 to recognize and reward outstanding graduate research in the field of corrosion science and/or engineering. The award consists of a certificate and the sum of $1,000. The award, for outstanding master’s or PhD work, is open to graduate students who have successfully completed all the requirements for their degrees, as testified to by the students’ advisers, within a period of two years prior to the nomination submission deadline. Materials are due by December 15, 2019.

Charles W. Tobias Young Investigator Award

Minkyu Kim

2019 Winner of the ECS Korea Section Student Award Minkyu Kim is a PhD student in the Department of Materials Science and Engineering at the Pohang University of Science and Technology. As a PhD candidate under Byoungwoo Kang, he has been working on developing high energy density cathode material based on promising 3.9V fully cation-disordered triplite LiFeSO4F for lithium-ion battery. Kim tried to understand the reason why fully cation-disordered materials, triplite LiFeSO4F, show good electrochemical performances such as high rate capability. Based on this understanding, his study clearly demonstrates that certain types of the cation disorder can be more easily controlled and then fully exploited to achieve full electrochemical performance, an unlikely general belief on the cation-disordered materials. This will extend the scope of electrode materials to the cation-disordered materials in addition to the cation-ordered materials.

Nomination Deadline: October 1, 2019 The Electrochemical Society Interface • Summer 2019 • www.electrochem.org

NE W MEMBERS ECS is proud to announce the following new members for January, February, and March 2019.

Members

Asem Abdulahad, New Orleans, LA, United States Taner Akbay, Fukuoka, Fukuoka, Japan Bihag Anothumakkool, Eindhoven, Noord Bra, Netherlands Netz Arroyo, Baltimore, MD, United States Philip Ash, Oxford, Oxfordshire, United Kingdom Cesar Barbero, Rio Cuarto, Cordoba, Argentina Louise Berben, Davis, CA, United States Sibani Biswal, Houston, TX, United States Pierre-Yves Blanchard, Montpellier, Occitanie, France Marina Cabrini, Dalmine (BG), Lombardia, Italy C Barry Carter, Coventry, CT, United States Tzu-Hsuan Chang, Atlanta, GA, United States Wiebren De Jong, Delft, Zuid Holl, Netherlands Qiuchen Dong, Saint Paul, MN, United States James Duchamp, Emory, VA, United States John Freiderich, Oak Ridge, TN, United States Dongsheng Geng, Beijing, Hebei, China Johanna Goodman, Lincoln, MA, United States Branimir Grgur, Belgrade, Serbia Don-Hyung Ha, Seoul, Gyeonggi, South Korea Nathan Hahn, Albuquerque, NM, United States Ray Hicks, Ormond Beach, FL, United States Tomohiro Higashino, Sakyo Ward, Kyoto, Japan Ian Hosein, Syracuse, NY, United States Shu Hu, New Haven, CT, United States Akihiro Ishii, Wako, Japan Charl Jafta, Oak Ridge, TN, United States Kun Jiang, Berkeley, CA, United States T Jow, Adelphi, MD, United States Somayyeh Kalami, Austin, TX, United States Yuichiro Kato, Wako, Saitama, Japan Yumiko Kawano, Kofu, Yamanashi, Japan Edwin Khoo, Singapore, Singapore David Baekyun Kim, Sacramento, CA, United States Tae-Hyun Kim, Incheon, Gyeonggi, South Korea Younghee Kim, Los Alamos, NM, United States Alexander Kneer, Kirchheim, BademWurttemberg, Germany Dong-Kyun Ko, Millburn, NJ, United States

Leeor Kronik, Rehovoth, Israel Jie Lin, Oxford, Oxfordshire, United Kingdom Long Luo, Troy, MI, United States G Madhavi, Tirupati, AP, India Weijie Mai, Golden, CO, United States Guangzhao Mao, Detroit, MI, United States Thomas Markland, Stanford, CA, United States María Martinez-Ibanez, Vitoria-Gasteiz, Alava, Spain Ricardo Matute, Santiago, RM, Chile Philip Mousley, Didcot, Oxfordshire, United Kingdom David Naughton, Orion, MI, United States Eun-Suok Oh, Ulsan, South Gyeongsang, South Korea Hiroshi Okano, Takamatsu, Kanagawa, Japan Athanasios Papaderakis, Thessaloniki, Greece Eun Joo Park, Santa Fe, NM, United States Mukul Parmananda, West Lafayette, IN, United States Anisha Patel, Coventry, United Kingdom Prashanth Poddutoori, Duluth, MN, United States Kaius Polikarpus, Grand Blanc, MI, United States Kamal Prakash, Houston, TX, United States Charlie Ren, Chicago, IL, United States Nathan Rourke, El Cajon, CA, United States Justin Sambur, Fort Collins, CO, United States Lingzi Sang, Edmonton, AB, Canada Marie-Pierre Santoni, Paris, Ile-de-France, France Hitoshi Shiku, Sendai, Miyagi, Japan Meenesh Singh, Chicago, IL, United States Stephen Smith, Easley, SC, United States Samuel Sudler, Elkridge, MD, United States Chun Tan, London, England, United Kingdom Yong Teck Tan, Singapore, Singapore Selvamani Vadivel, Wangchan, Rayong, Thailand Keti Vezzù, Padova, Veneto, Italy Masaki Wadaguchi, Cambridge, MA, United States Jian Wang, Hefei, Anhui, China Min Wang, Golden, CO, United States Steve Weiss, Fall River, MA, United States Natalie Wint, Swansea, Swansea, United Kingdom Changshi Xiao, Wuhan, China Yoko Yamakoshi, Zuerich, Switzerland Mengyu Yan, Seattle, WA, United States Gaoqiang Yang, Tullahoma, TN, United States

The Electrochemical Society Interface • Summer 2019 • www.electrochem.org

Guang Yang, Oak Ridge, TN, United States Venkata Raviteja Yarlagadda, Rochester, MI, United States Matthias Young, Columbia, MO, United States gloria zanotti, Monterotondo Scalo, Italy, Italy Jana Zaumseil, Heidelberg, Baden Wur, Germany Menglian Zheng, Hangzhou, Zhejiang, China Hong Zhou, Belmont, MA, United States Yunlong Zi, Shatin, NT, Hong Kong

Students

Abhilash A, Cochin, Kerala, India Sreejith A Y, Cochin, Kerala, India Miguel AbregoTello, Fayetteville, AR, United States Sreekumar Achary, Kochi, Kerala, India Keegan Adair, London, ON, Canada Rachyl Adams, Crown Point, IN, United States Ashish Agarwal, Hsinchu City, Hsinchu, Taiwan Harsh Agarwal, Ann Arbor, MI, United States Nashaat Ahmed, New Cairo, Cairo, Egypt Taher Al Najjar, New Cairo, Cairo, Egypt Kristen Alanis, Bloomington, IN, United States Sasha Alden, Bloomington, IN, United States Basant Ali, Alexandria, Alexandria, Egypt Noura Alkhaldi, Arlington, TX, United States Mustafa Alsalem, London, England, United Kingdom Faisal Alzahrani, Leeds, United Kingdom Aya Amin, Alexandria, Alexandria, Egypt Kiana Amini, Waterloo, ON, Canada Samson Anuchi, London, England, United Kingdom Soha Anwar, New Cairo, Cairo, Egypt Islam Asselah, Saint-leonard, QC, Canada Nada Atef, Asharquia, Sharqia, Egypt Maria Aviles, London, ON, Canada Hazem Badawy, New Cairo, Cairo, Egypt Zhenyuan Bai, Harbin, Heilongjiang, China Samuel Baker, Sleepy Hollow, IL, United States Nandan Baradanahalli Kenchappa, Potsdam, NY, United States Austin Barnes, Goleta, CA, United States Joshua Beeler, Bloomington, IN, United States Jose Belisario, Miami, FL, United States Ido Ben-Barak, Tel Aviv, Israel Romil Bhandavat, Beaverton, OR, United States (continued on next page) 81

NE W MEMBERS (continued from previous page)

Tynee Bhowmick, Kharagpur, WB, India Lindsay Braithwaite, London, ON, Canada Alfredo Cepeor, Miami, FL, United States Vinicius Cerveira, Porto Alegre, Rio Grande do Sul, Brazil Averey Chan, London, England, United Kingdom Ho Lun Chan, Rosemead, CA, United States Shuen-Wen Chan, Hsinchu City, Taiwan Uttam Chanda, Bhubaneswar, Odisha, India Wesley Chang, Princeton, NJ, United States Yvonne Chart, Evanston, IL, United States Ke Chen, Brookings, SD, United States Qian Chen, East Lansing, MI, United States Shuo-Wen Chen, Hsinchu City, Taiwan Poramane Chiochan, Bangkok, Bangkok, Thailand Jin Yi Choi, Seoul, Gyeonggi, South Korea, Richard Chukwu, Tallinn, Estonia Jacy Conrad, Guelph, ON, Canada Marc Cormier, Halifax, NS, Canada Tommaso Costantini, London, England, United Kingdom Georgi Cowan, Tallahassee, FL, United States Tongming CUI, Shanghai, China, China Jin Dai, East Lansing, MI, United States Himadri Das, Kalapet, TN, India Shuvodeep De, Tuscaloosa, AL, United States Peter Defnet, Kirkland, WA, United States Abera Demeke, Johannesburg, Gauteng, South Africa Ramila Devi, Chennai, TN, India Joao Luiz Diverio Feijo, Porto Alegre, Rio Grande do Sul, Brazil Anna Dobkowska, London, ON, Canada Anthony Dragun, Austin, TX, United States Jonathan Edwards, Aurora, ON, Canada Farah El Diwany, Alexandria, Alexandria, Egypt Rodrigo Elizalde Segovia, Los Angeles, CA, United States Manar El-Naggar, New Cairo, Cairo, Egypt Jake Entwistle, Rossendale, United Kingdom Evan Erickson, Austin, TX, United States Nicolas Eshraghi, Liege, Wallonia, Belgium Anna Espinoza Tofalos, Milano, Italy, Italy Sherif Fahmy, Nasr City, Cairo, Egypt Chaker Fares, Gainesville, FL, United States Conner Fear, Lafayette, IN, United States Alexis Fenton, Jr., Cambridge, MA, United States Alba Maria Ferna¡ndez-Sotillo, Madrid, Madrid, SPAIN Aura Figueroa, Mexico City, D.F., Mexico Miriam Figueroa-Santos, Ann Arbor, MI, United States Kae Fink, Lakewood, CO, United States

Charlotte Flatebo, Houston, TX, United States Paraskevi Flouda, College Station, TX, United States Juan Forero-Saboya, Bellaterra, Catalonia, Spain Rebecca Frederick, Plano, TX, United States Anu Garg, Arlington, TX, United States Katarina Gavalierova, Kosice, Slovakia Lijin George, Kochi, Kerala, India Sajjad Ghobadi, Richmond, VA, United States Timothy Goh, Stanford, CA, United States Ritambhara Gond, Bangalore, KA, India Jonathan Grunewald, Atlanta, GA, United States Joaquin Guillamon, Kingsville, TX, United States Niloofar Hamzelui, Aachen, North RhineWestphalia, Germany Md Alamgir Mojibul Haque, Athens, OH, United States Robyn Hollfelder, Austin, TX, United States Taylor Hope, Montreal, QC, Canada Cheng Ta Hsieh, Hsinchu, Taiwan, Taiwan Kaixiang Huang, Bloomington, IN, United States Hanyu Huo, London, ON, Canada Siavash Jafarzadeh, Lincoln, NE, United States Li Jiao, Boston, MA, United States Matthew Jordan, Baton Rouge, LA, United States Frenson Jose, Muvattupuzha, Kerala, India Woohyeon Kang, Seoul, Gyeonggi, South Korea Katerina Karmazinova, Brno, South Mor, Czech Republic Priya Karna, Barbourville, KY, United States MD Niazul Islam Khan, Somersworth, NH, United States Chams Kharbachi, Toulouse, Occitanie, France Soochan Kim, Suwon, Gyeonggi, South Korea Alexander Klementiev, Atlanta, GA, United States Udari Kodithuwakku Arachchige, Lexington, KY, United States Snehal Kolhekar, New York, NY, United States Alessandra Konrath, Porto Alegre, Rio Grande do Sul, Brazil Isaac Kretzmer, Seattle, WA, United States Atiweena Krittayavathananon, Wangchan, Rayong, Thailand Krishnapriya Kuttykrishnan, Palakkad, Kerala, India Martina Kvitkovicova, Tallahassee, FL, United States

Jianwei Lai, Baton Rouge, LA, United States John LaJoie, Tallahassee, FL, United States Benjamin Lambert, Lausanne, Vaud, Switzerland Cody Landry, Beresford, NB, Canada Giang Le, Seattle, WA, United States Ryan Lee, Bloomington, IN, United States Sydney Legge, London, ON, Canada Baochen Li, Seattle, WA, United States Feng Li, Waterloo, ON, Canada Hongyang Li, Halifax, NS, Canada Junjie Li, London, ON, Canada Mingqian Li, College Station, TX, United States Hangqi Liao, Gainesville, FL, United States Hwai En Lin, Meguro-ku, Tokyo, Japan John Lin, Stanford, CA, United States Xiaoqian Lin, London, England, United Kingdom Baichen Liu, Hangzhou, Zhejiang, China Chia-Chen Liu, Hsinchu City, Taiwan Ershuai Liu, Boston, MA, United States Xinye Liu, Arlington, VA, United States Natalia Lopes, Porto Alegre, Rio Grande do Sul, Brazil Sarah Lowe, London, England, United Kingdom Matthew Lu, Evanston, IL, United States Bingyuan Ma, Saint Louis, MO, United States Jiarong Ma, Shanghai, China, China Oluwaniyi Mabayoje, Austin, TX, United States Mohamed Mandour, Mokattam City, Cairo, Egypt Rafaela Marques, Porto Alegre, Rio Grande do Sul, Brazil Edward Matios, Hanover, NH, United States James McAllister, Glasgow, Scotland, United Kingdom Danielle McRae, London, ON, Canada Carolina Menezes, Porto Alegre, Rio Grande do Sul, Brazil Xiaotong Meng, London, England, United Kingdom Rajesh Menon M. R, Kochi, KL, India Laurence Middlemiss, Sheffield, South Yorkshire, United Kingdom Veronika Mikhaylova, San Diego, CA, United States Allie Mikos, Geneva, IL, United States Ji Yun Min, Seoul, South Korea Boshan Mo, Boston, MA, United States Shaswat Mohanty, Mumbai, MH, India Santanu Mondal, Miami, FL, United States Austen Moss, Flower Mound, TX, United States Nadin Moustafa, London, London, United Kingdom Caroline Mueller, Mineola, NY, United States

The Electrochemical Society Interface • Summer 2019 • www.electrochem.org

NE W MEMBERS Logan Mulderrig, Tallahassee, FL, United States De-Shaine Murray, London, England, United Kingdom Nomaan Nabi, London, England, United Kingdom Tatsuichiro Nakamoto, Sendai, Miyagi, Japan Fei Ning, Shanghai, China, China Archith Nirmalchandar, Los Angeles, CA, United States Sibo Niu, San Marcos, TX, United States Nazgol Norouzi, Richmond, VA, United States Chance Norris, West Lafayette, IN, United States David Novak, Pervenka, Moravia, Czech Republic Tyler Nugen, Indianapolis, IN, United States Rose Oates, London, England, United Kingdom Brian O’Farrell, Southwest Ranches, FL, United States Nelson Okpowe, Miami, FL, United States Pengfei Ou, Montreal, QC, Canada Sebnem Ozbek, Rapid City, SD, United States Rahul Pai, Philadelphia, PA, United States Yu-Ping Pao, Hsinchu City, Taiwan Benjamin Paren, Philadelphia, PA, United States Eun Ji Park, Ansan, Gyeonggi, South Korea Sungguk Park, Seoul, Gyeonggi, South Korea Rajesh Pathak, Brookings, SD, United States Ksenia Pavlova, La Jolla, CA, United States Kevin Peuvot, Stockholm, Uppland, Sweden Nutthaphon Phattharasupakun, Wangchan, Rayong, Thailand Lisa Pierinet, Grenoble, Isere, France Ilana Porter, Hayward, CA, United States Madalyn Puckett, Orland Hills, IL, United States Milla Puolamaa, London, Gtr London, United Kingdom Ratheesh R, Ernakulam, Kerala, India Aldyla Raditya, London, England, United Kingdom Ayda Rafie, Ardmore, PA, United States Md Sohel Rana, Lexington, KY, United States Md Golam Rasul, Chicago, IL, United States Dalius Ratautas, Vilnius, Lithuania Lennart Reuter, Garching, Bavaria, Germany Ramin Rojaee, Chicago, IL, United States Indroneil Roy, Elmhurst, NY, United States Prantik Saha, Irvine, CA, United States Touhami Salah, Vandœuvre-les-Nancy, Lorraine, France

Yasamin Salamat, Boston, MA, United States Mahmoud Saleh, Mallawi, El Minia, India Nora Sanchez-Padilla, Saltillo, Coahuila, Mexico Vivek Saraswat, Madison, WI, United States Mrittunjoy Sarker, Merced, CA, United States Swathy Sassendran, Muvattupuzha, Kerala, India Leanna Schulte, Irvine, CA, United States Kevin Schweinar, Duesseldorf, North Rhine-Westphalia, Germany Christian Sedlmeier, Garching, Baveria, Germany Nora Shaheen, Cleveland Heights, OH, United States Wei Shang, Cayce, SC, United States Shikha Sharma, Bangalore, Karnataka, India Xuyang Shen, London, England, United Kingdom Vishal Shrivastava, Amritsar, Punjab, India Abhinav Shukla, College Station, TX, United States Bo Si, Durham, NH, United States Prabhakar Sidambaram, Dublin, Leinster, Ireland Natasha Siepser, Bloomington, IN, United States Benedict Simon, London, England, United Kingdom Stephan Sinzig, Munich, Baveria, Germany Pichamon Sirisinudomkit, London, England, United Kingdom Daniela Solano, Tallahassee, FL, United States Yoon Jun Son, Austin, TX, United States Lucas Souto, Porto Alegre, Rio Grande do Sul, Brazil Taylor Stamm, Tallahassee, FL, United States Nathaniel Stanley, Tallahassee, FL, United States Jia Quan Su, College Station, TX, United States Xiaoyu Sui, Milwaukee, WI, United States Yipeng Sun, London, ON, Canada Poonam Sundriyal, Kanpur, UP, India Sandeep Sundriyal, Roorkee, UT, India Shashank Sundriyal, Dehradun, UT, India Manar Taha, Mokattam, Cairo, Egypt Rupesh Tamgadge, New Delhi, DL, India Shibi Thomas, Ernakulam, Kerala, India Zenzele Thomas, Tallahassee, FL, United States Yumeng Tian, Harbin, Heilongjiang, China Chanikarn Tomon, Wangchan, Rayong, Thailand Fabio Trinddad, Tallahassee, FL, United States Dhruv Trivedi, Lancaster, Lancashire, United Kingdom

The Electrochemical Society Interface • Summer 2019 • www.electrochem.org

Chia-Ping Tseng, Houston, TX, United States Suchakree Tubtimkuna, Wangchan, Rayong, Thailand Nazym Tuleushova, Montpellier, Hauts-deFrance, France Victor Vanpeene, Varennes, Quebec, Canada Carlos Vargas, Miami Lakes, FL, United States Janine Viscardi, Gravataí, Rio Grande do Sul, Brazil Andreas Wagner, Cambridge, United Kingdom Cheng Wang, Potsdam, NY, United States Chuanlong Wang, Hanover, NH, United States Haizhen Wang, Las Cruces, NM, United States Qi Wang, Changsha Shi, Hunan, China Shaoyang Wang, College Station, TX, United States Austin Way, Madison, WI, United States Justin Weeks, Oxford, Oxon, United Kingdom Xiaochu Wei, London, England, United Kingdom Martha Welander, Bozeman, MT, United States Kuo Wen-Che, Hsinchu, Taiwan, Taiwan Evangeline Wheeler-Jones, Coventry, W Mids, United Kingdom Yanuar Philip Wijaya, Vancouver, BC, Canada Kody Wolfe, Nashville, TN, United States Chang-Run Wu, Hsinchu City, Taiwan Phatsawit Wuamprakhon, Wangchan, Rayong, Thailand Brian Wuille Bille, Davis, CA, United States Juthaporn Wutthiprom, Wangchan, Rayong, Thailand Muhang Xiao, London, England, United Kingdom Hengbin Xu, Harbin, Heilongjiang, China Cheng Yeh, Hsinchu City, Taiwan Shuaihang Yin, London, England, United Kingdom Wenyan Yin, Harbin, Heilongjiang, China Gayeon Yoo, Suwon, Gyeonggi, South Korea Sarah Youssef, New Cairo, Cairo, Egypt Li Zeng, Guelph, ON, Canada Jinfeng Zhang, Calgary, AB, Canada Kun Zhang, Shanghai, Jiangsu China Zhiyong Zheng, Kongens Lyngby, Byen Kobenhavn, Denmark Hu Zhou, Montreal, QC, Canada Cheng Zhu, Bloomington, IN, United States Di Zhu, Harbin, Heilongjiang, China (continued on next page)

NE W MEMBERS It is with great pleasure that we recognize the following ECS members who have

reached their 30, 40, 50, and 60 year anniversaries with the Society in 2019. Member Anniversaries Congratulations to all!

60 Year

Thomas F. Kassner Harvey N. Seiger Isaac Trachtenberg Aiji A. Uchiyama

50 Year

Richard C. Alkire Fred C. Anson Badr E. G. Ateya Wishvender K. Behl Klaus D. Beyer Robert F. Brebrick Stanley Bruckenstein Kathryn R. Bullock Ronald E. Enstrom James N. Fordemwalt Marco V. Ginatta Robert A. Huggins Chung-Chiun Liu Carl E. Mueller John S. Newman Kotaro Ogura Carlton M. Osburn Dirk Pouli William H. Smyrl Roy F. Thornton Rene Winand

40 Year

Kuzhikalail M. Abraham Viola I. Birss David P. D. Noel Buckley David L. Chua Dennis W. Dees Thomas D. Gregory Timothy E. Griffin Lin R. Higley Steven Hinckley Robert R. Krebs Johna Leddy Michael McNallan Richard L. Middaugh Tetsuya Osaka Noboru Oyama Fred C. Redeker Maria Skyllas-Kazacos Mark T. Spitler Gery R. Stafford James S. Symanski John Van Zee John S. Wilkes

30 Year

Prosper K. Adanuvor Mark D. Allendorf Radoslav Atanasoski Peter R. Bergethon Ratnakumar V. Bugga Jean-Noel Chazalviel John F. Cooper S Elangovan Manfred Engelhardt Ingrid Fritsch Hubert Gasteiger Ignacio Gonzalez Terry E. Haas Rika Hagiwara Peter J. Hesketh Takayuki Homma Egwu E. Kalu Kiyoshi Kanamura Joseph J. Kopanski Sol Krongelb Mark C. Lefebvre Dan Little Meilin Liu

Jingli Luo Daniel Mandler G. Nicola Martelli Junichiro Mizusaki Mogens Mogensen Theodore D. Moustakas Toshikazu Okubo Dharmasena Peramunage Gautam Pillay Romeu C. Rocha-Filho Michael J. Root Sudipta Roy Hossein Sharifian David A. Shifler Masao Sudoh Dominique Thierry Paul C. Trulove Flavio F. Villa Anil V. Virkar Joseph Yahalom

We want to hear from you! Send your student chapter news and high resolution photographs to Shannon.Reed@electrochem.org We’ll spread the word around the Society. Plus, your student chapter may also be featured in an upcoming issue of Interface!

www.electrochem.org/student-center

The Electrochemical Society Interface • Summer 2019 • www.electrochem.org

SAVE THE DATE 2019

236th ECS Meeting ATLANTA, GA

October 13-17, 2019 Hilton Atlanta

Early registration deadline: September 9, 2019

www.electrochem.org/236

Save the Date! 2020

PRiME 2020 Honolulu, HI

October 4-9, 2020

Hawaii Convention Center & Hilton Hawaiian Village

The joint international meeting of: 238th Meeting of The Electrochemical Society 2020 Fall Meeting of the Electrochemical Society of Japan 2020 Fall Meeting of the Korean Electrochemical Society Start making your plans now, the call for papers will be published in November 2019!

The Electrochemical Society Interface â&#x20AC;˘ Summer 2019 â&#x20AC;˘ www.electrochem.org

ST UDENT NE WS

ECS 2019 Summer Fellowships 2019 Edward G. Weston Fellowship Recipient

2019 Summer Fellowship Committee

Bilen Akuzum received his BSc degree with a magna cum laude from the Department of Metallurgical and Materials Engineering at Middle East Technical University in Ankara, Turkey. For the past five years, he has been pursuing his doctoral studies under the supervision of E. Caglan Kumbur and Yury Gogotsi at Drexel University, where he received the 2019 College of Engineering Outstanding PhD Student Award. Akuzum’s PhD research focuses on understanding the relationship between electrochemical and rheological characteristics of capacitive flowable (semi-solid) electrodes. During his studies, he has also focused on electrochemical diagnostics of flow-assisted electrochemical systems including redox flow battery and capacitive deionization technologies. As a recipient of the ECS summer fellowship, Akuzum will be traveling to Lawrence Berkeley National Laboratory in Berkeley, California, where he will work alongside Jeff Urban and Ashok Gadgil to develop a self-regenerative ion selective water purification technology for the treatment of brackish groundwater sources.

ECS thanks the 2019 Summer Fellowship Committee for its time and effort in selecting this year’s recipients:

2019 F. M. Becket Fellowship Recipient

2020 Summer Fellowship Dates

Vimal Chaitanya, Committee Chair Director, Energy Research Lab New Mexico State University, USA Peter Mascher Professor and William Sinclair Chair in Optoelectronics McMaster University, Canada David Hall Postdoctoral Researcher Dalhousie University, Canada Kalpathy Sundaram Professor and Graduate Coordinator University of Central Florida, USA

Ritambhara Gond obtained her undergraduate and postgraduate degrees in chemistry from the Banaras Hindu University in Varanasi, Uttar Pradesh, India, in 2008 and 2013, respectively. Gond is currently a final-year PhD student at the Indian Institute of Science in Bangalore, India. She has authored/coauthored eight journal articles. Her research interests include the synthesis, characterization, and electrochemical studies of pyrophosphate and metaphosphate-based cathode materials for batteries as well as electrocatalysts for rechargeable metal-ion and metal-air batteries.

Application opens September 2019

Application deadline January 15, 2020

Calgary Student Chapter The ECS Calgary Student Chapter organized a community engagement event to celebrate Free the Science Week on the morning of April 3, 2019, at the University of Calgary. The chapter’s main goal was to raise awareness about ECS’s Free the Science initiative to the broader community. The event featured free snacks and coffee, as well as a screening of the documentary Paywall: The Business of Scholarship by Jason Schmitt, which discusses the current state of the academic publishing industry as well as the benefits of open access. The event attracted students, professors, and researchers from the University of Calgary’s faculty of science and the Schulich School of Engineering. Additionally, the chapter’s committee members briefly discussed the benefits of joining ECS, resulting in a gain of seven new members. During Free the Science Week (April 1–7, 2019), articles in the ECS Digital Library were made freely available, making scientific research more accessible to everyone. Awareness of this event was especially important to researchers on campus who use electrochemistry in their work, as the University of Calgary Library currently does not have a subscription to all ECS publications. 86

Annie Hoang, vice president of the ECS Calgary Student Chapter, shared the importance of ECS’s Free the Science initiative with chapter members at the University of Calgary.

The Electrochemical Society Interface • Summer 2019 • www.electrochem.org

ECS STUDENT PROGRAMS Awarded Student Membership

Student Chapter Membership

Our divisions offer free memberships to full-time students.You can re-apply to receive an awarded student membership for up to four years!

Apply for a free student membership for those involved in active ECS student chapters.You must apply or re-apply each year for a student chapter membership.

Check out www.electrochem.org/student-center for qualifications! Biannual Meeting Travel Grants

Make the Connection

Many ECS divisions offer funding to undergraduates, graduate students, postdocs, and young professionals that are presenting research at ECS biannual meetings.

The ECS Career Expo gives students the opportunity to meet with interested employers and advance their job search with various career services.

Visit www.electrochem.org/travel-grants to learn more!

More information at www.electrochem.org/career-expo.

Summer Fellowships

Enhance Your Resume

Apply for a $5,000 summer fellowship with ECS! The annual deadline for applications is January 15.

ECS equips our student members to be successful when starting their careers. The professional development workshops provide attendees with skills not often learned in the classroom.

Review candidate qualifications at www.electrochem.org/summer-fellowships.

Student Chapters

View offerings on www.electrochem.org/education.

There are more than 75 student chapters worldwide. ECS offers funding to support chapter events! Find the guidelines for starting a student chapter at www.electrochem.org/student-center.

The Electrochemical Society Interface â&#x20AC;˘ Summer 2019 â&#x20AC;˘ www.electrochem.org

ST UDENT NE WS Lewis University Student Chapter For the ECS Lewis University Student Chapter, the 2018–2019 academic year was focused on sharing passion for science with the community. One of the chapter’s standout events was a haunted house-themed event held just before Halloween, where ECS members were able to integrate science into the Halloween experience. Each room in the haunted house incorporated themes such as forensics, astrophysics, and optics that children of all ages enjoyed. The attendees’ attention was initially caught by fluorescent solutions and a scare from an intense demonstration with peroxyacetone. Some of the other demonstrations included a forensic “crime scene,” Jacob’s Ladder, a Rube Goldberg machine, density demonstrations, constellation projections, and ionic flame tests. For a more hands-on experience, participants were also able to work their way through a laser maze, launch candy corn with a catapult they built, and have discussions with members about the science behind each demonstration. Approximately 400 people attended the event, which resulted in a successful canned food drive. The food collected was donated to a local food pantry. Dedicated to reaching out to the community, the Lewis University Student Chapter has held demonstration shows throughout the academic year at various schools and libraries that promote STEM. Several of the chapter’s members presented research at the 233rd ECS Meeting in Seattle, Washington, and were accepted to present at the 235th ECS Meeting in Dallas, Texas. Chapter members were excited to be featured in an ECS email advertising International Open Access Week for their support of the initiative. In January 2019, the chapter’s faculty advisor, Dr. Jason J. Keleher, graduate student Tala Zubi, and other ECS members published a manuscript titled “Unraveling Slurry Chemistry/Nanoparticle/ Polymeric Membrane Adsorption Relevant to Cu Chemical Mechanical Planarization (CMP) Filtration Applications” in the ECS Journal of Solid State Science and Technology.

Dr. Dan Kissel (left), Dr. Jason Keleher (right), and members of the ECS Lewis University Student Chapter posed with their 2018 ECS Chapter of Excellence Award plaque.

Munich Student Chapter The ECS Munich Student Chapter hosted its second panel discussion on October 23, 2018, on the topic “Fueling Tomorrow – Energy Supply for Future Mobility” at the Technical University of Munich (TUM). Invited guests included Christian Wulff (Audi), Andreas Peschel (Linde), Lukas Köhler (FDP), Daniel Zellinger (FlixBus), and Andreas Jossen (TUM). The group debated current and future issues surrounding fuel cell and battery electric vehicles, as well as the required refueling infrastructure and the possibilities it could offer. After a short introduction of the student chapter by moderators Johannes Sicklinger and Gregor Harzer, Jossen gave his keynote presentation on current technologies for battery electric charging, its future, and its limitations. Furthermore, he mentioned hydrogenrefueling concepts and compared them to electric charging technologies in terms of time requirement and large-scale applicability. After Jossen’s presentation, the other panelists gave short opening statements to set the stage for the panel discussion to follow. Wulff stated that fuel cell electric vehicles would be the best choice for long-range travel; however, their widespread prevalence depends on the installation of a nationwide refueling network. The production and distribution of hydrogen was addressed by Peschel, who pointed out that refueling options are technologically available, but there are very few customers, underlining the chicken or egg dilemma (which came first) of hydrogen fuel cell cars and their infrastructure. Political aspects of hydrogen and battery cars were elucidated by Köhler, who proclaimed that the aforementioned chicken or egg dilemma is 88

currently being approached by the government, which promotes the fueling infrastructure, at least for battery vehicles. He added that it would take time for drivers to accept electric cars on a large scale. In the final opening statement, Zellinger introduced the business model of FlixBus and the company’s future vision for battery or fuel cell electric buses for long-distance travel. During the following hour and a half, the panelists debated passionately on the different aspects of emission-free propulsion technologies and their impact on the automotive industry. More than once the discussion turned to the chicken or egg dilemma of electric cars and their charging infrastructure. Köhler expects that consumer behavior will change severely in future generations—particularly in the way that personal belongings such as cars or vacation homes are shared—giving rise to novel concepts of mobility. He believes that, in cities, car sharing with battery electric cars will be part of daily life, whereas for longer trips and vacations, rented fuel cell cars will likely be the preferred means of transportation. When the discussion came back to the chicken or egg dilemma, which exists for both fuel cell and battery electric cars, the representatives of industry and politics both pointed out the achievements made so far. Both parties agreed that large-scale changes take time. However, Jossen illustrated that China offers 100 times as many charging stations as Germany. In this context, Wulff proposed a joint plan of industry and politics to make electric vehicles more attractive to the customer. Additionally, Köhler suggested CO2 The Electrochemical Society Interface • Summer 2019 • www.electrochem.org

ST UDENT NE WS certificates or taxes to support the transformation towards emission-free mobility, since, in the end, consumers will make decisions based on the total cost of car ownership. In the case of electric buses, the situation appears to be even more complicated. Zellinger conveyed that it was extremely difficult for his company to find manufacturers of battery electric buses, whereas hydrogen-powered public transportation might be a less expensive solution in the future. Peschel stated that the government often subsidizes the investment for a hydrogen fueling station, although the operation of the fueling station is not subsidized. He explained that, due to the low amount of fuel cell cars, most The lively discussion between panelists at the Technical University of Munich was moderated by two members hydrogen fueling stations make a loss of the ECS Munich Student Chapter. From left to right: Gregor Harzer, student chapter member; Christian Wulff, Audi AG; Andreas Peschel, Linde AG; Lukas Köhler, member of Bundestag; Daniel Zellinger, in operation, and hardly anyone wants FlixMobility Experience GmbH; Andreas Jossen, Technical University of Munich; and Johannes to invest. Köhler added that the public Sicklinger, student chapter member. budget on hydrogen infrastructure has only been spent minimally so far. The Munich Student Chapter kindly thanks all the supporters of this All the panelists agreed that fuel cell (as well as battery) electric event. In particular, the chapter thanks the five panelists for their time vehicles will become much more widespread in the years to come and commitment, as well as ECS and Fakultätsgraduiertenzentrum and that emission-free mobility will require large investments in the Chemie for the financial support. future.

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The Electrochemical Society Interface • Summer 2019 • www.electrochem.org

Call for Papers

237th ECS Meeting

May 10-15, 2020

MONTRÉAL, CANADA Palais des Congrès Montréal

2020

with the 18th International Meeting on Chemical Sensors (IMCS 2020)

Abstract Submission Deadline: November 15, 2019 For more information, please contact abstracts@electrochem.org

General Information

The 237th ECS Meeting and the 18th International Meeting on Chemical Sensors (IMCS 2020) will be held in Montreal, Canada, May 10-15, 2020 at the Palais des Congrès de Montréal. This joint international conference will bring together scientists, engineers, and researchers from academia, industry, and government laboratories to share results and discuss issues on related topics through a variety of formats, such as oral presentations, poster sessions, panel discussions, tutorial sessions, short courses, professional development workshops, a career fair, and exhibits. The unique blend of electrochemical and solid state science and technology at this meeting will provide an opportunity and forum to learn and exchange information on the latest scientific and technical developments in a variety of interdisciplinary areas.

Abstract Submission

To give an oral or poster presentation at the 237th ECS Meeting and/or IMCS 2020, you must submit an original meeting abstract for consideration via the ECS website, https://ecs.confex.com/ecs/237/cfp.cgi no later than November 15, 2019. Faxed, e-mailed, and/or late abstracts will not be accepted. Meeting abstracts should explicitly state objectives, new results, and conclusions or significance of the work. Once the submission deadline has passed, the symposium organizers will evaluate all abstracts for content and relevance to the symposium topic, and will schedule all acceptable submissions as either oral or poster presentations. In January 2020, letters of acceptance/invitation will be sent via email to the corresponding author of all accepted abstracts, notifying them of the date, time, and location of their presentation. Regardless of whether you requested a poster or an oral presentation, it is the symposium organizers’ discretion to decide how and when it is scheduled.

Paper Presentation

Oral presentations must be in English; LCD projectors and laptops will be provided for all oral presentations. Presenting authors MUST bring their presentation on a USB flash drive to be used with the dedicated laptop that will be in each technical session room. Speakers requiring additional equipment must make written request to meetings@electrochem.org at least one month prior to the meeting so that appropriate arrangements may be worked out, subject to availability, and at the expense of the author. Poster presentations must be displayed in English, on a board approximately 3 feet 10 inches high by 3 feet 10 inches wide (1.17 meters high by 1.17 meters wide), corresponding to their abstract number and day of presentation in the final program.

Meeting Publications

ECS Meeting Abstracts—All meeting abstracts will be published and copyrighted by ECS, and all abstracts become the property of ECS upon presentation. ECS Transactions—Select symposia will be publishing their proceedings in ECS Transactions (ECST). Authors presenting in these symposia are strongly encouraged to submit a full-text manuscript based on their presentation. Issues of ECST will be available for sale on a pre-order basis, as well as through the digital library and the ECS online store. Please see each individual symposium listing in this Call for Papers to determine if your symposium will be publishing an ECST issue. Please visit the ECST website for additional information, including overall guidelines, author and editor instructions, a downloadable manuscript template, and more. ECSarXiv—All authors are encouraged to submit their full-text manuscripts, posters, slides, or data sets to ECS’s preprint service, ECSarXiv. For more information on this offering, please visit http://www.electrochem. org/ecsarxiv. Please note that submission to ECSarXiv does not preclude submission to ECST. ECS Journals—Authors presenting papers at ECS meetings, and submitting to ECST or ECSarXiv, are also encouraged to submit to the Society’s technical journals: Journal of The Electrochemical Society and ECS Journal of Solid State Science and Technology. Although there is no hard deadline for the submission of these papers, it is considered that six months from the date of the symposium is sufficient time to revise a paper to meet the stricter criteria of the journals. Author instructions are available from http://www.electrochem.org/submit. In partnership with IMCS 2020, ECS will publish a focus issue related to the meeting in the Journal of The Electrochemical Society. The call for papers release date is slated for May 2020. Visit www.electrochem.org/focusissues for up-to-date information on the IMCS 2020 issue.

Contact Information If you have any questions or require additional information, contact ECS.

Short Courses

Five short courses will be offered on Sunday, May 10, 2020, 0900-1630h. Short courses require advanced registration and may be cancelled if enrollment is under 10 registrants in the respective course. The following short courses are scheduled: (1) Basic Impedance Spectroscopy, (2) Fundamentals of Electrochemistry Basic Theory and Thermodynamic Methods, (3) Introduction to Micro/Nanofabrication, C-MEMS and Applications of Chemical Gas Sensors, (4) AC Electrical Measurements and Modelling of Gas Sensors, and (5) Electrochemical Biosensors. Registration opens February 2020.

Technical Exhibit

The 237th ECS Meeting and IMCS 2020 will include a technical exhibit, featuring presentations and displays by dozens of manufacturers of instruments, materials, systems, publications, and software of interest to meeting attendees. Coffee breaks are scheduled in the exhibit hall along with evening poster sessions. Interested in exhibiting at the meeting with your company? Exhibitor opportunities include unparalleled benefits and provide an extraordinary chance to present your scientific products and services to key constituents from around the world. Exhibit opportunities can be combined with sponsorship items and are customized to suit your needs. Please contact sponsorship@electrochem.org for further details.

Meeting Registration

All participants—including authors and invited speakers—are required to pay the appropriate registration fees. Hotel and meeting registration information will be posted on the ECS website as it becomes available. The deadline for discounted early registration is April 6, 2020.

Hotel Reservations

The 237th ECS Meeting and IMCS 2020 will be held at the Palais des Congrès de Montréal. Please refer to the meeting website for the most up-to date information on hotel availability and information about the blocks of rooms where special rates have been reserved for participants attending the meeting. The hotel block will be open until April 6, 2020 or until it sells out.

Letter of Invitation

In January 2020, letters of invitation will be sent via email to the corresponding authors of all accepted abstracts, notifying them of the date, time, and location of their presentation. Anyone else requiring an official letter of invitation should email abstracts@electrochem.org; such letters will not imply any financial responsibility of ECS.

Financial Assistance

ECS divisions and sections offer travel grants to students, postdoctoral researchers, and young professionals to attend ECS biannual meetings. Applications are available beginning November 1, 2019 at www.electrochem. org/travel-grants and must be received no later than the submission deadline of Monday, February 10, 2020. Additional financial assistance is very limited and generally governed by symposium organizers. Individuals may inquire directly to organizers of the symposium in which they are presenting to see if funding is available. For general travel grant questions, please contact travelgrant@electrochem.org.

Sponsorship Opportunities

ECS biannual and IMCS meetings offer a wonderful opportunity to market your organization through sponsorship. Sponsorship allows exposure to key industry decision makers, the development of collaborative partnerships, and potential business leads. ECS and IMCS welcomes support in the form of general sponsorship at various levels. Sponsors will be recognized by level in the meeting program, meeting signage, and on the website. In addition, sponsorships are available for the plenary, meeting keepsakes, and other special events. In addition, ECS and IMCS offer specific symposium sponsorship. By sponsoring a symposium your company can help offset travel expenses, registration fees, complimentary proceedings, and/or host receptions for invited speakers, researchers, and students. Advertising opportunities for the meeting program as well as in Interface magazine are also available. Please contact sponsorship@electrochem.org for further details.

The Electrochemical Society

65 South Main Street, Pennington, NJ, 08534-2839, USA tel: 1.609.737.1902, fax: 1.609.737.2743 meetings@electrochem.org

The Electrochemical Society Interface • Summer 2019 • www.electrochem.org

www.electrochem.org

237th ECS Meeting

with the 18th International Meeting on Chemical Sensors (IMCS 2020)

MONTRÉAL, CANADA

SYMPOSIUM TOPICS AND DEADLINES

May 10-15, 2020

Palais des Congrès de Montréal A— Batteries and Energy Storage A01— Battery and Energy Technology Joint General Session A02— Lithium Ion Batteries and Beyond A03— Large Scale Energy Storage 11 A04— Student Battery Slam 4 A05— Lead Acid Batteries B— Carbon Nanostructures and Devices B01— Carbon Nanostructures for Energy Conversion and Storage B02— Carbon Nanostructures in Medicine and Biology B03— Carbon Nanotubes - From Fundamentals to Devices B04— NANO in La Francophonie B05— Fullerenes - Endohedral Fullerenes and Molecular Carbon B06— 2D Layered Materials from Fundamental Science to Applications B07— Light Energy Conversion with Metal Halide Perovskites, Semiconductor Nanostructures, and Inorganic/Organic Hybrid Materials B08— Porphyrins, Phthalocyanines, and Supramolecular Assemblies B09— Nano for Industry C— Corrosion Science and Technology C01— Corrosion General Session D— Dielectric Science and Materials D01— Dielectrics for Nanosystems 8: Materials Science, Processing, Reliability, and Manufacturing D02— Nanoscale Luminescent Materials 6 D03— Surface Characterization and Manipulation for Electronic Applications 2 D04— Plasma Electrochemistry and Catalysis E— Electrochemical/Electroless Deposition E01— Surfactant and Additive Effects on Thin Film Deposition, Dissolution, and Particle Growth 2

L— Physical and Analytical Electrochemistry, Electrocatalysis, and Photoelectrochemistry L01— Physical and Analytical Electrochemistry, Electrocatalysis, and Photoelectrochemistry General Session L02— Electrocatalysis 10 L03— Biological Fuel Cells 9 L04— Nanoporous Materials 2 L05— Composite Electrodes L06— Electronic Structure Theory and Simulations for Energy and Electronics L07— Invited Perspectives and Tutorials on Electrolysis Z— General Z01— General Student Poster Session IMCS— 18th International Meeting on Chemical Sensors (IMCS 2020) IMCS 01—Artificial Intelligence, Machine Learning, Chemometrics, and Sensor Arrays IMCS 02—Chemical and Biosensors, Medical/Health, and Wearables 2020 IMCS 03—Electrochemical and Metal Oxide Sensors IMCS 04—Sensors for Agricultural and Environmental Applications IMCS 05—Recent Advances and Future Directions in Chemical and Bio Sensor Technology IMCS 06—Internet of Things, Infrastructure, and Signal Processing for Sensors IMCS 07—MEMS/NEMS, FET Sensors, and Resonators IMCS 08—Microfluidic Devices and Sensors IMCS 09—Optical Sensors, Plasmonics, Chemiluminescent, and Electrochemiluminescent Sensors IMCS 10—Sensors for Breath Analysis, Biomimetic Taste, and Olfaction Sensing IMCS 11—Chemical and Biosensing Materials and Sensing Interface Design

E02— Nucleation and Growth Processes Enabling Energy Conversion and Storage E03— Electrodeposition of Alloys, Intermetallic Compounds, and Eutectics F— Electrochemical Engineering F01— Advances in Industrial Electrochemistry and Electrochemical Engineering G— Electronic Materials and Processing G01— Silicon Compatible Materials, Processes, and Technologies for Advanced Integrated Circuits, Emerging Materials, and Devices for Post CMOS Applications 10 H— Electronic and Photonic Devices and Systems

IMPORTANT DATES AND DEADLINES Meeting abstract submission opens.............................................July 2019 Meeting abstracts submission deadline...................November 15, 2019 Notification to presenting authors of abstract acceptance or rejection................................. January 20, 2020

H01— Wide-Bandgap Semiconductor Materials and Devices 21

Technical program published online................................ January 27, 2020

H02— Advanced CMOS-Compatible Semiconductor Devices 19

Meeting registration opens.................................................. February 2020

H03— Solid-State Electronics and Photonics in Biology and Medicine 7

ECS Transactions manuscript submission site opens...................................................... January 27, 2020

I— Fuel Cells, Electrolyzers, and Energy Conversion I01— Electrosynthesis of Fuels 6: In Honor of Mogens Mogensen I02— Hydrogen or Oxygen Evolution Catalysis for Water Electrolysis 6 I03— Materials for Low Temperature Electrochemical Systems 6 I04— Renewable Fuels via Artificial Photosynthesis or Heterocatalysis 5 I05— Mechano-Electro-Chemical Coupling in Energy Related Materials and Devices 4 I06— Energy Conversion Systems Based on Nitrogen 3 K— Organic and Bioelectrochemistry K01— 14th Manuel M. Baizer Memorial Symposium on Organic Electrochemistry

Travel grant application deadline................................... February 10, 2020 ECS Transactions submission deadline..........................February 21, 2020 Meeting sponsor and exhibitor deadline (for inclusion in printed materials).................................February 28, 2020 Travel grant approval notification...................................... March 16, 2020 Hotel and early registration deadlines................................ April 6, 2020 Anticipated release date for ECS Transactions issues..............May 1, 2020 237th ECS Meeting with 18th International Meeting on Chemical Sensors (IMCS 2020).................................... May 10-15, 2020

K02— Electron-transfer Reactions in the Characterization of Biological Systems 92

The Electrochemical Society Interface • Summer 2019 • www.electrochem.org

ECS Institutional Members The Electrochemical Society values the support of its institutional members. These organizations help ECS support scientific education, sustainability, and innovation. Through ongoing partnerships, ECS will continue to lead as the advocate, guardian, and facilitator of electrochemical and solid state science and technology.

2019 Leadership Circle Awards Silver Level – 10 years

Gelest Inc.

Los Alamos National Laboratory Bronze Level – 5 years

El-Cell GmbH

Ford Motor Company

Benefactor

AMETEK-Scientific Instruments (38) Bio-Logic USA/Bio-Logic SAS (11) Duracell (62) Gamry Instruments (12) Gelest, Inc. (10) Hydro-Québec (12) Pine Research Instrumentation (13)

Sponsoring

BASi (4) Central Electrochemical Research Institute (26) DLR-Institut für Vernetzte Energiesysteme e.V. (11) EL-CELL GmbH (5) Ford Motor Corporation (5) GS Yuasa International Ltd. (39) Honda R&D Co., Ltd. (12) Medtronic Inc. (39) Nissan Motor Co., Ltd. (12) Panasonic Corporation, AIS Company (25) Permascand AB (16) Technic Inc. (23) Teledyne Energy Systems, Inc. (20) The Electrosynthesis Company, Inc. (23) Tianjin Lishen Battery Joint-Stock Co., Ltd. (5) Yeager Center for Electrochemical Sciences (21) ZSW (15)

Ion Power

Tianjin Lishen Battery Joint Stock Co., Ltd.

SanDisk

Patron 3M (30) Energizer (74) Faraday Technology, Inc. (13) GE Global Research Center (0) Lawrence Berkeley National Laboratory (15) Scribner Associates, Inc. (23) Toyota Research Institute of North America (11)

Sustaining Axiall Corporation (24) General Motors Holdings LLC (67) Giner, Inc./GES (33) Hydrogenics Corporation (0) IBM Corporation Research Center (62) Ion Power Inc. (5) Kanto Chemical Co., Inc. (7) Karlsruher Institut für Technologie (3) Leclanché SA (34) Los Alamos National Laboratory (11) Microsoft Corporation (2) Occidental Chemical Corporation (77) Sandia National Laboratories (43) SanDisk (5)

04/30/2019

Please help us continue the vital work of ECS by joining as an institutional member today. Contact Shannon.Reed@electrochem.org for more information.