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In conventional LiPF\n                    <jats:sub>6<\/jats:sub>\n                    \u2010based electrolytes containing fluoroethylene carbonate (FEC), LiPF\n                    <jats:sub>6<\/jats:sub>\n                    decomposition generates Lewis\u2010acid species that trigger FEC defluorination and HF formation, causing progressive interphase degradation. Here we report a multifunctional gel polymer electrolyte (MGPE) that integrates solvation regulation with polymer\u2010network confinement and interrupts the PF\n                    <jats:sub>5<\/jats:sub>\n                    \u2013FEC degradation pathway via strong PF\n                    <jats:sub>6<\/jats:sub>\n                    <jats:sup>\u2212<\/jats:sup>\n                    binding. The fluorinated aromatic additive 1,1,2,2\u2010tetrafluoroethoxybenzene modulates the Li\n                    <jats:sup>+<\/jats:sup>\n                    solvation structure and promotes preferential formation of a stable cathode\u2010electrolyte interphase, enhancing oxidative stability up to 5.0\u00a0V. Meanwhile, in situ polymerization of 3,5\u2010bis(trifluoromethyl)styrene constructs a fluorinated aromatic network with strong affinity toward PF\n                    <jats:sub>6<\/jats:sub>\n                    <jats:sup>\u2212<\/jats:sup>\n                    , suppressing Lewis\u2011acidic PF\n                    <jats:sub>5<\/jats:sub>\n                    formation. The synergistic interplay between solvation regulation, PF\n                    <jats:sub>5<\/jats:sub>\n                    suppression, and fluorinated\u2010network confinement steers interphase evolution toward dense LiF\u2010rich layers on both electrodes, enabling Li||LiCoO\n                    <jats:sub>2<\/jats:sub>\n                    cells to retain 82.6% capacity after 400 cycles at 4.5\u00a0V and 90.3% after 200 cycles at a cathode loading of \u223c11\u00a0mg\u00a0cm\n                    <jats:sup>\u22122<\/jats:sup>\n                    . Furthermore, 1.3\u00a0Ah pouch cells (N\/P\u00a0=\u00a01.1) show 80.7% capacity retention after 30 cycles under practical conditions. This work provides an electrolyte\u2010engineering strategy to suppress PF\n                    <jats:sub>5<\/jats:sub>\n                    \u2010induced degradation and stabilize interphase evolution, enabling safer high\u2010energy lithium metal batteries.\n                  <\/jats:p>","DOI":"10.1002\/anie.6028878","type":"journal-article","created":{"date-parts":[[2026,8,27]],"date-time":"2026-08-27T06:10:56Z","timestamp":1787811056000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Synergistic Molecular and Polymer Network Design Enables Stable LiPF\n                    <sub>6<\/sub>\n                    \u2010Based Gel Polymer Electrolytes for Lithium Metal Batteries"],"prefix":"10.1002","volume":"65","author":[{"given":"Min","family":"Wang","sequence":"first","affiliation":[{"name":"Guangdong Provincial Key Laboratory of Thermal Management Engineering &amp; Materials Tsinghua Shenzhen International 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