Reaction Mechanism of Methyl Trifluoroacetate (CH 3 TFA) with Lithium Polysulfides (Li 2 S 6 ) in Gas and Solvent Phase

Abstract

In this DFT study, we have evaluated the reaction mechanism of lithium polysulfide (Li2S6) with the electrolyte additive methyl trifluoroacetate (CH3TFA) in the gas and solvent (dimethoxyethane (DME)) phase at room temperature (298 K) by locating transition states (TS) for the methyl group transfer from CH3TFA to Li2S6, which is reported to produces organosulfur ((CH3)2S6). All the reported methyl transfer reactions that lead to the formation of organosulfur are having high barrier energy. The barrier energy difference between gas and solvent phase is maximum of 7 kcal/mol and both the reactions are in extreamely slow regime. therefore, the methyl transfer reaction for the formation of organosulfur implausible at room temperature.