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However, most studies have focused on ion\u2010stacking structures, overlooking the role of bond characteristics in ionic transport. Here, we investigate bond dynamics and the superionic transition (SIT) in bromide electrolyte, Li\n                    <jats:sub>3<\/jats:sub>\n                    InBr\n                    <jats:sub>6<\/jats:sub>\n                    , using synchrotron X\u2010ray techniques and ab initio molecular dynamics (AIMD) simulations. We demonstrate that the SIT in halide SSEs is driven by a thermally induced transition in bonding character (ionic to covalent) rather than a change in crystal phase. AIMD simulations further reveal enhanced Li\u207a diffusion and collective anion motion at elevated temperatures. Expanding our study to Li\n                    <jats:sub>3<\/jats:sub>\n                    LnBr\n                    <jats:sub>6<\/jats:sub>\n                    (Ln\u00a0=\u00a0Gd, Tb, Ho, Tm, and Lu), we confirm the widespread occurrence of SIT in this material class, with Li\n                    <jats:sub>3<\/jats:sub>\n                    GdBr\n                    <jats:sub>6<\/jats:sub>\n                    exhibiting the highest ionic conductivity (5.2 mS cm\n                    <jats:sup>\u22121<\/jats:sup>\n                    at 298\u00a0K). More importantly, the ionic\u2010covalent transition is highly tunable through electrolyte modifications, such as cation\/anion substitution and synthesis methods. Our findings provide a new perspective on ionic transport, highlighting the critical role of chemical bond characteristics in halide SSEs.\n                  <\/jats:p>","DOI":"10.1002\/anie.202508835","type":"journal-article","created":{"date-parts":[[2025,5,29]],"date-time":"2025-05-29T02:13:57Z","timestamp":1748484837000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":16,"title":["Chemical Bond Covalency in Superionic Halide Solid\u2010State Electrolytes"],"prefix":"10.1002","volume":"64","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-1874-111X","authenticated-orcid":false,"given":"Jiamin","family":"Fu","sequence":"first","affiliation":[{"name":"Department of Mechanical and Materials Engineering University of Western Ontario  London Ontario N6A 5B9 Canada"},{"name":"Department of Chemistry University of Western Ontario  London Ontario N6A 5B7 Canada"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Han","family":"Su","sequence":"additional","affiliation":[{"name":"Department of Mechanical and Materials Engineering University of Western Ontario  London Ontario N6A 5B9 Canada"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jing","family":"Luo","sequence":"additional","affiliation":[{"name":"Department of Mechanical and Materials Engineering University of Western Ontario  London Ontario N6A 5B9 Canada"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xiaona","family":"Li","sequence":"additional","affiliation":[{"name":"Ningbo Key Laboratory of All\u2010Solid\u2010State Battery Ningbo Institute of Digital Twin Eastern Institute for Advanced Study Eastern Institute of Technology  Ningbo Zhejiang 315200 P.R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jianwen","family":"Liang","sequence":"additional","affiliation":[{"name":"China Automotive Battery Research Institute Co., Ltd.  Beijing 100088 P.R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Changhong","family":"Wang","sequence":"additional","affiliation":[{"name":"Ningbo Key Laboratory of All\u2010Solid\u2010State Battery Ningbo Institute of Digital Twin Eastern Institute for Advanced Study Eastern Institute of Technology  Ningbo Zhejiang 315200 P.R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jung Tae","family":"Kim","sequence":"additional","affiliation":[{"name":"Department of Mechanical and Materials Engineering University of Western Ontario  London Ontario N6A 5B9 Canada"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yang","family":"Hu","sequence":"additional","affiliation":[{"name":"Department of Mechanical and Materials Engineering University of Western Ontario  London Ontario N6A 5B9 Canada"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Feipeng","family":"Zhao","sequence":"additional","affiliation":[{"name":"Department of Mechanical and Materials Engineering University of Western Ontario  London Ontario N6A 5B9 Canada"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Shumin","family":"Zhang","sequence":"additional","affiliation":[{"name":"Department of Mechanical and Materials Engineering University of Western Ontario  London Ontario N6A 5B9 Canada"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hui","family":"Duan","sequence":"additional","affiliation":[{"name":"School of Metallurgy and Environment Central South University  Changsha 410083 P.R. 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