The Interactions between Ionic Liquids and Lithium Polysulfides in Lithium-Sulfur Batteries: A Systematic Density Functional Theory Study.

Ionic liquids (ILs) based on hybrid anions have recently garnered attention as beguiling alternative electrolytes for energy storage devices. This attention stems from the potential of these asymmetric anions to reduce the melting point of ILs and impede the crystallization of ILs. Furthermore, they uphold the advantages associated with their more conventional symmetric counterparts. In this study, we employed dispersion-corrected density functional theory (DFT-D) calculations to scrutinize the interplay between two hybrid anions found in ionic liquids [FTFSA] and [MCTFSA] and the [Cmpyr] cation, as well as in lithium polysulfides in lithium-sulfur batteries. For comparison, we also examined the corresponding ILs containing symmetric anions, [TFSA] and [FSA]. We found that the hybrid anion [MCTFSA] and its ionic liquid exhibited exceptional stability and interaction strength. Additionally, our investigation unveiled a remarkably consistent interaction between ionic liquids (ILs) and anions with lithium polysulfides (and S) during the transition from octathiocane (S) to the liquid long-chain LiS (4 ≤ n ≤ 8). This contrasts with the gradual alignment observed between cations and lithium polysulfides during the intermediate state from LiS to the solid short-chain LiS and LiS. We thoroughly analyzed the interaction mechanism of ionic liquids composed of different symmetry anions and their interactions with lithium polysulfides.