The 2019 Nobel Prize in Chemistry was announced, and American chemists Stanley Whittingham, John Goodenough and Japanese chemist Akira Yoshino won this year’s awards.
At 17:45 Beijing time on October 9th, the 2019 Nobel Prize in Chemistry was announced. American chemists Stanley Whittingham (Stanley Whittingham), John Goodenough (John Goodenough) and Japanese chemists Akira Yoshino won this year’s award for his outstanding contributions to the field of lithium-ion batteries.
In the 1970s, Stanley Whittingham, who worked for Exxon Oil Company in the United States, invented the lithium battery. He used titanium sulfide as the positive electrode material and metallic lithium as the negative electrode material to make the first lithium-ion battery. Goodenough is the inventor of the rechargeable lithium-ion battery and led the project team to invent the lithium-ion battery and lithium iron phosphate battery technology that can be mass-produced. The project team he led and SONY company jointly developed a rechargeable ion battery based on carbon material positive electrode and lithium cobalt oxide LiCoO2 material negative electrode, which is currently widely used lithium ion battery technology.
In 1983, Akira Yoshino filed a patent application for the lithium-ion battery we know today, taking the original concept and making it safe, efficient and reliable. He replaced the unstable lithium metal on the anode with a safe, conductive plastic called polyacetylene. He also introduced a polyethylene-based heat-sensitive film between the reaction layers. When the battery overheats, the membrane melts and acts as a fuse to stop the entire structure from catching fire. This is the first lithium-ion battery design to enter the market and for consumer use.
Commercial lithium-ion batteries were introduced in Japan in the 1990s, driven by the research work of Whittingham, Goodenough, Akira Yoshino, and others. Over the decades, lithium-ion batteries have been used in almost every portable electronic device on the planet.
John Goodenough, born in 1922, is an American solid-state physicist, member of the National Academy of Engineering and the National Academy of Sciences. Goodenough received his MS and PhD degrees in physics from the University of Chicago in 1951 and 1952, respectively, and after graduation he worked at the Massachusetts Institute of Technology Lincoln Laboratory, where he laid the foundation for the development of random-access memory (RAM) for digital computers. . After leaving MIT, he joined Oxford University as Director of the Laboratory of Inorganic Chemistry from 1976 to 1986. During this period, Goodnoff discovered that the use of lithium cobalt oxide as an electrode could significantly improve the energy density of lithium batteries. Many of his discoveries became the foundation of the later lithium battery industry. He joined the University of Texas at Austin in 1986, where he teaches and conducts research to this day. Last year, the 95-year-old Goodenough also led a team to develop the first all-solid-state battery.
Stanley Whittingham was born in 1941 and received his PhD from Oxford University in 1968. After graduation, Dr. Whittingham went to Stanford University as a postdoc. He worked at ExxonMobil Research and Engineering from 1972 to 1984. He then worked at Schlumberger for four years before becoming a professor at Binghamton University. As a pioneer of lithium-ion batteries, Whittingham has been predicted by the media as a popular candidate for the Nobel Prize in Chemistry, and the scientific community has always had a high voice for him to win the Nobel Prize in Chemistry. Whittingham, 78, is still at the forefront of lithium-ion battery research, like Goodenough.
Akira Yoshino Born on January 30, 1948, Japanese chemist, researcher of Asahi Kasei Corporation, and professor of Meijo University.
Before reading this article, you may have never heard of John Bannister Goodenough. But you must know what he studies, and in fact there is a good chance that you have his “work”.
Look back at the technological leaps of the past six or seven decades: the polio vaccine, spaceships, the ARPANET (predecessor of the Internet), and more. In addition to these, there are two other inventions that have far-reaching effects on economic and social development. Without this invention, people’s lives around the world would be completely different.
The first major invention was the transistor, born at Bell Labs in 1947. Its advent transformed electronics and laid the foundations of the global economy and modern civilization. The second invention is the lithium battery. In 1991, Sony Corporation began commercial production of lithium batteries, and then lithium battery products gradually replaced bulky electronic devices that rely on transistors.
Lithium batteries have broadened the application range of transistors. Without lithium batteries, there would be no smartphones, tablets, and laptops, and the devices you’re reading this on right now. Of course, there will be no Apple, Samsung, Tesla, etc.
In 1980, 57-year-old physicist Goodenough invented the most important component in lithium batteries, the cobalt oxide cathode. Such cathodes are now used in portable electronic devices all over the world.
Now, in his 90s, Mr. Goodenough still commutes to his small office at the University of Texas at Austin every day. To this he explained that my work was not done. Thirty-five years after the invention of the cobalt oxide cathode, electric energy vehicles still cannot compete on price with conventional internal combustion engine vehicles. And the storage cost of solar and wind power generation is too high, and it can only be used immediately. Our outlook is grim: while oil is cheap now, it is bound to rise according to the cyclical pattern of commodity price fluctuations; and climate change is a growing problem.
In short, the world needs super batteries. “Otherwise, I can only say that in the future we will be fighting for the last energy source, and global warming will be uncontrollable,” Goodenough said.
The good news is that Goodenough is working on a new idea with his postdoctoral assistants. “I want to fix this before I die, I’m in my 90s and I still have time,” he said.
Soil for battery research
A battery is a device that causes charged ions to move in a direction between two electrodes. The directional movement of the electric charge produces a current that supplies the appliance to work.
Making a battery requires two electrodes, between which ions move. The electrolyte solution between the electrodes acts as a medium for the movement of ions. The negative electrode is the anode, and the positive electrode is the cathode. The movement of cations from anode to cathode creates an electric current when a battery is discharged (such as powering an appliance). When the rechargeable battery is charged by an external power source, the cations return to the anode to store electrical energy.
Almost all battery designs ultimately boil down to the choice of anode, cathode, and electrolyte materials. They determine the battery’s power storage capacity and discharge rate.
As early as 1859, Gaston Planté invented the lead-acid battery (using a lead electrode and a sulfuric acid electrolyte). In the early twentieth century, electric vehicles using lead-acid batteries appeared to outperform combustion-engine vehicles using gasoline. Internal combustion engines are loud and dirty, and crank the heavy handle when starting. By contrast, electric vehicles are easy to operate and quiet. However, a series of inventions, such as the electronic ignition device for automobiles, gradually gave the internal combustion engine an advantage. For decades, few believed that electric vehicles would replace internal combustion engine vehicles.
Business Innovation The idea of using electricity to replace internal combustion engines is making a comeback. Researchers around the world are scrambling to work on batteries in hopes of being the next Ford. All of a sudden, Goodenough, who was at MIT at the time, said that all of a sudden, battery research was no longer boring. The frenzy continued into the next decade, and intensified with the effects of the Arab oil embargo.
Electricity is back on the stage, and Goodenough has joined the fray. Over the next two decades, he invented or co-invented nearly every major achievement in the development of modern batteries.
The first generation of lithium battery
While Goodenough was at Oxford University, British chemist Stan Whittingham made a major breakthrough in batteries. Together with colleagues at Stanford University, he discovered a layered electrode material that stores lithium ions between layers of titanium sulfide. Lithium ions can shuttle back and forth between electrodes, are rechargeable, and operate at room temperature. Wittingham named this type of storage after the chemical term intercalation.
The news attracted widespread attention. Oil giant ExxonMobil invited Whittingham to secretly develop a new battery based on his work at Stanford. In 1976, ExxonMobil applied for a patent for the invention of lithium batteries.
For the past 60 years, the standard battery for consumer electronics was the single-use carbon-zinc battery. (By comparison, lead-acid batteries are so large and heavy that they can only be used in cars.) Also used are nickel-cadmium batteries. Whittingham’s result surpasses both of these batteries by being light and full of power. If the research is successful, it could power smaller and more portable devices.
But there is another law of physics standing in the way. The electrochemical reactions in which lithium batteries work make them prone to explosions. When overcharged, the battery may spontaneously ignite. Even if you take care to avoid these problems, batteries will gradually degrade over repeated charge and discharge. Lab explosions and battery decay plagued Whittingham’s work.
Goodenough thinks he can design a more efficient battery without fatal flaws. Mobil’s batteries use titanium sulfide as the anode material for storing lithium ions. Goodenough, on the other hand, was familiar with metal oxide materials from his time at MIT. In his judgment, oxide electrodes allow for higher voltage charge and discharge. According to the laws of physics, more energy can be stored and less likely to explode. It’s worth a try.
Lithium cobaltate, spinel, iron phosphate
But there is a potential problem. The more mobile lithium ions stored between the electrodes, the more energy the electrodes release. Goodenough considered that if lithium is a large part of the cathode material, when lithium ions are transferred to the anode, the cathode is likely to collapse due to the loss of a large number of ions hollow. Is there a metal oxide that can withstand this effect? If so, which one would it be? What should be the ratio of this material to lithium?
Goodenough directed two postdoctoral assistants to methodically investigate a range of metal oxide structures. He asked his assistants to determine the voltage needed to dissociate lithium (his expectation was much higher than the 2.2V of the Whittingham battery) and the proportion of free lithium ions.
The results showed that the electrode could withstand a voltage of 4 volts, and half of the lithium was released. This is enough for a reusable battery. Of the oxides they tested, the assistants found that cobalt oxide was the best and most stable material.
Goodenough (second from left, front row) with colleagues, taken at Oxford University in 1982.
In 1980, four years after Goodenough arrived at Oxford, the cobalt oxide cathode material for lithium batteries became a huge breakthrough. This is the world’s first lithium-ion battery capable of powering large, complex devices and is far superior to other batteries on the market. The battery can store two to three times as much energy as room-temperature rechargeable batteries on the market. Not only is it smaller but also performs the same or better.
In 1991, Sony produced the world’s first commercial rechargeable lithium-ion battery by combining Goodenough’s cathode and carbon anode technologies, which became an overnight sensation. Sony also uses lithium-ion batteries for cameras. Lighter and more beautiful Sony cameras quickly became popular everywhere.
Sony’s rivals quickly introduced similar batteries and handheld cameras, and put lithium-ion batteries into laptops and cell phones, creating a multibillion-dollar industry. Sony’s breakthrough sparked an upsurge in lithium-ion battery research, with labs around the world searching for smaller, more energy-storing lithium-ion battery structures.
Before this, no one expected such a huge commercial market for this research.
In commonly used cobalt cathode materials, atoms are stacked in layers, and the lithium ions stored in them can only move between atomic layers. Goodenough thinks the spinel’s atoms are arranged in a way that allows ions to move in three dimensions, so that ions have more paths in and out of the electrode plates, increasing the rate of charge and discharge. In 1982, Mike Thackeray, a postdoctoral assistant at Goodenough University of Oxford, invented a more advanced manganese spinel electrode. The electrodes are safer and cheaper than Goodenough’s cobalt oxide electrodes from a year ago.
Padhi and Okada, a researcher working in Goodenough’s lab at NTT Corporation in Japan, were looking for a better spinel material.
They tried different materials, such as cobalt, manganese and vanadium, without success. In the end they only had one ferrophosphorus compound on their list, and Goodenough thought they had to choose spinel. After telling Padhi the idea, he went on vacation.
When Goodenough returned, he learned from Padhi that, as he had predicted, Padhi had indeed not acquired the spinel structure. But he discovered a new naturally occurring olivine structure, and successfully extracted and put back lithium ions from the olivine structure. Upon inspection, Goodenough found the results to be stunning. This is the third time! First cobalt oxides, then spinel, and now iron phosphate, Goodenough’s lab has spawned three major commercial lithium-ion battery cathode materials.
Although Padhi’s research results were stolen by Shigeto Okada, a researcher at Japan’s NTT Company, he took the lead in applying for a patent in Japan. Goodenough’s lab was forced into a patent battle with Japan’s NTT Corporation and MIT Yet-Ming Chiang’s company A123. But the industry generally believes that all the technology originated in Goodenough’s laboratory.
A great inventor in his nineties gets a lot of credit, and so does Goodenough. He is nominated for the Nobel Prize almost every year, usually along with the Japanese chemist Akira Yoshino. Akira Yoshino combined an American-invented cathode with a graphite anode to create the first lithium-ion battery that made Sony a hit. In 2013, Goodenough was awarded the National Medal of Science by President Barack Obama; in 2009, he received the Fermi Award. In fact, there are also awards named after Goodenough. Since 2009, the Royal Society of Chemistry has awarded the “John B. Goodenough Award” annually in the field of materials chemistry.
But Goodenough seems to want to end his scientific career with a great new invention. He’s working on a super battery that will truly rival electric cars and combustion-engine vehicles, and he hopes it can store wind and solar energy economically.
His chosen research direction involves one of the hardest problems in battery science: how to make battery anodes from pure lithium or sodium? If successful, the battery could store 60 percent more energy than existing lithium-ion batteries. This will immediately give electric vehicles the strength to compete with gasoline-powered vehicles. Over the years, many scientists have made failed attempts. For example, in the 1970s, the Stan Whittingham laboratory of Exxon Company caught fire many times because of lithium battery research.
While Goodenough hasn’t spelled out new ideas, he thinks he already has some clues. And based on his previous work, scholars in the battery field are not too skeptical. Thackeray, a South African who now works at Argonne National Laboratory in the United States and discovered manganese spinel under the guidance of Goodenough, said: “He is still sharp, his thinking is still breaking through”, “The breakthrough in this field must be Unexpected ways. Goodenough is the type of person who breaks the rules.”
The stakes for this study are high, and Goodenough refutes many of his competing research methods. For example, Tesla’s Elon Musk, in his view, is content to “sell electric cars to the rich in Hollywood,” leaving middle-class car battery research to other scientists. This accusation is not entirely true. While Musk sells cars to the elite for $80,000 to $100,000 each, he is gradually improving the battery, promising to produce a $35,000 car to satisfy a larger market by 2018.
Goodenough also dismisses studies that only improve cell efficiency by 7% to 8% per year. “We need some noticeable improvements, not just a little bit at a time,” he said.
No one, including himself, can be sure that Goodenough will succeed this time, he just hasn’t given up. The development of super batteries is really difficult. Goodenough says everyone should keep trying to break through. He pointed out that we have 30 years to develop and commercialize new batteries before the devastating energy crisis and environmental problems hit. He thinks time is enough. “Many people are working on lithium batteries, and these people are very smart. I can’t say I’m the only one who can solve this problem,” he said.
However, he is likely to solve this problem. That’s why those who know him have been following John Bannister Goodenough.