Revealing the Impact of Cl Substitution on the Crystallization Behavior and Interfacial Stability of Superionic Lithium Argyrodites

Abstract

AbstractAll‐solid‐state batteries are believed to be the next‐generation energy storage device that can meet the ever‐growing market demand for high energy density and safety. The ionic conductivity and electrochemical stability of the solid electrolyte are two crucial properties that can affect battery performance. Herein, with an optimized crystallization process, the Cl‐rich argyrodite possesses high ionic conductivity, good dendrite inhibition capability, as well as enhanced interfacial stability against decomposition. Ab initio molecular dynamics simulation and radial distribution function analysis are utilized to probe into the interfacial phenomenon between argyrodite electrolyte and lithium metal. LiNi0.8Co0.1Mn0.1O2‐based all‐solid‐state battery using the Cl‐rich argyrodite electrolyte also delivers more stable cyclic performance. This study shows the multiple enhancements of argyrodite electrolyte brought by Cl doping, which provides important guidance in selecting electrolytes for all‐solid‐state batteries.