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Here we propose an electrolyte design strategy based on molecular fluorination symmetry. This approach employs difluoro\u2010symmetric substitution to precisely steer decomposition pathways towards preferential ring\u2010opening reactions, thereby effectively suppressing defluorination decomposition and the concomitant formation of acidic byproducts at elevated temperatures. Through rational molecular engineering of synergistic fluorination, we achieve directed interfacial chemistry control. Under harsh operational conditions (4.5\u00a0V, 45\u00b0C), the modified cells retain 83% of their capacity after 300 cycles, along with significantly reduced gas generation and an elevated thermal runaway onset temperature. Furthermore, 2\u00a0Ah graphite||LiNi\n                    <jats:sub>0.8<\/jats:sub>\n                    Co\n                    <jats:sub>0.1<\/jats:sub>\n                    Mn\n                    <jats:sub>0.1<\/jats:sub>\n                    O\n                    <jats:sub>2<\/jats:sub>\n                    pouch cells exhibit a capacity retention of 90% after 480 cycles at 45\u00b0C and 91% after 200 cycles at 60\u00b0C. These results establish molecular fluorination symmetry as a practical design principle for electrolytes that enhance high\u2010temperature performance and intrinsic safety in Ni\u2010rich cathodes under demanding operational conditions.\n                  <\/jats:p>","DOI":"10.1002\/anie.5558984","type":"journal-article","created":{"date-parts":[[2026,5,28]],"date-time":"2026-05-28T09:18:37Z","timestamp":1779959917000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":1,"title":["Tuning Reaction Pathways via Symmetric Fluorination Enables High\u2010Temperature and High\u2010Voltage Electrolytes"],"prefix":"10.1002","volume":"65","author":[{"given":"Fangyuan","family":"Cheng","sequence":"first","affiliation":[{"name":"Eastern Institute for Advanced Study Eastern Institute of Technology  Ningbo China"},{"name":"Zhejiang Key Laboratory of All\u2010Solid\u2010State Battery Ningbo Key Laboratory of All\u2010Solid\u2010State Battery  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