September 22, 2016: 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. Stanley Whittingham is one of that elite handful that can claim to be one of the lithium battery’s founding fathers.
Reaching into the depths to unleash lithium’s power
It was so 1970s. Diversification was the new name of the corporate game. In 1972 it seemed a no-brainer for Exxon Research and Engineering to look at alternative energy production and storage. And so, with the deepest pockets of perhaps the most profitable oil giant in the world, it set about seeking the best scientists in the world for the project.
Among this elite was a 31-year-old graduate, then a more than up-and-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. And 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”.
However, such enthusiasm had died out by the end of the decade. Profiting from Whittingham’s pioneering breakthrough, Japan later turned lithium ion batteries into a highly profitable industry.
Michael Whittingham’s career really took off after leaving Oxford with his DPhil in 1967. After a short spell doing research work for the Gas Council, he 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 post-doctoral 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.”
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, 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,” he says.
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.
Although he was torn between the 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 research 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 battery,” he says. “This was the beginning of interest in lithium batteries.”
The patents arrive
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.
“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.”
By this time Whittingham was missing doing any pure scientific research himself. In 1984, he went to work at 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,” he says.
“What they did not 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.
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 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 made efforts to develop a hydrothermal synthesis of new materials, initially of vanadium compounds, then used the technique to make cathode materials. It 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 cathode and of a new tin-based anode.
Taking it to the limit
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 Society-NERM 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, Whittingham’s recent work has been focusing on the synthesis and characterization of novel microporous and nano-oxides and phosphates for possible electrochemical and sensor applications.