Materials Chemistry - Li-ion Batteries

Updated: Aug 6

Victor Luca, 10-Jan-21.


Materials chemistry & engineering discussions here.


I have been involved in Materials Chemistry research for more than thirty years and I will be posting some highlights in materials chemistry of past and ongoing developments over those years that are expected make a major impact on people's lives going forward.


Lithium ion Batteries were first discovered in the late eighties by university-based researchers and later commercialized by Sony Corporation. The first university researcher to describe intercalation electrodes used in Li-ion batteries was Professor Stanley Whittingham who together with Professor John B. Goodenough received the Nobel Prize in Chemistry in 2019 for their pioneering development of these batteries.


Li-ion batteries have become an indispensable part of our lives initially due to the portable electronics revolution and now their importance in transportation. Li-ion batteries have very much enabled these technologies. Li-ion batteries are only one of many chemical energy storage systems that number in the thousands.


An article by Whittingham & Dines published 1977 [1] and subsequent work relating to the insertion of Li into various metal oxides caught my eye in 1995. I realized some time earlier that energy storage was going to represent an important weapon in our battle to fight anthropogenic climate change which I considered an obvious problem for humanity that required urgent attention. I realized that we were going to have to revolutionize our energy generation system and electrify transport. It was clear to me that zero-emissions and more efficient energy storage and conversion technologies would be indispensable.


Since I had a long standing interest in the chemical properties of nano-crystalline semi-conducting oxides such as V2O5 and TiO2, and since I was involved in an ARC-funded project on the photo-chemistry of TiO2 under the auspices of Professor Russell Howe at the University of New South Wales (UNSW), I decided to investigate what happened to TiO2 at the structural level when Li was inserted. Whittingham and others had shown some potential for this oxide.


I had learned later in 1996 that just across the road from the Chemistry building at the UNSW was the electrochemical engineering laboratory of Professor Maria Skyllas-Kazacos. Maria had been working on redox flow batteries for more than a decade and had such a battery installed in golf-cart that used to be driven around the university. I made contact, and later when I moved institutions we formed a collaboration to research Li-ion batteries. She is rightly credited as being the inventor of the vanadium redox flow battery.


These flow batteries had significant potential in stationary grid-level energy storage applications but were not considered viable for transportation applications due to their limited capacity. Today, there are many of these batteries installed for grid storage.


Later in 1997 when I took up a position at the Australian Nuclear Science and Technology Organization (ANSTO), I continued to have energy storage as one of my research themes and approached Maria to form a formal collaboration on Li-ion batteries in which TiO2 replaces graphite on the anode side. Batteries with TiO2 anodes have lower voltage and capacity than conventional Li-ion batteries but have excellent cyclability, long life, better low temperature performance and don't burst into flames since they do not contain carbon.


Today Toshiba Corporation markets such a batteries under the trade-name SCiB.



References


[1] Whittingham, S.M. Dines, M.B. n-Butyllithium - An Effective, General Cathode Screening Agent. J. Electrochem. Soc., 1977, 124(9), 124 1387.


[2] Whittingham, M.S. Lithium Batteries and Cathode Materials. Chem. Rev. 2004, 104, 4271 −4301.


[3] Luca, V.; Djajanti, S.; Howe, R. F. Structural and electronic properties of sol-gel titanium oxides studied by X-ray absorption spectroscopy. J. Phys. Chem. B 1998, 102, 10650-10657.


[4] Luca, V.; Hanley, T. L.; Roberts, N. K.; Howe, R. F. NMR and X-ray absorption study of lithium intercalation in micro- and nanocrystalline anatase. Chem. Mater. 1999, 11, 2089-2102.


[5] Luca, V.; Hunter, B.; Moubaraki, B.; Murray, K. S. Lithium Intercalation in Anatase-Structural and Magnetic Considerations. Chem. Mater. 2001, 13, 796-801.


[6] Milne, N. A.; Griffith, C. S.; Hanna, J. V.; Skyllas-Kazacos, M.; Luca, V. Lithium Intercalation Into the Titanosilicate Sitinakite. Chem. Mater. 2006, 18, 3192-3202.


[7] Lindsay, M. J. ; Blackford, M. G.; Attard, D. J.; Luca, V.; Skyllas-Kazacos, M.; Griffith, C. S. Anodic titania films as anode materials for lithium ion batteries. Electrochim. Acta 2007, 52, 6401-6411.


[8] Milne, N. A.; Skyllas-Kazacos, M.; Luca, V. Crystallite size dependence of lithium intercalation in nanocrystalline rutile. J. Phys. Chem. C 2009, 113, 12983-12995.


[9] Luca, V. Comparison of Size-dependent structural and electronic properties of anatase and rutile nanoparticles. J. Phys. Chem. C 2009, 113, 6367-6380.


[10] Lindsay, M. J. ; Skyllas-Kazacos, M.; Luca, V. Anodically synthesized titania films for lithium batteries: Effect of titanium substrate and surface treatment. Electrochim. Acta 2009, 54, 3501-3509.





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