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This study explores the development of a novel sodium salt, sodium (benzenesulfonyl)(trifluoromethanesulfonyl) imide (NaBTFSI), for all\u2010solid\u2010state sodium metal batteries (ASSSMBs). NaBTFSI offers a promising electrolyte option by improving sodium\u2010ion transference number (), conductivity, and stability of sodium metal (Na\u00b0) anode cycling. When combined with poly(ethylene oxide), NaBTFSI forms safe solid polymer electrolytes with high mechanical strength, effectively mitigating dendrite growth and polarization issues common in sodium anodes. Characterization shows NaBTFSI enhances the electrochemical performance through \u03c0\u2013\u03c0 stacking interactions, which stabilize the polymer matrix and increase ionic conductivity (\u22484.0\u2009\u00d7\u200910\n                    <jats:sup>\u2212<\/jats:sup>\n                    <jats:sup>4<\/jats:sup>\n                    \u2009S\u2009cm\n                    <jats:sup>\u22121<\/jats:sup>\n                    ) at elevated temperatures (70\u2009\u00b0C). NaBTFSI\u2010based electrolytes exhibit higher stability with sodium anodes than the conventional sodium bis(trifluoromethanesulfonyl)imide salt, supporting prolonged cycling in Na\n                    <jats:sup>o<\/jats:sup>\n                    ||Na\n                    <jats:sup>o<\/jats:sup>\n                    symmetric cells and demonstrating potential for sustainable, high\u2010performance ASSSMBs.\n                  <\/jats:p>","DOI":"10.1002\/cssc.202500245","type":"journal-article","created":{"date-parts":[[2025,5,8]],"date-time":"2025-05-08T07:55:04Z","timestamp":1746690904000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":2,"title":["Asymmetric Benzene Sulfonamide Sodium Salt Enabling Stable Cycling in Solid\u2010State Sodium Metal Batteries"],"prefix":"10.1002","volume":"18","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-6099-1593","authenticated-orcid":false,"given":"Itziar","family":"Aldalur","sequence":"first","affiliation":[{"name":"Centre for Cooperative Research on Alternative Energies (CIC energiGUNE) Basque Research and Technology Alliance (BRTA)  \u00c1lava Technology Park, Albert Einstein 48 01510 Vitoria\u2010Gasteiz Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jorge Luis","family":"Olmedo\u2010Martinez","sequence":"additional","affiliation":[{"name":"POLYMAT and Department of Polymers and Advanced Materials: Physics, Chemistry and Technology, Faculty of Chemistry University of the Basque Country UPV\/EHU  Paseo Manuel de Lardiz\u00e1bal 3 20018 Donostia\u2010San Sebasti\u00e1n Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Lorena","family":"Garcia","sequence":"additional","affiliation":[{"name":"Centre for Cooperative Research on Alternative 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Plaza Euskadi 5 48009 Bilbao Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Michel","family":"Armand","sequence":"additional","affiliation":[{"name":"Centre for Cooperative Research on Alternative Energies (CIC energiGUNE) Basque Research and Technology Alliance (BRTA)  \u00c1lava Technology Park, Albert Einstein 48 01510 Vitoria\u2010Gasteiz Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7023-0392","authenticated-orcid":false,"given":"Mar\u00eda","family":"Martinez\u2010Iba\u00f1ez","sequence":"additional","affiliation":[{"name":"Centre for Cooperative Research on Alternative Energies (CIC energiGUNE) Basque Research and Technology Alliance (BRTA)  \u00c1lava Technology Park, Albert Einstein 48 01510 Vitoria\u2010Gasteiz 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