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However, current AFSBs are usually confined to room\/low temperatures, and pouch cell\u2010level AFSBs capable of stable cycling &gt;25\u00b0C have rarely been reported. Here we report high\u2010temperature AFSBs via spatially strengthened ion\u2010dipole electrolyte chemistry. Specifically, a novel solvent, namely, ethyl tetrahydrofurfuryl ether (ETFE) is designed. The reversely anchored rigid cyclic head endows ETFE molecule with weakened steric hindrance effect and stronger cyclic ethereal O\u2500Na\n                    <jats:sup>+<\/jats:sup>\n                    interaction accordingly, hence spatially strengthening overall ion\u2010dipole interaction. Consequently, less vulnerable free solvents, ameliorated electrolyte decomposition, and formation of stable electrode\/electrolyte interphases enable highly reversible Na plating\/stripping behaviors at elevated temperatures. Further, an ampere hour (Ah)\u2010level pouch cell capable of 200 cycles at 45\u00b0C with a capacity retention of 89.1% is realized even after initial 300\u2010cycle ageing at 25\u00b0C, featuring the first long\u2010term HT evaluation toward pouch cell\u2010level AFSBs. This work should expedite the practicability of AFSBs.\n                  <\/jats:p>","DOI":"10.1002\/adma.73421","type":"journal-article","created":{"date-parts":[[2026,5,20]],"date-time":"2026-05-20T07:02:22Z","timestamp":1779260542000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":4,"title":["Spatially Strengthened Ion\u2010Dipole Electrolyte Enables High\u2010Temperature Anode\u2010Free Sodium Batteries"],"prefix":"10.1002","volume":"38","author":[{"given":"Hao","family":"Lan","sequence":"first","affiliation":[{"name":"State Key Laboratory of Bioinspired Interfacial Materials Science Bioinspired Science Innovation Center Hangzhou International Innovation Institute Beihang University  Hangzhou China"},{"name":"School of Chemistry Beihang University Beijing China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Sicong","family":"Wang","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Bioinspired Interfacial Materials Science Bioinspired Science Innovation Center Hangzhou International Innovation Institute Beihang University  Hangzhou China"},{"name":"School of Chemistry Beihang University Beijing China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jiangchun","family":"Chen","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Bioinspired Interfacial Materials Science Bioinspired Science Innovation Center Hangzhou International Innovation Institute Beihang University  Hangzhou China"},{"name":"School of Chemistry Beihang University Beijing China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Liqiang","family":"Wu","sequence":"additional","affiliation":[{"name":"Beijing Xibei Power Technology Co., Ltd. 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