Anion‐Involved Solvation Structure of Lithium Polysulfides in Lithium–Sulfur Batteries

Lithium polysulfides (LiPSs) are pivotal intermediates involved in all the cathodic reactions in lithium–sulfur (Li–S) batteries. Elucidating the solvation structure of LiPSs is the first step for rational design of electrolyte and improving Li–S battery performances. Herein, we investigate the solvation structure of LiPSs and find that Li salt anions tend to enter the first solvation sheath of LiPSs and form contact ion pairs in electrolyte. The anion‐involved solvation structure of LiPSs significantly influences the intrinsic kinetics of the sulfur redox reactions. In particular, the LiPS solvation structure modified by lithium bis(fluorosulfonyl)imide endows Li–S batteries with reduced polarization and enhanced rate performances under high sulfur areal loading and lean electrolyte volume conditions. This work updates the fundamental understanding of the solvation chemistry of LiPSs and highlights electrolyte engineering for promoting the performances of Li–S batteries.