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Here, we reveal the insertion electrochemistry of VX<jats:sub>3<\/jats:sub> (X=Cl, Br, I) by introducing a compatible halide solid\u2010state electrolyte with a wide electrochemical stability window. X\u2010ray absorption near\u2010edge structure analyses reveal a two\u2010step lithiation process and the structural transition of typical VCl<jats:sub>3<\/jats:sub>. Fast Li<jats:sup>+<\/jats:sup> insertion\/extraction in the layered VX<jats:sub>3<\/jats:sub> active materials and favorable interface guaranteed by the compatible electrode\u2010electrolyte design enables high rate capability and stable operation of all\u2010solid\u2010state Li\u2010VX<jats:sub>3<\/jats:sub> 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.<\/jats:p>","DOI":"10.1002\/anie.202217081","type":"journal-article","created":{"date-parts":[[2023,1,26]],"date-time":"2023-01-26T03:09:08Z","timestamp":1674702548000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":45,"title":["Halide Layer Cathodes for Compatible and Fast\u2010Charged Halides\u2010Based All\u2010Solid\u2010State Li Metal Batteries"],"prefix":"10.1002","volume":"62","author":[{"given":"Jianwen","family":"Liang","sequence":"first","affiliation":[{"name":"Department of Mechanical and Materials Engineering University of Western Ontario  1151 Richmond St London Ontario N6A 3K7 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