Effects of different glass formers on Li 2 S–P 2 S 5 –MS 2 (M = Si, Ge, Sn) chalcogenide solid‐state electrolytes

Abstract Chalcogenide solid‐state electrolytes (SSEs) have been receiving growing attentions due to their high ionic conductivity and suitable mechanic properties, especially the Li 2 S–P 2 S 5 systems incorporated with a second glass network formers (Si, Ge, Sn, and so on) besides P. Although the ionic conductivities are generally enhanced with the second glass network formers, the comprehensive effects of different glass formers on other properties, including electrochemical, cycling, and air stability, remain elusive. To acquire deeper understanding, herein, three common but representative glass network formers (SiS 2 , GeS 2 , and SnS 2 ) were introduced into Li 2 S–P 2 S 5 , and their individual effects were investigated systematically. The results of multiscale characterizations before and after lithium stripping/plating cycling confirmed that the introduction of metal cations (Ge, Sn) generally leads to worse electrochemical stability and shorter cycle life of these SSEs toward lithium metal compared with SSEs with nonmetal cation (Si) modification. However, the air stability is related to the binding energy of M–S (M = Si, Ge, Sn), which is consistent with the hard base soft acid theory. This work provides valuable understanding for designing pragmatic Li 2 S–P 2 S 5 –MS 2 ‐based SSEs with high electrochemistry, cycling, and air stability.