Cation-Directed Selective Polysulfide Stabilization in Alkali Metal–Sulfur Batteries

Alkali metal sulfur redox chemistry offers promising potential for high-energy-density energy storage. Fundamental understanding of alkali metal sulfur redox reactions is the prerequisite for rational designs of electrode and electrolyte. Here, we revealed a strong impact of alkali metal cation (Li +, Na +, K +, and Rb + ) on polysulfide (PS) stability, redox reversibility, and solid product passivation. We employed operando UV–vis spectroscopy to show that strongly negatively charged short-chain PS (e.g., S 4 2– /S 3 2– ) is more stabilized in the electrolyte with larger cation (e.g., Rb + ) than that with the smaller cation (e.g., Li + ), which is attributed to a stronger cation–anion electrostatic interaction between Rb + and S 4 2– /S 3 2– owing to its weaker solvation energy. In contrast, Li + is much more strongly solvated by solvent and thus exhibits a weaker electrostatic interaction with S 4 2– /S 3 2– . The stabilization of short-chain PS in K + –, Rb + –sulfur cells promotes the reduction of long-chain PS to short-chain PS, leading to high discharge potential. However, it discourages the oxidation of short-chain PS to long-chain PS, leading to poor charge reversibility. Our work directly probes alkali metal–sulfur redox chemistry in operando and provides critical insights into alkali metal sulfur reaction mechanism.