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Here, we report a fast\u2010ion\u2010conductor multiscale nanoconfinement strategy that enables continuous high\u2010throughput Na\n                    <jats:sup>+<\/jats:sup>\n                    migration in CPEs by embedding polyethylene glycol (PEG)\u2010confined boron\u2010rich covalent organic framework (BCOF) nanotubes into a poly(ethylene oxide) (PEO) matrix. Size\u2010compatible PEG oligomers as fast\u2010ion\u2010conductors are effectively confined within the well\u2010defined nanopores\/tunnels of BCOF nanotube via Lewis acid\u2010base interactions, creating interconnected Na\n                    <jats:sup>+<\/jats:sup>\n                    migration pathways. Simultaneously, the intermolecular interactions between Lewis\u2010acidic boron sites in BCOF and oxygen atoms in PEO\/PEG weaken Na\n                    <jats:sup>+<\/jats:sup>\n                    \u2500O coordination strength, further boosting Na\n                    <jats:sup>+<\/jats:sup>\n                    transport kinetics. This pioneering design allows the constructed CPEs to achieve exceptional ionic conductivity of up to 1.99 mS cm\n                    <jats:sup>\u22121<\/jats:sup>\n                    at 60\u00b0C and 0.36 mS cm\n                    <jats:sup>\u22121<\/jats:sup>\n                    at 30\u00b0C, with a high Na\n                    <jats:sup>+<\/jats:sup>\n                    transference number of 0.89. As such, the Na\/Na symmetric cell delivers stable Na plating\/stripping over 3200\u00a0h at 0.1\u00a0mA cm\n                    <jats:sup>\u22122<\/jats:sup>\n                    . High\u2010loading all\u2010solid\u2010state pouch cells exhibit exceptional cycling stability, maintaining 90.7 % capacity retention over 800 cycles at 1 C and near\u2010ambient conditions. This study emphasizes the significant impact of multiscale nanoconfinement chemistry on the advancement of all\u2010solid\u2010state batteries.\n                  <\/jats:p>","DOI":"10.1002\/adma.202518830","type":"journal-article","created":{"date-parts":[[2025,12,31]],"date-time":"2025-12-31T13:50:45Z","timestamp":1767189045000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":10,"title":["Fast\u2010Ion\u2010Conductor Multiscale Nanoconfinement Overcomes Ion\u2010Transport Limitations in All\u2010Solid\u2010State Sodium Batteries"],"prefix":"10.1002","volume":"38","author":[{"given":"Junhong","family":"Guo","sequence":"first","affiliation":[{"name":"The Key Laboratory of Synthetic and Biological Colloids School of Chemical and Material Engineering Ministry of Education International Joint Research Laboratory for Nano Energy Composites Jiangnan University  Wuxi 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Laboratory for Nano Energy Composites Jiangnan University  Wuxi China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Feili","family":"Lai","sequence":"additional","affiliation":[{"name":"Department of Chemistry KU Leuven  Leuven Belgium"},{"name":"Max Planck Institute For Polymer Research  Mainz Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Zi\u2010Feng","family":"Ma","sequence":"additional","affiliation":[{"name":"Shanghai Electrochemical Energy Devices Research Center Department of Chemical Engineering Shanghai Jiao Tong University  Shanghai China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Johan","family":"Hofkens","sequence":"additional","affiliation":[{"name":"Department of Chemistry KU Leuven  Leuven Belgium"},{"name":"Max Planck Institute For Polymer Research  Mainz Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Tianxi","family":"Liu","sequence":"additional","affiliation":[{"name":"The 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