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Herein, fluorinated nanochannels are constructed by grafting flexible perfluoroalkyl chains into porous aromatic frameworks (PAF\u20101\u2010F), generating a weakly coordinating environment that promotes ion\u2010pair dissociation and fluorine\u2010polarization\u2010assisted Na\n                    <jats:sup>+<\/jats:sup>\n                    transport. The resulting PAF\u20101\u2010F quasi\u2010solid\u2010state electrolyte exhibits an impressive ionic conductivity of 2.79\u00a0\u00d7\u00a010\n                    <jats:sup>\u22124<\/jats:sup>\n                    S\u00a0cm\n                    <jats:sup>\u22121<\/jats:sup>\n                    , a high Na\n                    <jats:sup>+<\/jats:sup>\n                    transference number of 0.562, and a wide electrochemical stability window of 4.98\u00a0V. The fluorine\u2010rich nanochannels further induce the formation of uniform NaF\u2010rich interphases, enabling stable Na plating\/stripping for over 5700\u00a0h with suppressed dendritic growth. When evaluated in full cells, the PAF\u20101\u2010F quasi\u2010solid\u2010state electrolyte achieves stable cycling over 1300 cycles with 91.3% capacity retention and maintains durable operation for more than 4000 cycles even at \u221220\u00b0C. This work establishes nanochannel\u2010mediated weak coordination as a strategy for coupling ion transport and interfacial stability in quasi\u2010solid\u2010state electrolytes.\n                  <\/jats:p>","DOI":"10.1002\/anie.7843737","type":"journal-article","created":{"date-parts":[[2026,9,23]],"date-time":"2026-09-23T05:55:04Z","timestamp":1790142904000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Manipulating Fluorinated Nanochannels in Porous Aromatic Frameworks for Ultra\u2010Stable Sodium\u2010Ion Transport"],"prefix":"10.1002","author":[{"ORCID":"https:\/\/orcid.org\/0009-0000-1760-8096","authenticated-orcid":false,"given":"Zihao","family":"Wang","sequence":"first","affiliation":[{"name":"Key Laboratory of Polyoxometalate and Reticular Material Chemistry of Ministry of Education and Faculty of Chemistry Northeast Normal University  Changchun P. R. 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