Temperature Influence on Silicon-Based Anodes for Li-Ion Batteries

Nowadays, with the aim of reducing the pollution derived from the utilization of fossil fuel powered cars, the environmentally friendly hybrid (HEVs) and electric vehicles (EVs) are gaining importance[1], [2]. Although EVs already circulate on the roads, the search for next-generation lithium-ion batteries (LIBs) with larger specific capacity and, therefore, higher energy density is necessary to achieve similar driving performance (e.g., range and power) to those provided by internal combustion engines. A strategy to upgrade the specific capacity of current LIBs consists of replacing graphite, the anode par excellence in this technology, with other materials that can supply much larger capacities[3], [4]. In this sense, silicon is postulated as one of the most promising anode materials, since it is capable of delivering a capacity (~3579 mAh/g) almost 10 times larger than that of graphite (~370 mAh/g)[5], [6]. Additionally, silicon is the second most abundant element in the earth’s crust, making it an affordable substitute of carbonaceous anode materials for LIBs[7]. However, although numerous scientific studies have been performed on silicon anodes for LIBs, a parameter that has not been evaluated and that would be of interest is the impact that temperature would have on its cycle-life. To fill in this gap, we have performed galvanostatic experiments at different temperatures with silicon-based anodes in half-cells with and without fluoroethylene carbonate (FEC) as electrolyte additive. The different capacity fading behavior observed and the possible kinetic mechanisms behind them will be discussed here. We gratefully acknowledge support from the U. S. Department of Energy (DOE), Vehicle Technologies Office. Argonne National Laboratory is operated for DOE Office of Science by UChicago Argonne, LLC, under contract number DE-AC02-06CH11357. The U.S. government retains for itself, and others acting on its behalf, a paid-up nonexclusive, irrevocable worldwide license in said article to reproduce, prepare derivative works, distribute copies to the public, and perform publicly and display publicly, by or on behalf of the government. [1] M. Armand and J-M. Tarascon. Nature 2008, 451 , 652-657. Building better batteries. [2] C. C. Chan. EEE 1999 International Conference on Power Electronics and Drive Systems, PEDS’99, Hong Kong. The Past, Present and Future of Electric Vehicle Development. [3] W-J. Zhang, J. Power Sources 2011, 196 (1), 12-24. A review of the electrochemical performance of alloy anodes for lithium-ion batteries. [4] V. Etacheri, R. Marom, R. Elazari, G. Salitra and D. Aurbach. Energy Environm. Sci. 2011, 4 , 3243-3262. Challenges in the development of advanced Li-ion batteries: a review. [5] X. Su, Q. Wu, J. Li, X. Xiao, A. Lott, W. Lu, B. W. Sheldon and J. Wu. Adv. Energy Mater. 2014, 4 , 1300882. Silicon-Based Nanomaterials for Lithium-Ion Batteries: A Review. [6] H. Wu and Y. Cui. Nanotoday 2012, 7 (5), 414-429. Designing nanostructured silicon anodes for high energy lithium ion batteries. [7] U. Kasavajjula, C. Wang and A. J. Appleby. Journal of Power Sources 2007, 163 , 1003. Nano- and bulk-silicon-based insertion anodes for lithium-ion secondary cells.