BATTERY HEROES: STANLEY WHITTINGHAM The creation of the lithium ion battery cell was the work — often collaborative but equally often on a competitive basis — of a handful of scientists around the world. And Stanley Whittingham, as batteries historian Kevin Desmond reports, was one of that elite handful that can claim to be one of the lithium battery’s founding fathers.
Exxon, Whittingham and the joys of lithium It was so 1970s. Diversification was the new name of the corporate game. And, in 1972 it seemed a no-brainer for Exxon Research and Engineering to look at alternative energy production and storage. So, with the deepest pockets of perhaps the most profitable oil giant in the world, Exxon set about seeking the best scientists in the world for its project. And among this elite was a 31-yearold graduate, then a more than upand-coming researcher at Stanford University by the name of Stanley Whittingham. Exxon’s investment in Whittingham and this scientific elite paid off. Following his investigations of the properties of tantalum disulfide, Whittingham and his colleagues made a remarkable discovery. Their breakthrough? Understanding the role of intercalation electrodes in battery reactions. This would eventually result in the first commercial lithium rechargeable batteries. The batteries were based on a titanium disulfide cathode and a lithium-aluminum anode. Although other entities including General Motors, Sohio and the US Argonne National Laboratory were developing lithium-based batteries at the same time, only Whittingham’s invention worked at room temperature. The implications for the oil major — and the rest of the world — could have been tremendous. In 1976, Forbes magazine declared that “the electric car’s rebirth is as sure as the need to end our dependence on imported oil”. Sadly such enthusiasm had died out by the end of the decade. Profiting from Whittingham’s pioneering breakthrough, later on Japan turned lithiumion batteries into a highly profitable industry. 122 Batteries International Spring 2013
Beginnings Michael Stanley Whittingham was born near Nottingham in the UK in 1941. His interest in science stemmed from his father, a civil engineer, and his chemistry teacher in school. In the early 1960s he read inorganic chemistry at Oxford University, obtained his masters in 1967 and his DPhil the year after that. Whittingham recalls his days in Oxford: “Initially we studied catalytic ac-
tivity and how all that changed with the changes in the electronic properties of the material. There was a great deal of interest in the crystal structure, or rather the band structure, that controls the catalytic activity. “We chose a very simple reactant: mainly oxygen atoms, and we just looked at how they recombine at the surface of tungsten bronzes, NaxWO3, because it was very easy to change their catalytic behaviour by changing the amount of sodium. www.batteriesinternational.com
BATTERY HEROES: STANLEY WHITTINGHAM “This was at the time of Sputnik and the US Air Force paid for the research through their London office. They were interested in how various gaseous species reacted on the surface of their space ships. That was for my Masters.” Oxford always had a very active programme in solid state. There were three or four faculty there interested in solid-state. His DPhil continued on tungsten oxides and tungsten bronzes and looked at the same materials as catalysts potentially for gas production. Within a few months of his starting the research, the UK struck natural gas in the North Sea and the sponsor of his research, the Gas Council, changed the emphasis to the mechanism of reduction of the tungsten oxide bronzes, to form tungsten metal. Whittingham realised that to obtain an academic or an industrial job, he had to go the US, and where better than the warmth of California? In February 1968 he became a postdoctoral fellow, investigating solid-state electrochemistry under professor Robert Huggins at Stanford University. It was quite a switch. “In the UK, France, and Germany, solid-state chemistry was a respectable subject,” he recalls. “Chemistry departments did solid-state chemistry. In the US you could count the number of solid-state chemists on the fingers of one hand. So I went to a materials science department, not to a chemistry department.” He loved his new-found country and for relaxation he travelled most weekends to the national parks in California and Oregon. And it was in Stanford that he met his wife, Georgina, after she attended the university to get her PhD in Latin-American Literature. His two children and four grandchildren, are all natives of the state. But the turning point of his career was fast approaching. In 1971, his published findings on fast-ion transport, particularly in the conductivity of the solid electrolyte beta-alumina won Whittingham the Young Author Award of the Electrochemical Society. And this was the springboard to greater things. “Soon after the award,
A younger Whittingham investigating molecular structure and catalytic activity
I was approached by Ted Geballe, professor of applied physics who had been asked to find people to go to Exxon which was starting up a new corporate research lab in Linden, New Jersey. Their mission? They wanted to be prepared for the company to survive when oil ran out — a major theme of corporate thinking in the 1970s.
An offer he could not refuse Although he was torn between a conflicting offer of a job in the material science department at Cornell University, Exxon made Whittingham an offer he could not refuse. They included him in a six-strong interdisciplinary group, led by physical chemist, Fred Gamble, who had also been at Stanford, alongside an organic chemist and several physicists. “If you needed something for your re-
“We had an incredibly good patent attorney. They would write up your invention and then ask you: why can’t you do it this or that way? And they provoked us into building a battery fully charged or fully discharged.” www.batteriesinternational.com
search you asked for it, and it would be there in a week. Money was no issue,” Whittingham says. “They invested in a research laboratory like they invested in drilling oil. You expect one out of five wells/ideas to pay off. The Exxon research team began to look at tantalum disulfides. They found that by intercalating different atoms or molecules between the sheets of tantalum disulphide, they could change the superconductivity transition temperature. The potassium compound showed the highest superconductivity. Whittingham realized that this compound was very stable, unlike potassium metal so the reaction must involve a lot of energy. So this suggested the possible use for this intercalation reaction for electrical energy storage. “We looked at lithium and sodium, not potassium, because it turns out that potassium is very dangerous. We also looked at the titanium disulfides, because they are lighter in weight than tantalum, and moreover were good electronic conductors,” he says. Meanwhile a Japanese company had come out with a carbon fluoride battery which was used by fisherman for night fishing. “And that was a primary Batteries International Spring 2013 123
BATTERY HEROES: STANLEY WHITTINGHAM battery,” he says. “This was the beginning of interest in lithium batteries.” Towards the end of 1972 Whittingham and his colleagues informed their Exxon bosses that they had a new battery, and patents were filed within a year. Within a couple of years Exxon Enterprises wheeled out prototype 45Ah lithium cells and started work on hybrid vehicles. The Exxon battery promised to make a huge impact. At the time, Bell Labs had built up a similar research group, again made up of chemists and physicists from Stanford. “We were competing head-on for a while, also in publications. If you look at our publications on the battery, you will see a lot of basic science with no mention of batteries at all. Exxon came up with the key patents early on,” he says.
Applications of the patents “These early batteries were quite remarkable, and some of the smaller ones, used for marketing, are sill operating today, more than 35 years later. “We had an incredibly good patent attorney. They would write up your invention and then ask you: why can’t you do it this or that way? And they provoked us into building a battery fully charged or fully discharged.” The latter is the way almost all of today’s batteries are constructed. In 1977, Whittingham teamed up with John Goodenough to publish a book called “Solid State Chemistry of Energy Conversion and Storage”. To better disseminate information about the field, in 1981, Whittingham launched a new journal Solid State Ionics, which he would edit for the next 20 years. “Exxon was run by scientists and engineers, not by lawyers or MBAs. Their philosophy was that if you were a good scientist then you might also be a good director,” he says. “So within a few years I became director of their chemical engineering division. I was responsible for technology, for synthetic fuels in those days, chemical plants, and refineries. It sounded challenging at the time and I stayed there four years.” But tougher times were just around the corner. “At that time there began to be greater interest in shale oil and coal gasification. It was a boom period. My job was to employ as many chemical engineers as I could lay my hands on. But soon the writing was on the wall and the slump was coming. We started laying off people.” By this time Whittingham was missing doing any pure scientific research himself. In 1984, he went to work at 124 Batteries International Spring 2013
the Schlumberger-Doll Research Centre in Ridgefield, Connecticut. “Schlumberger was the Rolls-Royce of the oil field. They built very expensive analytical logging equipment which they put down oil wells to determine whether there was any oil down there and what the rock foundations were like. They would put these probes worth millions of dollars down the well, pull them up slowly and you would get wiggles and charts! And if they could reproduce the wiggles they would sell it. It was a very low-key company. In those days they probably made more money than all but two or three of the biggest oil companies. “What they didn’t have were chemists, those who tried to understand what these measurements actually meant. They did have a large number of physicists and electrical engineers building the instruments. Then they decided to build up a basic rock science group, the job of which was to try to understand what was measured.” For the next four years, Whittingham headed this analytical group, bringing together instrument builders and chemical engineers. It was more satisfying than his managerial post at Exxon. “But as my wife said, I was doing far too much travel. Schlumberger had labs in Texas, Connecticut, Tokyo, Paris, and Cambridge, England. During my first year I was in the US maybe half of the time.”
The next step Four years later, with US industrial research activities starting to slow up, Whittingham realised that it was time to move on. After 16 years in industry, in 1988, he joined the Binghamton campus
“Money was no issue. They invested in a research laboratory like they invested in drilling oil. You expect one out of five wells/ ideas to pay off. If you needed something you asked for it, and it’d be there in days.” of the State University of New York as a professor of chemistry to initiate an academic programme in materials chemistry. By this time Japanese companies, in particular Sony, had made great strides in the commercialization of lithium rechargeable batteries. When Whittingham returned to battery research, the Japanese lead was becoming dominant, embodied in a raft of patents. For five years, he worked as the university’s vice provost for research and outreach. He also was vice-chair of the Research Foundation of the State University of New York for six years. Whittingham’s group developed a strong effort in the hydrothermal synthesis of new materials, initially of vanadium compounds, then used this technique for making cathode materials, which is now being used commercially for the manufacture of lithium iron phosphate by Phostech/Süd-Chemie in Montreal, Canada. The group also developed a fundamental understanding of the olivine
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An original lithium battery cell from the 1970s — and still working www.batteriesinternational.com
BATTERY HEROES: STANLEY WHITTINGHAM cathode and of a new tin based anode. He co-chaired the US Department of Energy study of Chemical Energy Storage in 2007, and is now director of the Northeastern Center for Chemical Energy Storage, a DOE Energy Frontier Research Center at Stony Brook University.
AND INTO THE FUTURE …
Understanding the electrode This centre has as its goal a fundamental understanding of the electrode reactions in lithium batteries. Without such an understanding the ultimate limits of energy storage will never be met. The centre comprises top scientists from around the country, including MIT, Cambridge, Berkeley and Michigan. Regarded as one of the fathers of the lithium-ion battery, Whittingham received from the Electrochemical Society the Battery Research Award in 2004, and was elected a fellow in 2006 for his contributions to lithium battery science and technology. In 2010, he received the American Chemical SocietyNERM Award for Achievements in the Chemical Sciences, and the GreentechMedia top 40 innovators for contributions to advancing green technology. In 2012 he received the Yeager Award from the International Battery Association for his life-time contributions to lithium batteries. Still at Binghamton, 71-year-old Stanley Whittingham’s recent work has been focussing on the synthesis and characterization of novel microporous and nano-oxides and phosphates for possible electrochemical and sensor applications. He still travels a lot, visiting around the world as well as relatives in England and our children and grandchildren in the West of the US. In 2012 he wrote “History, Evolution, and Future Status of Energy Storage”, which describes the evolution of lithium batteries and probes into the future. [IEEE Proceedings, 100, 1518 (2012)]
This centre has as its goal a fundamental understanding of the electrode reactions in lithium batteries. Without such an understanding the ultimate limits of energy storage will never be met. www.batteriesinternational.com
In his own website, Whittingham write “The research interests of the materials chemistry group are in the preparation and chemical and physical properties of novel inorganic oxide materials, using in particular soft chemistry (chimie douce) approaches. Much of our effort is targeted at finding new materials for advancing energy storage and production. “Recently we have reported the first layered vanadium and molybdenum oxides containing organic cations, simple layered alkali manganese dioxides formed from the hydrothermal decomposition of permanganates, and hydrothermal synthesis methods for the formation of a group of iron phosphates that are being used as the cathodes in a range of commercial applications. “The chemistry of materials is one of the two areas of chemistry experiencing the greatest growth at the present time both in academic institutions and industry. This popularity can be associated with the pervasiveness of solids throughout our lives, from semiconductors through energy storage to geological/biological systems, and to a number of recent breakthroughs, including high-temperature
inorganics superconductors. “One of our goals is to find new synthetic routes to prepare metastable compounds that cannot be prepared by traditional techniques. Primary emphasis is on reacting ions in solution with solids, so that the ions diffuse into the solids giving, for example, enhanced superconductivity. In many cases it is possible to form previously unknown open structures, such as layered VO2, by diffusing ions out of existing structures creating vacant tunnels or layers in which chemistry may be performed or separations/catalysis carried out. “Another goal is the understanding and exploitation of ionic motion in solids and its use in electrochromic devices and batteries. Here much emphasis is on intercalation compounds of the transition metal oxides,. Closely related is an investigation of aluminosilicates which can swell in the presence of water and other solvents and have been implicated as playing a critical role in diagenetic processes. These compounds are excellent systems for performing chemistry on the molecular level, and have the potential for revolutionizing the area of nanocomposites.
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