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Creating a rechargeable world

2022; Elsevier BV; Volume: 8; Issue: 2 Linguagem: Inglês

10.1016/j.chempr.2022.01.011

2451-9308

Yuming Chen, Maowen Xu, Yunhui Huang, Arumugam Manthiram,

Advanced Battery Technologies Research

John B. Goodenough is a towering solid-state physicist and was awarded the 2019 Noble Prize in Chemistry when he was 97. As the author of more than 800 research articles and 8 books, he has had a significant impact on interdisciplinary science by being a strong force in bridging chemistry, physics, and materials engineering. He has made a seminal breakthrough in the development of lithium-ion batteries (LIBs), particularly the discovery of cathode materials, including LiCoO2, LiMn2O4, and LiFePO4. His contributions also cover other energy-conversion systems and the Goodenough-Kanamori rule. This article is dedicated to Prof. Goodenough for his upcoming 100th birthday. John B. Goodenough is a towering solid-state physicist and was awarded the 2019 Noble Prize in Chemistry when he was 97. As the author of more than 800 research articles and 8 books, he has had a significant impact on interdisciplinary science by being a strong force in bridging chemistry, physics, and materials engineering. He has made a seminal breakthrough in the development of lithium-ion batteries (LIBs), particularly the discovery of cathode materials, including LiCoO2, LiMn2O4, and LiFePO4. His contributions also cover other energy-conversion systems and the Goodenough-Kanamori rule. This article is dedicated to Prof. Goodenough for his upcoming 100th birthday. Goodenough collaborated with Junjiro Kanamori to formulate the Goodenough-Kanamori rule, the law of magnetic exchange that played a key role in the development of computers.Thanks to his years of experience in oxide research at the Lincoln Laboratory, Goodenough thought that layered metal oxides already containing Li would be desirable cathodes.The recognition of the power of inductive effect to drastically increase voltage led Goodenough’s group to identify LiFePO4 as a cathode. John B. Goodenough was born in Jena, Germany, on July 25, 1922. As a child, he had severe dyslexia that seriously affected his learning, but he did not give up on overcoming his handicap and eventually graduated from private boarding school Groton School with a scholarship. He entered Yale University in 1940 to earn his bachelor’s degree. Besides his major, he studied many different courses, such as classical literature, philosophy, and chemistry. In 1944, he obtained a bachelor’s degree in mathematics with honor from Yale University. As World War II broke out, he served as a meteorologist in the US Army Air Force after his undergraduate graduation. The desire to become a solid-state physicist led Goodenough to study physics at the University of Chicago after serving in the army. However, his decision was questioned because, in the eyes of others, anyone who had ever made significant contributions to the field of physics had already done so by the time they were his age. For example, Einstein put forward the theory of relativity at 26, Bohr proposed the Bohr model at 28, and Edison lit the incandescent lamp at 32. But Goodenough firmly believed that physics was fundamental to science and chose to continue studying it at 30 for his PhD. Clearly, his persistence turned out to be worthwhile. During his PhD program, Goodenough studied under the supervision of Prof. Clarence Zener, a famous American scientist of applied physics (the inventor of the Zener diode). His mentor used two illuminating tips to guide him on how to engage in research: the first was to find the research problem, and the second was to solve it. His main doctoral study was called “A theory of the deviation from close packing in hexagonal metal crystals,”1Goodenough J.B. A theory of the deviation from close packing in hexagonal metal crystals.Phys. Rev. 1953; 89: 282-294Google Scholar which laid a solid theoretical foundation for subsequent physics research. Goodenough received his master’s and PhD degrees in solid-state physics from the University of Chicago in 1951 and 1952, respectively. Then, he began his career in the Lincoln Laboratory at the Massachusetts Institute of Technology to develop random-access memory (RAM) for digital computers. Goodenough collaborated with Junjiro Kanamori to formulate the Goodenough-Kanamori rule,2Goodenough J.B. Theory of the role of covalence in the perovskite-type manganites [La, M (II)] MnO3.Phys. Rev. 1955; 100: 564Google Scholar, 3Goodenough J.B. An interpretation of the magnetic properties of the perovskite-type mixed crystals La1-xSrxCoO3-λ.J. Phys. Chem. Solids. 1958; 6: 287-297Google Scholar, 4Kanamori J. Theory of the magnetic properties of ferrous and cobaltous oxides, I.Prog. Theor. Phys. 1957; 17: 177-196Google Scholar, 5Kanamori J. Superexchange interaction and symmetry properties of electron orbitals.J. Phys. Chem. Solids. 1959; 10: 87-98Google Scholar the law of magnetic exchange that played a key role in the development of computers. The Goodenough-Kanamori rule states that superexchange interactions are antiferromagnetic where the virtual electron transfer is between overlapping orbitals that are each half-filled, but they are ferromagnetic where the virtual electron transfer is from a half-filled to an empty orbital or from a filled to a half-filled orbital. The Goodenough-Kanamori rule is the same for both superexchange and semicovalent exchange. These magnetism rules are also useful for characterizing electrode materials of rechargeable batteries, such as perovskites. In 1967, Ford Motor Company asked Goodenough to monitor the development of Na-S batteries, which are energy-storage devices with high energy density. As his first foray into research on electrochemistry and batteries, this project captivated his imagination and curiosity. The working temperature of the new Na-S battery was as high as 300°C; Na melted at 98°C and would therefore catch fire when exposed to air, which carried a big potential safety hazard. Concerned about the problem of energy shortage (the oil crisis) in the US, Goodenough turned his research attention to energy materials. In 1976, Oxford University invited 54-year-old Goodenough to serve as the head of the Inorganic Chemistry Laboratory because of his excellent work at the Lincoln Laboratory. In the same year, British scientist Stan Whittingham successfully published a rechargeable Li battery—with layered TiS2 as the cathode and Li metal as the anode—with the lowest electrochemical potential (−3.04 V versus standard hydrogen electrode).6Cheng X.B. Zhang R. Zhao C.Z. Zhang Q. Toward safe lithium metal anode in rechargeable batteries: A review.Chem. Rev. 2017; 117: 10403-10473Google Scholar The designed battery displayed a high voltage of 2 V (1.5 V for alkaline batteries), which exhibited much higher energy density and worked at room temperature. In the late 1970s, the Canadian company Moli Energy produced a large number of lithium batteries (Li/MoS2), which were used in the “Big Brother” mobile phones. However, incidents of battery fires and explosions triggered a large-scale recall of the product. The first commercialization of rechargeable Li-metal batteries failed, and Moli was acquired by the Japanese company NEC. The main reason for the explosion was that the dendritic Li formed during cycling would pierce the separator between the two electrodes, causing a short circuit inside the battery, and the entire battery would heat up violently and explode. Goodenough made an in-depth analysis of how to solve the battery safety issue. Although Li has a small mass and would be “stuffed” into the battery as much as possible, Li is a very active metal and reacts violently when it encounters water. Developing a high-efficiency battery requires Li to be well controlled. It had been a challenge to find a suitable electrode material for use in batteries with Li+ intercalation. Thanks to his years of experience in oxide research at the Lincoln Laboratory, Goodenough thought that layered metal oxides already containing Li would be desirable cathodes. Ensuring the generation of battery electromotive force requires the maintenance of a certain amount of ion movement inside the battery. However, excessive extraction of Li+ would lead to a collapse of the layered structure of the electrode material, which must be addressed. After years of research, Goodenough and his group first proposed “solid-solution oxides for storage-batter electrodes”7Goodenough J.B. Mizushima K. Takeda T. Solid-solution oxides for storage-battery electrodes.Jpn. J. Appl. Phys. 1980; 19: 305Google Scholar and then developed a fantastic LixCoO2 material in 1980,8Mizushima K. Jones P.C. Wiseman P.J. Goodenough J.B. LixCoO2 (0<x<-1): A new cathode material for batteries of high energy density.Mater. Res. Bull. 1980; 15: 783Google Scholar which would enable the reversible release of more than half of the Li+ ions. LixCoO2 is a layered structure like a sandwich, where Li ions are sandwiched in the middle by the “bread slice” formed by Co-O2 layers. The as-made battery exhibited a high voltage of around 4 V. This breakthrough fundamentally changed the design principle of rechargeable batteries. The layered structure of LixCoO2 limited the transport of Li ions to a two-dimensional plane. Goodenough led a team, including Dr. Michael Thackeray and Dr. Peter Bruce, to look for a new cathode material with a better structure. They believed that the three-dimensional spinel structure was much better than the layered structure for the transport of Li+. Initially, they found in 1982 that some spinel oxides, such as Fe3O4 and α-Fe2O3, can be lithiated.9Thackeray M.M. David W.I.F. Goodenough J.B. Structural characterization of lithiated iron oxides LixFe3O4 and LixFe2O3 (0<x<2).Mater. Res. Bull. 1982; 17: 785Google Scholar The following year, they further found that Li ions would also be inserted into Mn3O4 and Li[Mn2]O4 at room temperature.10Thackeray M.M. David W.I.F. Bruce P.G. Goodenough J.B. Lithium insertion into manganese spinels.Mater. Res. Bull. 1983; 18: 461Google Scholar Finally, Goodenough and his research group discovered another, more cost-effective cathode material (LixMn2O4)11Thackeray M.M. Johnson P.J. de Picciotto L.A. Bruce P.G. Goodenough J.B. Electrochemical extraction of lithium form LiMn2O4.Mater. Res. Bull. 1984; 19: 179-187Google Scholar and came up with the key concept that Lix[Mn2]O4 would also enable the electrochemical extraction of Li for an attractive cathode material of Li cells. Compared with LixCoO2, it showed advantages in terms of low cost, better thermal stability in the charge state, and good rate performance. The rapid technological development in Japan in the 1980s led their electronic products to quickly occupy the international market. Because of the experience of Moli Energy, no company in the West dared to try any new Li battery technology. In the late 1980s, Sony stood up and combined graphite anode with LiCoO2 cathode to assemble a full cell. In 1991, Sony successfully realized the commercialization of Li-ion batteries (LIBs). This new type of battery was much safer because it abandoned the Li-metal anode. As soon as this new battery came out, it was immediately welcomed and directly changed the course of the electronic industry. Portable electronic devices—such as cameras, Walkmans, and mobile phones—were popular all over the world. Sony became a giant in the electronic device industry, in part thanks to significant contributions made by Goodenough. However, LiCoO2 suffered from two main drawbacks: Co is too expensive, and charged Li1-xCoO2 has low thermal stability. Recognizing the cost and thermal-instability concerns of LiCoO2, Arumugam Manthiram and Goodenough explored a series of Fe-containing polyanion oxide cathodes Fe2(XO4)3 in the late 1980s.12Manthiram A. Goodenough J.B. Lithium insertion into Fe2(MO4)3 frameworks: Comparison of M = W with M = Mo.J. Solid State Chem. 1987; 71: 349-360Google Scholar,13Manthiram A. Goodenough J.B. Lithium insertion into Fe2(SO4)3 framework.J. Power Sources. 1989; 26: 403-406Google Scholar They discovered a drastic increase in cell voltage by more than 1 V when going from a simple oxide such as Fe2O3 to a polyanion oxide such as Fe2(SO4)3 as a result of the inductive effect caused by the more covalent SO4 group. During this period, Goodenough and Manthiram transitioned from Oxford to the University of Texas at Austin, where the 64-year-old Goodenough in 1986 became the Virginia H. Cockrell Centennial Chair in Engineering at the Cockrell School of Engineering. The recognition of the power of inductive effect to drastically increase voltage led Goodenough’s group to identify LiFePO4 as a cathode 10 years later in 1997.14Padhi A.K. Nanjundaswamy K.S. Goodenough J.B. Phospho-olivines as positive-electrode materials for rechargeable lithium batteries.J. Electrochem. Soc. 1997; 144: 1188-1194Google Scholar Although its energy performance was slightly lower than that of LiCoO2, LiFePO4 showed some typical superior advantages, such as high stability, low cost, and a wide working temperature range. Nowadays, LiFePO4-based rechargeable batteries are widely used in electric vehicles, large grid-scale energy-storage systems, solar-energy installations, etc. It is amazing that the three classes of layered, spinel, and polyanion oxide materials that his group discovered remain the sole cathodes for commercial LIBs to date.15Manthiram A. A reflection on lithium-ion battery cathode chemistry.Nat. Commun. 2020; 11: 1550Google Scholar The power-generation principle of a fuel cell is similar to that of a primary battery. It is an energy-conversion device that would convert the chemical energy of a fuel directly into electricity. In addition, environmental pollution due to fuel cells is much lower that due to traditional thermal power generation. However, how to improve the working efficiency of fuel cells is challenging. In the early 2000s, Goodenough and his group developed new electrolyte and electrode materials for solid-oxide fuel cells. In 2006, Goodenough and Yunhui Huang discovered double perovskites as anode materials for solid-oxide fuel cells operating on natural gas.16Huang Y.H. Dass R.I. Xing Z.L. Goodenough J.B. Double perovskites as anode materials for solid-oxide fuel cells.Science. 2006; 312: 254-257Google Scholar Such double-perovskite anodes showed high power density and high stability during cycling. Moreover, compared with traditional materials, this anode exhibited excellent tolerance to sulfur and tolerated up to 50 ppm H2S. Fuel cells did not supplant Goodenough’s efforts in LIBs. Indeed, in the history of battery development, the problem of Li dendrites has never been fundamentally solved, and potential safety hazards still exist. Therefore, when he was 90 years old, Goodenough believed that the world needed a “super battery,” and he predicted that the state-of-the-art solid-state Li-metal battery would be that super battery. His group has developed several techniques to enable ultra-low interfacial resistance for solid-state Li-metal batteries. Additionally, Goodenough collaborated with Yuming Chen, Ziqang Wang, and Ju Li to identify the Li plating-stripping mechanism and proposed a Coble-creep engine for all-solid-state Li-metal batteries.17Chen Y. Wang Z. Li X. Yao X. Wang C. Li Y. Xue W. Yu D. Kim S.Y. Yang F. et al.Li metal deposition and stripping in a solid-state battery via Coble creep.Nature. 2020; 578: 251-255Google Scholar Moreover, Goodenough has also made important contributions to other energy-storage devices, such as liquid Na-K batteries18Xue L. Gao H. Zhou W. Xin S. Park K. Li Y. Goodenough J.B. Liquid K-Na alloy anode enables dendrite-free potassium batteries.Adv. Mater. 2016; 28: 9608-9612Google Scholar and Na-ion batteries.19Xu M.W. Xiao P.H. Stauffer S. Song J. Henkelman G. Goodenough J.B. Theoretical and experimental study of vanadium-based fluorophosphate cathodes for rechargeable batteries.Chem. Mater. 2014; 26: 3089-3097Google Scholar Prof. John B. Goodenough is an ageless legend who has dedicated 70 years to interdisciplinary science and engineering to bridge chemistry and physics and has cultivated hundreds of students and postdocs along the way. He is a very kind and inspirational person with a sense of purpose, thoughtfulness, curiosity, and respect for everyone. He often shares encouraging words, such as, “Some of us are like tortoises, walking slowly, struggling all the way, and can’t find a way out in the year of standing. But the tortoise knows that he must go on, and let’s take it one step at a time.” Goodenough is also a good listener and always looks to learn from others. Anyone can talk to him about any topic, and he will entertain them with that loud and happy laugh. He is a role model to everyone not only in science but also in everyday life. His secret to being a successful scientist is recognizing the opportunity, having the freedom to choose how to take advantage of the opportunity, enjoying hard work, and recognizing that most problems are solved through sharing contributions with others. Until a couple of years ago, he still drove to work at the age of 96, but he currently works at home because of coronavirus disease 2019 (COVID-19). In 2019, Goodenough became the oldest Nobel laureate in history at 97. As he said, if you live long enough, you never know what will happen. Maybe his next huge breakthrough will be in the near future. Prof. Goodenough’s 100th birthday is coming up on July 25, 2022, and here we honor his legend by dedicating this article to him.Crystal structures of LixCoO2, LixMn2O4, and LiFePO4.View Large Image Figure ViewerDownload Hi-res image Download (PPT) The authors were fortunate to work with Prof. John B. Goodenough as students and postdoctoral researchers and are deeply indebted to him forever. The authors declare no competing interests.