Lithium Ion batteries and the Nobel Prize in Chemistry - 2019

Dr Goutam Singh Ningombam *

2019 Nobel Prize in Chemistry was jointly awarded to John Bannister Goodenough, Michael Stanley Whittingham and Akira Yoshino “for the development of lithium-ion batteries”. It was announced on the 9th October 2019. In a press release by The Royal Swedish Academy of Sciences, a line read as “They created a rechargeable world”.

Many of us must have heard and experience about the lithium ion (Li-ion) batteries. This type of battery has now become an indispensable component in the present era of technological advancements. They are rechargeable; possess lightweight and high energy density power sources which make them highly beneficial for use in many useful devices as compared to other batteries like dry cell, lead storage batteries.

They are used in almost all of the handheld smart electronic devices such as smartphones, laptops, tablets,smart watches, digital cameras etc. Such as in electric cars, many small lithium ion batteries are connected in parallel to provide efficient power supply. In the context of environmental issues also, the Li-ion batteries are categorized as non-hazardous class of batteries.

The components of this battery do not contain any metal of high toxicity concern. The metals like iron, copper, nickel and cobalt present in the battery constitution also do not pose any unsafe consequences for incinerators and landfills and can be recycled as well.

The first commercialized Li-ion battery was brought to the market by Sony in 1991. And in 1992, the A&T Battery (joint venture Company of Asahi Kasei and Toshiba) stared commercialization of the Li-ion Battery. It has now become one of the demanding and promising materials in the market sector of portable electronic devices. However, the actual chemistry of the development of Li-ion battery was started during the oil crisis in 1970s.

It was the sincere relentless efforts of this year’s three Nobel laureates that the Li-ion battery has been gifted for the benefits and comfortable lifestyles of the mankind. The fruit of their inquisitiveness and enthusiasms have made us enjoy the revolution of smart electronic devices; and made our environment safer by the reduction of the use of fossil fuels as well as from the hazardous trash of other form of batteries.

Their scientific efforts in the development of Li-ion batteries have been presented here for information to the readers. The information can also be obtained from the also website - www.nobelprize.org for the press release and scientific backgrounds.

Michael Stanley Whittingham

Professor M. Stanley Whittingham is a British-American Chemist born in 1941 in the United Kingdom. He did his Ph.D. in 1968 from Oxford University, United Kingdom. His current affiliation isBinghamton University, State University of New York, New York, USA. He holds the position of director of both the Institute for Materials Research and The Materials Science and Engineering program at the university.

He was recognized as the Founding Father of the rechargeable lithium batteries. He developed the concept of intercalation electrodes for the so called Li-ion batteries in the 1970s. Actually, Whittingham proposed the concept of intercalation electrodes as early as 1973 with the Exxon (Exxon Research and Engineering Company) and the demonstrated in 1976 in the form of a rechargeable battery.

By then, the Whittingham’s rechargeable Li-ion battery was composed of titanium disulphide (TiS2) as the cathode and lithium metal as the anode. They are also called intercalation batteries.At the molecular level, the cathode has spaces that can house lithium ions. In a simpler term, it behaves like putting jam in a sandwich. And the metallic lithium of the anode has a strong drive to release electrons. He used LiPF6 as the electrolyte in propylene carbonate as the solvent.

The rechargeable battery developed had the capacity to produce just over two volts, about 2.5 volts and an initial current density of 10 milliampere per square centimeter (mA/cm2).During the discharging process, the intercalation of lithium metal into the titanium disulfide lattice and form the lithiated cathode - LiTiS2. Again during the reverse charging process, it starts with the lithiated titanium disulfide.

However, the discovery is still lauded with a limitation that themetallic lithium is reactive and the battery was too explosive to be viable. Further, the reversibility was very challenging and less impressive. He was awarded the Battery Division Research Award by The Electrochemical Society, United States in 2003 in recognition of his research and development of the intercalation electrodes.

The Internal Battery Materials Association (IBA) also awarded him the IBA Yeager Award for Lifetime contribution to Lithium Battery Materials Research. He had been honored and recognized by many learned scientific bodies for his pioneering works in energy storage materials.

John Bannister Goodenough

Professor J. B. Goodenough is an American solid-state physicist born in 1922 in Jena Germany to an American parent. He did his Ph.D. in 1952 from the University of Chicago, USA. He is a professor of mechanical engineering and materials science and also served as the Cockrell Chair in Engineering at the University of Texas, Austin, USA.He became the oldest Nobel laureate (at 97 years old) in history. He is still working to find another breakthrough in battery technology.

After the development made by Whittingham, several attempts were made by others to increase the charging and discharging efficiency. Most importantly, Exxon have improvised the method for commercial batteries which used lithium metal as the anode and titanium disulfide as the cathode. However, it encourages the use of Lithium perchlorate in dioxolane as the solvent. It was later replaced by tetramethyl borate as the electrolyte.

Still, the battery developed by Exxon faced the issue of short circuiting and a potential fire hazard. Then in 1979-1980,the efforts of Goodenoughhave enabledto double the potential of the Whittingham’s rechargeable Li-ion battery from just two volts to four volts. At Oxford University, along with his coworkers, he found out that lithiated cobalt dioxide (LixCoO2) which was analogous to lithiated titanium disulfide (LixTiS2) could serve as cathode material.

He systematically demonstrated that cobalt oxide with intercalated lithium ions is more advantageous than the titanium sulphide and can produce as much as four to five volts. His study proved that the lithium ions were sufficiently mobile in close packed oxygen arrays. It created a powerful battery with higher energy storage capacity and discharging efficiency. In their studies, LiBF4 in propylene carbonate is used as electrolyte and lithium metal or lithium doped vanadium pentoxide (Li0.1V2O5) as counter/reference electrodes.

Professor J. B. Goodenough received a number of awards in due recognition of his contribution to battery technology. He was awarded the Charles StarkDraper Prize in 2014 by the U.S. National Academy of Engineering. He received the Welch Award in Chemistry in 2017 which was conferred by the Robert Alonzo Welch Foundation to encourage and recognize basic chemical research for the benefit of mankind.

The Royal Society, formally The Royal Society of London for Improving Natural Knowledge, awarded him the Copley Medal in 2019 “in recognition of his exceptional contributions to the science and technology of materials, including his discovery that led to rechargeable lithium batteries”. Also, he has been awarded the National Medal of Science by the President Barack Obama of the United States in 2013.

The Royal Society of Chemistry granted the John B. Goodenough Award in honor of this Nobel laureate to those who contribute to the fields of materials chemistry. Many more memberships and awards were garnered in his credits.

Akira Yoshino

Professor Akira Yoshino is a Japanese Chemist at the Meijo University in Nagoya. He was born in 1948. With Goodenough’s cathode as a basis, Akira Yoshino created the first commercially viable lithium-ion battery in 1985. Rather than using reactive lithium in the anode, he used petroleum coke, a carbon material that, like the cathode’s cobalt oxide, can intercalate lithium ions.

His idea of the presently known form of the safe and reliable Li-ion battery was patented in 1983 at the European Patent Office. It was the extended research of this patent that has presented the production-viable rechargeable battery used commonly nowadays in many portable smart electronic devices. The Li-ion battery developed by Yoshino is based on what is called ion transfer cell configuration.

The anode is lithium packed carbonaceous material and thecathode is Goodenough’slithiated cobalt dioxide material typically containing a small amount of tin. In his battery, the lithium perchlorate (LiClO4) in propylene carbonate was used as electrolyte and a polyethylene or propylene as separator layer. His newly developed battery can be damaged by a weight without causing any fires or explosions.

Ultimately, the discovery and the subsequent developments lead to the release of commercial Li-ion battery in 1991. The first commercialized Li-ion battery used a petroleum-coke base anode material, lithiated cobalt dioxide as the cathode and a water-free electrolyte composed of LiPF6 in propylene carbonate. This battery has a charging voltage of upto 4.1 V, with a recorded energy density of about 80 Wh/kgor 200 Wh/L.

And the Li-ion battery became the toughest competitor in the battery market. He did his Ph.D. in 2005 from Osaka University, Japan. He is currently an Honorary Fellow at Asahi Kasei Corporation, Tokyo, Japan. He heads the Japan’s Lithium Ion Battery Technology and Evaluation Centre. He continues his works at the Asahi Kasei to boost the safety and efficiency of Li-ion batteries.

He was awarded the Chemical Technology Prize (March 1999) by the Chemical Society of Japan, BatteryDivision Research Award(October 1999)by The Electrochemical Society, United States for achievements in the development of the lithium-ion battery.

In 2001, the New Technology Development Foundation (Ichimura Foundation) conferred him the Ichimura Prizes in Industry - Meritorious Achievement Prize for his efforts in the development and commercialization of the lithium-ion battery.

Some other mentionable awards include the Global Energy Prize (2013), Charles Stark Draper Prize (2014) and the Japan Prize (2018). Recently, he had been awarded the European Inventor Award this year by the European Patent Office. He had also garnered several other awards from various learned scientific bodies.