Investigation of the Impact of High Concentration LiTFSI Electrolytes on Silicon Anodes with Reactive Force Field Simulations

Abstract

The initial formation cycles are critical to the performance of a lithium-ion battery (LIB), particularly in the case of silicon anodes, where the high surface area and extreme volume expansion during cycling make silicon susceptible to detrimental side reactions with the electrolyte. The solid electrolyte interface (SEI) that is formed during these initial cycles serves to protect the surface of the anode from a continued reaction with the electrolyte, and its composition reflects the composition of the electrolyte. In this work, ReaxFF reactive force field simulations were used to investigate the interactions between ether-based electrolytes with high LiTFSI salt concentrations (up to 4 mol/L) and a silicon oxide surface. The simulation investigations were verified with galvanostatic testing and post-mortem X-ray photoelectron spectroscopy, revealing that highly concentrated electrolytes resulted in the faster formation and SEIs containing more inorganic and silicon species. This study emphasizes the importance of understanding the link between electrolyte composition and SEI formation. This ReaxFF approach demonstrates an accessible way to tune electrolyte compositions for optimized performance without costly, time-consuming experimentation.

Caracal: A Versatile Ring Polymer Molecular Dynamics Simulation Package

“…If breaking and forming of chemical bonds shall be included as well, reactive force fields like ReaxFF can be used. − ReaxFF has proven to be of huge benefit for the large-scale simulation of many reactive systems, but it relies again on a thorough initial parametrization or adjustment to the current system of interest. Further, it is hard to parametrize ReaxFFs such that reaction barriers are reproduced with the quality needed, considering that k ( T ) values depend exponentially on potential energy barriers.…”