Although several crystalline materials have been developed as Li-ion conductors for use as solid electrolytes in all-solid-state batteries (ASSBs), producing materials with high Li-ion conductivities is timeconsuming and cost-intensive. Herein, we introduce a superionic halogen-rich Li-argyrodite (HRLA) and demonstrate its innovative synthesis using ultimate-energy mechanical alloying (UMA) and rapid thermal annealing (RTA). UMA with a 49 G-force milling energy provides a one-pot process that includes mixing, glassification, and crystallization, to produce as-milled HRLA powder that is ∼70% crystallized; subsequent RTA using an infrared lamp increases this crystallinity to ∼82% within 25 min. Surprisingly, this HRLA exhibits the highest Li-ion conductivity among Li-argyrodites (10.2 mS cm −1 at 25 °C, cold-pressed powder compact) reported so far. Furthermore, we confirm that this superionic HRLA works well as a promising solid electrolyte without a decreased intrinsic electrochemical window in various electrode configurations and delivers impressive cell performance (114.2 mAh g −1 at 0.5 C).

The composite cathode of an all-solid-state battery composed of various solid-state components requires a dense microstructure and a highly percolated solid-state interface different from that of a conventional liquid-electrolyte-based Li-ion battery. Indeed, the preparation of such a system is particularly challenging. In this study, quantitative analyses of composite cathodes by three-dimensional reconstruction analysis were performed beyond the existing qualitative analysis, and their microstructures and reaction interfaces were successfully analyzed. Interestingly, various quantitative values of structure properties (such as the volume ratio, connectivity, tortuosity, and pore formation) associated with material optimization and process development were predicted, and they were found to result in limited electrochemical charge/discharge performances. We also verified that the effective two-phase boundaries were significantly suppressed to ∼23% of the total volume because of component dispersion and packing issues.

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.