Halide Layer Cathodes for Compatible and Fast‐charged Halides‐based All‐solid‐state Li Metal Batteries

Insertion-type compounds based on oxides and sulfides have been widely identified and well-studied as cathode materials in lithium-ion batteries. However, halides have rarely been used due to their high solubility in organic liquid electrolytes. Here, we reveal the insertion electrochemistry of VX (X=Cl, Br, I) by introducing a compatible halide solid-state electrolyte with a wide electrochemical stability window. X-ray absorption near-edge structure analyses reveal a two-step lithiation process and the structural transition of typical VCl . Fast Li insertion/extraction in the layered VX active materials and favorable interface guaranteed by the compatible electrode-electrolyte design enables high rate capability and stable operation of all-solid-state Li-VX batteries. The findings from this study will contribute to developing intercalation insertion electrochemistry of halide materials and exploring novel electrode materials in viable energy storage systems.