Unveiling the Reaction Mystery Between Lithium Polysulfides and Lithium Metal Anode in Lithium–Sulfur Batteries

Abstract Lithium‐sulfur (Li–S) batteries are widely regarded as one of the most promising next‐generation high‐energy‐density energy storage devices. However, soluble lithium polysulfides (LiPSs) corrode Li metal and deteriorate the cycling stability of Li–S batteries. Understanding the reaction mechanism between LiPSs and Li metal anode is imperative. Herein, the reaction rate and products of LiPSs with Li metal anode, the composition and structure of the as‐generated solid electrolyte interphase (SEI), and the mechanism of lithium nitrate (LiNO₃) additives for inhibiting the corrosion reactions are systematically unveiled. Concretely, LiPSs react with Li metal anode more rapidly than Li salt and generate a Li₂S‐rich SEI. The Li₂S‐rich SEI is highly reactive with LiPSs, which exacerbates the formation of dendritic Li and the continuous corrosion of active Li. LiNO₃ functions dominantly by modulating the solvation structure of LiPSs and inherently reducing the reactivity of LiPSs, rather than the conventional understanding of LiNO₃ participating in the formation of SEI. This work reveals the reaction mechanism between LiPSs and Li metal anode and inspires rational regulating of the solvation structure of LiPSs for stabilizing Li metal anode in Li–S batteries.