Pioneers of Energy Storage

Analysis and Features

Published on: November 24, 2015 7:00 amBy: ESJ
Pioneers of Energy Storage

John Goodenough

Where would we be without lithium ion batteries? From the mobile phone to the laptop to energy storage and management at the grid level, these batteries are creating our future. John Goodenough is the man who discovered the cathode material of choice and so made the lithium ion battery truly portable and rechargeable. Kevin Desmond reports.

The father of the lithium ion cell

In the early 1970s, the first energy crisis alerted the international community to its vulnerability to dependence on foreign oil. Alternatives to fossil fuels as energy sources were nuclear, solar, and wind energy, all of which require electrical energy storage for optimal use; and the rechargeable battery stores electrical energy as chemical energy.

In 1968, scientists at the Ford Motor Co had invented and started development of the sodium-sulfur battery, which uses molten electrodes and a solid electrolyte rather than solid electrodes and a liquid electrolyte.

However, this battery needs an operating temperature of 300°C-350°C, which has — mostly — limited its use to non-mobile applications such as grid energy storage. Nevertheless, this development alerted scientists to the possibility of increasing the energy density of a battery cell by using a non-aqueous electrolyte.

In the early 1970s, chemists in France and Germany were pioneering investigations of room-temperature reversible lithium insertion into layered transition-metal (M) sulfides and selenides MS2 and MSe2, which led to the suggestion that a rechargeable lithium-MS2 battery would be feasible since lithium (Li) non-rechargeable (primary) batteries were known; they have an organic electrolyte for transporting Li+ ions inside the battery.

In 1976, a rechargeable room-temperature Li-TiS2 battery cell was demonstrated; it had an acceptable rate of charge and discharge and offered an energy density higher than can be achieved with conventional batteries that have an aqueous electrolyte transporting H+ ions. However, the Li anode was not replated smoothly on recharge but developed dendrites that grew across the flammable organic electrolyte on repeated recharge to give an internal short-circuit with disastrous consequences. This effort was, therefore, abruptly abandoned.

It is at this point that an American physicist in his 50s, by the name of John Goodenough, accepted a position of professor and head of the Inorganic Chemistry Laboratory at Oxford University, England. He had been contemplating a move to the Ariya Mehr University in Iran to establish an energy institute there when a letter arrived inviting him to apply for the position at Oxford.

Early computers

Goodenough had been working as a research scientist at MIT’s Lincoln Laboratory where he had been part of an interdisciplinary team that developed the first random-access memory (RHM) for the digital computer.

Goodenough’s contribution was to the development of the ferrimagnetic, ceramic memory element, a contribution that put him in charge of a ceramics laboratory and that gave him a decade in which to explore the magnetic, transport, and structural properties of transition-metal compounds.

After moving to Oxford, Goodenough recognized that the layered sulfides would not give the voltage needed to compete with batteries using a conventional aqueous electrolyte, but that an oxide would provide a significantly higher voltage. From previous work, he knew that layered oxides analogous to the layered sulfides would not be stable, but that discharged LiMO2 oxides could have the same structural architecture as discharged LiTiS2.

Goodenough assigned a visiting physicist from Japan, Koichi Mizushima, the task of working with Goodenough’s postdoc, Philip Wiseman, and a student, Philip Jones, to explore how much Li could be extracted reversibly from layered LiMO2 cathodes, and with M = Co and Ni he found he could extract electrochemically over 50% of the Li at a voltage of around 4.0V versus a lithium anode, nearly double that for the sulfides, before the oxides began to evolve oxygen.

Their groundbreaking findings with Li1-xCoO2 were published in the Materials Research Bulletin 15, 783-789, (1980).

The report concluded with the statement, “Further characteristics of the intrinsic and extrinsic properties of this new system are being made.”

However, when Goodenough went to patent his cathodes, no battery company in England, Europe, or the US was interested in assembling a battery with a discharged cathode, so he gave the patent to the AERE Harwell Laboratory.

Nevertheless, with his postdoc Peter Bruce, now a professor in St Andrews, Scotland, and a new student, MGSK Thomas, Goodenough continued work at the Inorganic Chemistry Laboratory, South Parks Road in Oxford to demonstrate that the Li+-ion mobility in Li1-xCoO2 is even higher than that in the sulfide cathode LiTiS2. This finding meant that a Li1-xCoO2 cathode would provide the needed voltages and rates that would usher in the “wireless revolution”.

Meanwhile, Rachid Yazami in Switzerland, exploring Li insertion into graphite, reported that a discharged graphite anode did not have a problem with dendrites if the carbon/LiCoO2 cells were not charged too rapidly, and Akira Yoshino in Japan then assembled the discharged cell Carbon/LiCoO2 to demonstrate the Li-ion battery that was licensed to the SONY Corporation, which marketed it with the first cell telephone.

Today, almost everyone from five years upwards has an application of this battery in their pockets.

A call to arms

Michael Thackeray was working on the Zebra battery (see Batteries International passim), a modification of the sodium-sulfur battery, in South Africa when he read the article in the Materials Research Bulletin. He immediately applied for a sabbatical to work with Goodenough in Oxford.

He came to South Parks Road with the announcement that he was inserting Li reversibly into magnetite, the ferrimagnetic spinel Fe3O4 used by Greek sailors in an early version of the compass. He wished to replace cobalt (Co), which is expensive and toxic, with iron (Fe), which is abundant and benign. The spinels A[B2]O4 contain a three-dimensional framework of BO6/3 octahedra sharing edges; in the layered LiMO2 oxides they form two-dimensional layers.

The A atoms of a spinel occupy interstitial tetrahedral sites that are bridged by empty, face-sharing octahedra, and Goodenough realized from his earlier work on spinel memory elements that the Li inserted into
Fe[Fe2]O4 was entering and displacing that interstitial A-site Fe into the bridging interstitial octahedral sites to create a rock-salt structure with the
[Fe2]O4 framework remaining intact.

Bill David, now at the Rutherford Laboratory, had just joined Goodenough’s group from the Clarendon with a PhD involving structural analysis, so he and Thackeray demonstrated that Goodenough’s hypothesis was correct.

Meanwhile, Goodenough told Thackeray to investigate the electrochemical reversible insertion of Li into the spinel Li[Mn2]O4; it gave a voltage of 3.0 V versus lithium. Manganese (Mn) is also abundant and benign. On his return to South Africa, Thackeray showed his students that extraction of Li from Li[Mn2]O4 gives a voltage of 4.0 V versus lithium. A modification of the Li1-x[Mn2]O4 spinel cathode is now used by Nissan to power the Leaf electric car.

Goodenough’s own story

John Bannister Goodenough was born of US parents in Jena, Germany, on 25 July 1922. At that time, his father, Erwin Goodenough, was at Lincoln College, Oxford, writing a DPhil on the Church Fathers. The family returned to New Haven, Connecticut, in 1923 where his father had been appointed assistant professor of the History of Religion at Yale University. John was the second son; he went away to Groton School at the age of 12

The teenage Goodenough enjoyed playing individual and team sports of all kinds, and in the summer of 1939 he kayaked from the lakes of Finland down the Ivalo River in the north to Kirkenes in Norway, where his Finnish companion had to return home to prepare for the Russian invasion. After 10 days walking in the Jotunheimen Mountains of Norway, his six German companions were called home to serve the ambitions of Hitler, who had already moved into Poland.

After the bombing of Pearl Harbor, he volunteered for service, but was not called up until January 1943. This gave him time to complete his undergraduate degree in mathematics. He had entered Yale as a freshmen with a background in Latin and Greek and little idea of what he would do after the war was over.

He had taken an introductory course in chemistry during his freshman year as the science requirement for a liberal arts degree, but he had no thought of a career in science. “As a young man in search of a calling for my life, I became fascinated by the philosophy of science while struggling to come to terms with a spiritual awakening,” he says.

“While reading Whitehead one night, I decided that if I were ever to come back from the war and if I were to have the opportunity to go back to graduate school, I should study physics.”

During hostilities, as an Army Air Force meteorologist, Goodenough dispatched tactical aircraft across the Atlantic Ocean.

“In 1946, while I was still stationed on the tiny island of Terceira in the Azores awaiting my turn to go home, a telegram arrived telling me to report back to Washington in 48 hours.

Finding his calling

In Washington I was informed that I had been selected to study physics or mathematics at the University of Chicago or Northwestern University. My spirit recalled my earlier resolve, so from Washington I went immediately to the University of Chicago to register as a graduate student in Physics. When I arrived, the registration officer, professor Simpson, said to me, “I don’t understand you veterans. Don’t you know that anyone who has ever done anything interesting in physics had already done it by the time he was your age; and you want to begin?”

In 1946, Goodenough married Irene Wiseman, a history graduate, at Chicago. In the decades to come, the couple were to enjoy travel, mountain walking, and meeting scientists and Christians from many countries; invitations every year to lecture abroad would introduce them to western and eastern Europe, Russia, India and Nepal, the Middle East, North Africa, Australia, Mexico, and Argentina.

By 1952, still at the University of Chicago, Goodenough had completed his PhD under the supervision of Clarence Zener. This included taking two courses from Enrico Fermi on quantum mechanics and nuclear physics. In 1952, he joined the group at MIT Lincoln Laboratory charged with the development of a ferrimagnetic ceramic to enable the first random-access memory (RAM) for the digital computer.

“The air defence of this country depended on having a large digital computer, and the computer had no memory!” Goodenough says. “The rolled alloy tapes first tried did not switch fast enough. Although the Europeans who had developed ferrimagnetic spinels were convinced that it would be impossible to obtain the required squarish B-H hysteresis loop in a polycrystalline ceramic, the magnetic-core RAM was delivered within three years of my arrival with a read/rewrite cycle time of less than the required six microseconds.”

In the course of this work, Goodenough showed how cooperative orbital ordering gives rise to crystal distortions, and he used this ordering to articulate the rules for the sign of the spin-spin magnetic interactions in solids. These rules have subsequently provided a true guide to the design as well as the interpretation of the magnetic properties of solids; they are known as the Goodenough-Kanamori rules, and inspired the title of Goodenough’s first book, Magnetism and the Chemical Bond (Interscience-Wiley, 1963).

Since his proposals in the early 1970s to work on energy materials were assigned to the National Energy Laboratories because the Three-Mile Island incident had halted development in the USA of nuclear-power plants, Goodenough debated over the invitation to go to Oxford.

“My wife did not hesitate to recommend that I put my name in nomination; and I thought, ‘If the people at Oxford have that much imagination, then perhaps that is what I should do’. I was duly elected, and in 1976 I took up the post at Oxford,” he said.

Leaping over the Oxford years, by 1986, Goodenough was 64 years old. “With the approach of mandatory retirement in England in 1986, I was delighted with an invitation from the University of Texas at Austin to occupy the Virginia H Cockrell Centennial Chair in Engineering.”

Since then, as a member of the ME and ECE Departments, he helped to establish the Texas Materials Institute.

With the help of now professor Arumugan Manthiram, who had come with him from England as a postdoc in 1986, and of professor Jianshi Zhou, who came to him in 1987 as a PhD student, Goodenough has been able to establish a laboratory that includes in one group solid state chemistry, structural characterization, electrochemistry, and a variety of physical measurements as a function of temperature and pressure.

Still striving

This organization has enabled him to return to studies of the unusual physical properties imparted by orbital order, structural transformations, and the lattice instabilities encountered at the crossover from localized to itinerant electronic behaviour.

Some of this is summarized in his volume Localized to Itinerant Electronic Transitions in Perovskite Oxides (Springer-Verlag, 2001). He has also continued to develop solid electrolyte and electrode materials for the Li-ion battery and the solid oxide fuel cell (see his book with K Huang: Solid Oxide Fuel Cell Technology: Principles, Performance, and Operations (Woodhead Publishing, 2009).

The olivine cathode Li1-xFePO4 he developed in Texas is now being used for power tools and in a large battery being constructed in Quebec for the storage of electrical energy generated by a wind farm there.

Among his many publications is a very personal one: “Witness to Grace” (Publish America, 2008) in which he describes how his intellectual journey has also included “a religious quest for meaning in what or whom I would choose to serve with my life.”

Witness to Grace” also chronicles a struggle to find a calling to a career in the science of the solid state, a career that brought together physics, chemistry, and engineering. He leaves to the reader the decision as to what was the result of chance and what was the leading of the spirit of love.”

(Our thanks to John Goodenough and his assistant Melissa Truitt-Green, and Linda Webb of ICL for their invaluable help in this article.)

Some of the accolades

In 2001, Goodenough received the Japan Prize for his discoveries of the materials critical to the development of lightweight rechargeable batteries.

Goodenough is a member of the National Academy of Engineering, the French Academy of Sciences, and the Real Academia de Ciencias Exactas, Físicas y Naturales of Spain and the Royal Society of the United Kingdom.

He has written more than 700 articles, 90 book chapters and reviews, and five books, including two seminal works, Magnetism and the Chemical Bond (1963) and Les oxydes des métaux de transition (1973).

Goodenough is co-recipient of the 2009 Enrico Fermi Award. This presidential award is one of the oldest and most prestigious given by the US government and carries an honorarium of $375,000. He shares the honour with Siegfried Hecker, professor at the Management of Science and Engineering Department of Stanford University.

The RSC John B Goodenough Award, (previously advertised as the Materials Chemistry Forum Lifetime Award) was established in 2008. The John B Goodenough Award is to recognize exceptional and sustained contributions to the area of materials chemistry.

On November 30, 2010, the latest presentation of a Royal Society of Chemistry (RSC) National Chemical Landmark plaque took place in the Inorganic Chemistry Laboratory of the University of Oxford.

The plaque reads: “Inorganic Chemistry Laboratory where, in 1980, John B Goodenough with Koichi Mizushima, Philip Jones, and Philip Wiseman identified the cathode material that enabled the development of the rechargeable lithium-ion battery. This breakthrough ushered in the age of portable electronic devices.”

At the ceremony greetings were received as a pre-recorded speech from professor Goodenough from his laboratory in the US. Present at the ceremony itself were Mizushima, Wiseman, and Jones.

Now in his early 90s he remains active — and a highly popular figure with both faculty and students — with a full schedule leading graduate students and post docs in continued research on transition-metal oxides and lithium-ion battery design and production.

 

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