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Although high\u2010polarity fillers enhance dissociation, liberated Li\n                    <jats:sup>+<\/jats:sup>\n                    tends to be trapped on filler surfaces due to the spatial and dynamic mismatches, hindering Li\n                    <jats:sup>+<\/jats:sup>\n                    long\u2010range migration. To bridge this gap, we establish a consecutive Li\n                    <jats:sup>+<\/jats:sup>\n                    transport pathway by integrating dissociating stators and conducting rotors within an amphidynamic COF (AD COF)\u2010based polymer electrolyte. In the AD COF, the highly polar rigid skeletons (stators) facilitate ionic dissociation, while the tethered flexible oligo(ethylene oxide) side\u2010chains (rotors) with dynamic conformational mobility enable rapid short\u2010range Li\n                    <jats:sup>+<\/jats:sup>\n                    relay corresponding to a segmental relaxation time of 1.10\u00a0\u00d7\u00a010\n                    <jats:sup>\u22125<\/jats:sup>\n                    \u00a0s. Subsequently, Li\n                    <jats:sup>+<\/jats:sup>\n                    is directed into 1D channels of COFs where the confined polymer (PAPE) sustains long\u2010range migration. Benefiting from this rapid and seamless dissociation\u2010conduction synergy, the resulting dry polymer electrolyte (AD COF\u2010PAPE) achieves a room\u2010temperature ionic conductivity of 1.18 \u00d7 10\n                    <jats:sup>\u22124<\/jats:sup>\n                    S cm\n                    <jats:sup>\u22121<\/jats:sup>\n                    , surpassing the PAPE and the all\u2010rigid COF\u2010based polymer counterparts by 460% and 150%, respectively. The AD COF\u2010PAPE enables enhanced electrochemical performance in both Li symmetric cells and NCM\u2010based full cells, underscoring the critical importance of molecularly orchestrating spatial proximity and dynamic matching to overcome the intrinsic trade\u2010offs in SPEs.\n                  <\/jats:p>","DOI":"10.1002\/anie.1789437","type":"journal-article","created":{"date-parts":[[2026,4,24]],"date-time":"2026-04-24T05:24:52Z","timestamp":1777008292000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":4,"title":["Integrating Dissociating Stators and Conducting Rotors Within an Amphidynamic COF\u2010Based Solid\u2010State Polymer Electrolyte for Rapid and Consecutive Li\n                    <sup>+<\/sup>\n                    Transport"],"prefix":"10.1002","volume":"65","author":[{"ORCID":"https:\/\/orcid.org\/0009-0003-7259-3925","authenticated-orcid":false,"given":"Linchu","family":"Xu","sequence":"first","affiliation":[{"name":"State Key Laboratory of Advanced Fiber Materials College of Materials Science and Engineering Donghua University  Shanghai China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Feng","family":"Chen","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Advanced Fiber Materials College of Materials Science and Engineering Donghua University  Shanghai China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"He","family":"Liu","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Advanced Fiber Materials College of Materials Science and Engineering Donghua University  Shanghai 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