Modeling Electrochemical Decomposition of Fluoroethylene Carbonate on Silicon Anode Surfaces in Lithium Ion Batteries

By K. Leung, S. Rempe, M. E. Foster, Yuguang Ma, J. M. M. L. Hoz, Na Sai, P. Balbuena. 2014

155 citations recorded by the source corpus.

Fluoroethylene carbonate (FEC) shows promise as an electrolyte additive for improving passivating solid-electrolyte interphase (SEI) films on silicon anodes used in lithium ion batteries (LIB). We apply density functional theory (DFT), ab initio molecular dynamics (AIMD), and quantum chemistry techniques to examine excess-electron-induced FEC molecular decomposition mechanisms that lead to FEC-modified SEI. We consider one- and two-electron reactions using cluster models and explicit interfaces between liquid electrolyte and model Li(x)Si(y) surfaces, respectively. FEC is found to exhibit more varied reaction pathways than unsubstituted ethylene carbonate. The initial bond-breaking events and products of one- and two-electron reactions are qualitatively similar, with a fluoride ion detached in both cases. However, most one-electron products are charge-neutral, not anionic, and may not coalesce to form effective Li+-conducting SEI unless they are further reduced or take part in other reactions. The implications of these reactions to silicon-anode based LIB are discussed.

Subfields: Electrical and Electronic Engineering, Inorganic Chemistry

View Paper: https://www.semanticscholar.org/paper/e1e0b4cc9c6369efb11e32d858fc292ba269edbe

How researchers see this paper

The researchers whose trusted networks rank it highest, strongest advocate first. Every researcher gets a different order.

In Electrical and Electronic Engineering

1. Jianlin Li
2. D. Wood
3. Seong-Jin An
4. Hong Li
5. Yue Qi
6. Claus Daniel
7. S. Shi 施
8. Sanket Kadam

Citations in the corpus

• Review on modeling of the anode solid electrolyte interphase (SEI) for lithium-ion batteries (2018, background): “Overall, the two-electron transfer process is thermodynamically and kinetically favorable for FEC reduction.98,120 The F− can detach after the reduction of FEC, and combine with Li+ to form LiF.120 LiF is an important reduction product of FEC observed in the SEI with FEC additives.”
• The state of understanding of the lithium-ion-battery graphite solid electrolyte interphase (SEI) and its relationship to formation cycling (2016, background): “Certain interfacial reduction and oxidation reactions have been described in the literature using AIMD.[182-188] APPLE&P (Atomistic Polarizable Potential for Liquids, Electrolytes, & Polymers) is another many-body polarizable force field for MD simulations that can capture electrostatic interactions”