Functionalized Sulfide Solid Electrolyte with Air-Stable and Chemical-Resistant Oxysulfide Nanolayer for All-Solid-State Batteries

[Image: see text] Sulfide solid electrolytes (SEs) with high Li-ion conductivities (σ(ion)) and soft mechanical properties have limited applications in wet casting processes for commercial all-solid-state batteries (ASSBs) because of their inherent atmospheric and chemical instabilities. In this study, we fabricated sulfide SEs with a novel core–shell structure via environmental mechanical alloying, while providing sufficient control of the partial pressure of oxygen. This powder possesses notable atmospheric stability and chemical resistance because it is covered with a stable oxysulfide nanolayer that prevents deterioration of the bulk region. The core–shell SEs showed a σ(ion) of more than 2.50 mS cm(–1) after air exposure (for 30 min) and reaction with slurry chemicals (mixing and drying for 31 min), which was approximately 82.8% of the initial σ(ion). The ASSB cell fabricated through wet casting provided an initial discharge capacity of 125.6 mAh g(–1). The core–shell SEs thus exhibited improved powder stability and reliability in the presence of chemicals used in various wet casting processes for commercial ASSBs.