Goodenough’s Life History of Lithium Battery Industry丨TECH TUESDAY

Original link: https://www.latepost.com/news/dj_detail?id=1723

Lithium batteries are already the infrastructure of modern civilization in the physical world. Almost all electronic products within reach today, and more and more new energy vehicles on the road cannot do without its drive.

Like many other major world-changing technological breakthroughs, the popularity of lithium batteries is the result of decades of basic scientific research, engineering breakthroughs and commercial drivers combined. But it would have been much later had it not been for the extraordinary resilience of one key individual.

The story begins in 1946, the spring less than half a year after World War II ended. Captain John Goodenough, who had just retired from the military, reported to the Department of Physics at the University of Chicago for his master’s degree. He had just turned 24 years old when he had previously forecast weather changes on the battlefields of Europe.

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Gudenave during World War II. Image via the Nobel Prize Committee

This age full of infinite possibilities is ruthlessly classified as “disliked” in the physics world: Newton discovered the law of gravitation at the age of 24; Einstein discovered the special theory of relativity at the age of 26; Schrödinger proposed the glass force at the age of 26 study.

“I don’t understand you veterans.” His lecturer, John Simpson, a star nuclear physicist at the University of Chicago, was shocked: “Don’t you know that the top physicists at your age already made a significant contribution, and you want to start now?”

Simpson joined the Manhattan Project at the age of 27 and soon became the leader of the research team to build the atomic bomb. Although Goodenough studied as an undergraduate at Yale before joining the army, his elective subjects were ethics, aesthetics, psychology, and mathematics, and he never touched physics.

Goodenough is used to that feeling of being “closed out.” He was born into a family whose parents had an extremely bad relationship and treated him even worse. When his father, a college professor, heard that he had been admitted to Yale, he gave $35 “that’s all, kid.”—Yale’s annual tuition was $900 at the time. His mother did not want him to be born, and sent him to boarding school when he was 12 years old, and there was little contact thereafter. In his autobiography, referring to his childhood, Goodenough fondly recalls siblings, a housemaid and a dog named Mike. no parents.

Goodenough was not dissuaded by Simpson. Goodenough was given to the University of Chicago as a government project, and Simpson had no right to refuse.

Simpson does not exaggerate the difficulties of physical research. After receiving a Ph.D. in physics from the University of Chicago, Goodenough went to MIT to do materials research for 24 years. At the age of 54, the laboratory was shut down due to the adjustment of the division of labor of government departments, ending his career in physics research. During this period, he did not make a significant breakthrough comparable to Simpson, and he is most famous for his research that laid the foundation for the memory (RAM) in the computer. But more than 20 years of research in physics made him more familiar with the properties of various materials and played a role in his later research career.

After losing his job, he found a job at Oxford University, started chemical research, and researched lithium battery materials. In a later interview with the Journal of the American Chemical Society, he regarded this turning point as a new beginning: “I officially became a scholar, and I also became a chemist at the same time.”

His scientific research career started late, but lasted a long time, 47 years. His research results have a longer life – any product that uses lithium batteries will directly benefit from Goodenough’s research.

Three important breakthroughs, turning a concept into infrastructure

Goodenough is not the first academics to work on batteries. The world’s first battery was born in 1800, Italian physicist Alessandro Volta (Alessandro Volta) used copper plates, zinc plates and paper discs soaked in salt water to create the first energy battery. A battery that produces a steady current for a fixed amount of time.

This is how batteries are designed today, moving charged atoms (ions) from one point (the positive pole) to another (the negative pole) to create an electric current that powers the device.

After more than 100 years, except for the French inventor Gaston Plante (Gaston Plante) who used lead-acid batteries to solve the problem of repeated use and added technical routes such as carbon-zinc and nickel-cadmium as positive and negative electrodes, there was not much battery technology. progress.

Until the 1970s, European and American countries that encountered the oil crisis began to invest resources in finding oil substitutes, and research on more efficient batteries became a key funding project. Lithium has become the most popular research object. On the entire periodic table of elements, it is the lightest and most charged metal, and it is also the most suitable element to be used to make batteries.

A lot of resources have been poured into it. It took only fifteen years for scientists to make all the key technologies of lithium batteries:

  • In 1976, British scientist Stanley Whittingham (Stanley Whittingham) used lithium disulfide and pure lithium metal as positive and negative electrodes to make the first lithium battery, but there were safety problems and it was extremely prone to explosion.
  • In 1980, Goodenough invented the positive electrode of lithium cobalt oxide battery, which is a key step in improving the safety of lithium batteries and improving battery performance.
  • In 1985, Japanese scientist Akira Yoshino invented the graphite battery negative electrode, completing the last piece of the puzzle of the lithium battery architecture.
  • In 1991, Sony made a commercial lithium battery based on the research of Goodenough and others.

In 2019, Whittingham, Goodenough and Akira Yoshino shared the Nobel Prize in Chemistry. The positive electrode studied by Goodenough is the most critical component of the battery, which directly determines the performance of the battery. Therefore, the battery is usually named after the positive electrode material.

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Schematic diagram of a commercial lithium cobalt oxide battery. Image via the Nobel Prize Committee

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From left to right are Goodenough, Whittingham and Akira Yoshino. Image via the Nobel Prize Committee

The biggest challenge in the development of lithium batteries is lithium itself, which easily reacts with water and air, and is very easy to catch fire and explode. For a long time it was only used in lubricants for nuclear weapons and engines. Whittingham used the titanium disulfide material that cost US$1,000/kg (equivalent to RMB 37,400 at present) to reduce the risk of fire and explosion as much as possible, but the effect was not great.

Goodenough thinks he can develop batteries with higher energy density and safer. His confidence comes from metal oxide materials he studied at MIT. He believes that using oxide as the positive electrode of the battery can allow the battery to discharge stably in a higher voltage environment, which means that the battery has a higher energy density under the same weight.

Battery research is an extremely tough job. Researchers in the lithium battery industry will compare this process to “alchemy”, which requires constant adjustment of temperature, humidity and other factors to test the performance of various materials. No one knows what the result will be before the test.

When Goodenough was doing research, computers were just beginning to be popularized, mainly relying on human trial and error. Goodenough, who has accumulated more than 20 years of related research, took his team four years to find lithium cobalt oxide. And the ExxonMobil lab blew up a few times before giving up.

Although the price of cobalt is also very expensive, more than 300,000 yuan/ton, and half of the world’s reserves are located in the politically turbulent African Democratic Republic of the Congo. However, the energy density of the battery developed by Goodenough is 2.5-3 times higher than that of the nickel-cadmium battery at that time, and it is safe enough, and the cost has been low enough to be accepted by smartphone and computer companies.

DynaTAC, the world’s first commercial mobile phone released by Motorola in 1983, weighed 790 grams, which was equivalent to 4 and a half iPhones, and it could only talk for 30 minutes after charging for 10 hours. Limited by the battery, that’s the only way to go. Motorola used the most advanced nickel-cadmium battery at that time, and the battery that stored 1000 mAh of electricity weighed more than 90 grams.

Thirteen years later, Motorola’s new phone, the Startac, weighs only 85 grams and has double the talk time. The change mainly comes from the lithium battery used in the new mobile phone.

The rapid adoption of lithium-ion batteries in the consumer electronics industry has also aroused ambitions in the automotive industry. In 2008, Tesla used 6381 lithium cobalt oxide laptop batteries to create an electric sports car with a range of 393 kilometers and an acceleration of 3.7 seconds per 100 kilometers, which is not weaker than ordinary fuel vehicles.

The number of batteries needed to drive a car is 1300 times that of a mobile phone. To promote the popularization of electric vehicles, it is impossible to use lithium cobalt oxide batteries like luxury cars. Reducing the cost of batteries is also an important research and development direction after Goodenough developed lithium cobalt oxide batteries.

Now 99.9% of electric vehicles use ternary lithium batteries and lithium iron phosphate batteries. The starting point of these two battery technology routes is Goodenough’s team:

  • In 1982, Goodenough and his postdoc Mike Thackeray at Oxford University invented a ternary lithium (lithium manganese oxide) material that was cheaper and safer than lithium cobalt oxide.
  • In 1991, Goodenough’s postdoctoral fellow at the University of Texas, Akshaya Paddy, used a compound of phosphorus and iron to create a lithium iron phosphate material.

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At 97, Goodenough is still instructing students. Image via University of Texas

“Remember that we are competing with problems, not people.” Goodenough said in an interview after winning the Nobel Prize about how to do research, “Dialogue, dialogue, dialogue is always very important.”

Conflicts in research are common, and some winners who shared the Nobel Prize even refused to share the stage because of competition. But Whittingham and Akira Yoshino, who won the Nobel Prize together with Goodenough, regard him as friends for decades. After Whittingham retired, he was often dragged by Goodenough to discuss issues. “I tell my colleagues that as long as John is around, I’m still a working scientist,” Whittingham said in a 2019 interview.

In more than ten years, he has developed three world-changing battery cathode materials, which determines the incomparable position of Goodenough in lithium batteries, and is also known as the “father of lithium electronics”. In 2022, when Goodenough is 100 years old, researchers from all over the world will connect online to celebrate him. The Journal of Chemistry of Materials, a subsidiary of the American Chemical Society, will publish a journal to commemorate his achievements.

When he was 100 years old, a total of 957.7GWh of lithium batteries were produced worldwide, which are used in almost all consumer electronics products, used in almost every electric vehicle, and energy storage devices for solar and wind power generation. China’s Ministry of Industry and Information Technology estimates that these batteries alone are worth more than 1.2 trillion yuan.

Changed the world, but didn’t make money from patents

In his 47-year battery research career, Goodenough has won all the awards a chemist can get: the Nobel Prize in Chemistry, the Enrico Fermi Award, the National Medal of Science, the Franklin Medal, the Welch Prize in Chemistry, Copley Medal, Charles Stark Draper Award, Japan International Award, etc.

But he didn’t get any money from lithium battery patents. His income mainly came from his salary at several colleges and universities. Prize money from various awards has also been donated to research or established scholarships by him.

When Oxford University developed the positive electrode of lithium cobalt oxide battery, no one realized the potential of his research, and Oxford University refused to apply for a patent for it. He ended up patenting it through the UK Atomic Energy Agency, at the cost of forgoing the proceeds.

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Goodenough (front row, second from left) at Oxford University in 1982. Image via University of Texas

The question Goodenough was often asked afterwards was, “Did you anticipate what would happen when you dropped your patent?” His answer, too, was honest, “Of course not.” Dollars.” But he never showed any sign of chagrin. “It is enough to bring joy to the realization of technologies that make the lives of many people better,” he wrote in his Nobel autobiography.

His loss of patents for subsequent key research reflects the dark side of business. In 1993, at the age of 71, Goodenough had moved from Oxford University to the University of Texas at Austin to do research. The main reason was that he was about to retire when he reached the age at Oxford University, and he hoped to continue to do research.

This year, Goodenough, who is an authority on lithium batteries, received an application from Shigeto Okada, a materials scientist at NTT (Nippon Telegraph and Telephone Company), hoping to do research with him at his own expense. Goodenough agreed, setting him up with an Indian postdoc named Akshaya Padhi to find more energy-dense, safer lithium-ion batteries.

After several years of research, they discovered lithium iron phosphate under the guidance of Goodenough. During this period, Okada has been secretly disclosing the research results of Goodenough’s team to NTT. NTT conducted further research on this basis, and applied for a patent for lithium iron phosphate in 1995, which triggered a patent lawsuit between the two parties.

When the University of Texas was in a lawsuit with NTT, Jiang Yeming, a researcher at the Massachusetts Institute of Technology, developed his own version of lithium iron phosphate based on Goodenough’s research, applied for a patent, and also fought with the University of Texas. filed a lawsuit.

“After that, the impression in the industry was that Gudenner’s invention could appear anywhere.” said Steve LeVine, a writer who has long studied batteries. When the iron-lithium battery electric vehicle was launched, no one cared where its battery technology came from.

unfulfilled wish

“I want to solve the car problem, and I want to remove all carbon emissions from roads around the world.” In 2018, 96-year-old Goodenough said in an interview, “I want to see it before I die.”

Instead of waiting, he did it himself. A year before he said this, he and his team members published a paper introducing a “glass battery”. This is the most popular “solid-state battery” direction in current lithium battery research.

Current lithium batteries are not perfect energy storage tools. If the charging speed is too fast, “dendrites” will appear on the positive electrode, which will pierce the battery’s separator and cause the battery to short-circuit and catch fire—this is the main cause of spontaneous combustion in electric vehicles today. Moreover, the energy density of the current lithium battery is still not comparable to that of gasoline, and the battery life and charging speed are limited, which is the main reason why it is difficult for electric vehicles to replace fuel vehicles.

Solid-state batteries use solid electrolytes instead of liquid electrolytes, which is the ultimate battery solution known to mankind. It is expected to fully solve the safety problem of lithium batteries and greatly increase the charging speed and energy density. In recent years, it has been sought after by global battery companies and research institutions, CATL, Panasonic, LG, etc. are all investing resources in research.

Goodenough’s team used glass electrolyte instead of liquid electrolyte, with an alkali metal negative electrode, claiming that the energy density is three times that of current lithium batteries, it only takes a few minutes to fully charge, and it can charge and discharge 23,000 times, not the current thousands of times , and does not form dendrites — meaning no spontaneous combustion.

After their study was released, it was widely questioned because of the lack of comprehensive data. Also, researchers from institutions such as Princeton University commented that the battery working mechanism they proposed “violates the first law of thermodynamics.”

Goodenough sees such challenges as competition, and doesn’t let his research stop because of age. Until 2022, when he is 100 years old, there will be 3 papers on which he is the first author. The team led by him also published 6 papers on solid-state batteries this year.

Like all battery research in the past, solid-state batteries are still a research direction of repeated experiments, competition for toughness and time. Japan’s Toyota, Hitachi Zosen and other companies have tried tens of thousands of electrolyte formulations in the past 30 years before selecting dozens of materials for use in batteries.

Unlike earlier studies, lithium batteries have fully demonstrated commercial value. More and more scholars and companies are willing to invest. In the past year alone, CATL and LG New Energy, the world’s two largest battery companies, have invested 20 billion yuan, scrambling to find the next potential compound.

But this time, Goodenough could no longer participate. He died on June 25, one month shy of his 101st birthday.

The title image is from the University of Texas.

“TECH TUESDAY” series

In 1957, a man-made object entered space for the first time, orbiting the Earth for three weeks. Human beings can look up and see a small flash across the sky in the night, parallel to the stars in mythology.

Such a feat cut across races and ideologies, sparking joy across the globe. But not in the triumphant joy we might have guessed, touched by human feats. According to the political philosopher Hannah Arendt (Hannah Arendt) observed back then, people’s mood is closer to a long-awaited relief that science has finally caught up with expectations, “Humanity is finally on the way out of the cage of the earth. took the first step.”

People are always rapidly adjusting their expectations of the world based on technological exploration. When a fantasy of a science fiction writer becomes a reality, it is often that technology has finally caught up with people’s expectations, or in Arendt’s words, “technology has realized and affirmed that people’s dreams are neither crazy nor empty.”

At times like today, a little more dreaming is better.

This is also the expectation of “LatePost” launching the TECH TUESDAY column. We hope to regularly report on new scientific research and technological developments outside of the business world that “Later” focuses on on a daily basis.

These may be about the progress of a cutting-edge research, the observation of a technology application, or a tribute to some outstanding technologies or even an era.

This column will record the various changes in the world from the perspective of science and technology. During this journey, I hope readers can join us in gaining a little understanding of the world.

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