Boosting Solid‐State Diffusivity and Conductivity in Lithium Superionic Argyrodites by Halide Substitution

Abstract Developing high‐performance all‐solid‐state batteries is contingent on finding solid electrolyte materials with high ionic conductivity and ductility. Here we report new halide‐rich solid solution phases in the argyrodite Li 6 PS 5 Cl family, Li 6− x PS 5− x Cl 1+ x , and combine electrochemical impedance spectroscopy, neutron diffraction, and 7 Li NMR MAS and PFG spectroscopy to show that increasing the Cl − /S 2− ratio has a systematic, and remarkable impact on Li‐ion diffusivity in the lattice. The phase at the limit of the solid solution regime, Li 5.5 PS 4.5 Cl 1.5 , exhibits a cold‐pressed conductivity of 9.4±0.1 mS cm −1 at 298 K (and 12.0±0.2 mS cm −1 on sintering)—almost four‐fold greater than Li 6 PS 5 Cl under identical processing conditions and comparable to metastable superionic Li 7 P 3 S 11 . Weakened interactions between the mobile Li‐ions and surrounding framework anions incurred by substitution of divalent S 2− for monovalent Cl − play a major role in enhancing Li + ‐ion diffusivity, along with increased site disorder and a higher lithium vacancy population.