Superionic Halogen-Rich Li-Argyrodites Using In Situ Nanocrystal Nucleation and Rapid Crystal Growth

Abstract

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 time-consuming 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 similar to 70% crystallized; subsequent RTA using an infrared lamp increases this crystallinity to similar to 82% within 25 min. Surprisingly, this HRLA exhibits the highest Li-ion conductivity among Li-argyrodites (10.2 mS cm(-1) at 25 degrees 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).