Probing the thermodynamics and kinetics of ethylene carbonate reduction at the electrode-electrolyte interface with molecular simulations.

Abstract

Understanding the formation of the solid-electrolyte interphase (SEI) in lithium-ion batteries is an ongoing area of research due to its high degree of complexity and the difficulties encountered by experimental studies. Herein, we investigate the initial stage of SEI growth, the reduction reaction of ethylene carbonate (EC), from both a thermodynamic and a kinetic approach with theory and molecular simulations. We employed both the potential distribution theorem and the Solvation Method based on Density (SMD) to EC solvation for the estimation of reduction potentials of Li+, EC, and Li+-solvating EC (s-EC) as well as reduction rate constants of EC and s-EC. We find that solvation effects greatly influence these quantities of interest, particularly the Li+/Li reference electrode potential in EC solvent. Furthermore, we also compute the inner- and outer-sphere reorganization energies for both EC and s-EC at the interface of liquid EC and a hydroxyl-terminated graphite surface, where total reorganization energies are predicted to be 76.6 and 88.9 kcal/mol, respectively. With the computed reorganization energies, we estimate reduction rate constants across a range of overpotentials and show that EC has a larger electron transfer rate constant than s-EC at equilibrium, despite s-EC being more thermodynamically favorable. Overall, this manuscript demonstrates how ion solvation effects largely govern the prediction of reduction potentials and electron transfer rate constants at the electrode-electrolyte interface.