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Here, using cost\u2010effective LaCl<jats:sub>3<\/jats:sub> and CeCl<jats:sub>3<\/jats:sub> lattice (UCl<jats:sub>3<\/jats:sub>\u2010type structure) as the host and further combined with a multiple\u2010cation mixed strategy, we report a series of UCl<jats:sub>3<\/jats:sub>\u2010type SSEs with high room\u2010temperature ionic conductivities over 10<jats:sup>\u22123<\/jats:sup>\u2005S\u2009cm<jats:sup>\u22121<\/jats:sup> and good compatibility with high\u2010voltage oxide cathodes. The intrinsic large\u2010size hexagonal one\u2010dimensional channels and highly disordered amorphous phase induced by multi\u2010metal cation species are believed to trigger fast multiple ionic conductions of Li<jats:sup>+<\/jats:sup>, Na<jats:sup>+<\/jats:sup>, K<jats:sup>+<\/jats:sup>, Cu<jats:sup>+<\/jats:sup>, and Ag<jats:sup>+<\/jats:sup>. The UCl<jats:sub>3<\/jats:sub>\u2010type SSEs enable a stable prototype ASSLB capable of over 3000\u2005cycles and high reversibility at \u221230\u2009\u00b0C. Further exploration of the brand\u2010new multiple\u2010cation mixed chlorides is likely to lead to the development of advanced halide SSEs suitable for ASSLBs with high energy density.<\/jats:p>","DOI":"10.1002\/anie.202306433","type":"journal-article","created":{"date-parts":[[2023,10,6]],"date-time":"2023-10-06T15:17:19Z","timestamp":1696605439000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":80,"title":["The Universal Super Cation\u2010Conductivity in Multiple\u2010cation Mixed Chloride Solid\u2010State Electrolytes"],"prefix":"10.1002","volume":"62","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-6713-2997","authenticated-orcid":false,"given":"Xiaona","family":"Li","sequence":"first","affiliation":[{"name":"Eastern Institute for Advanced Study Eastern Institute of Technology  Ningbo Zhejiang 315200 P. R. 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