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In light of these conflicting factors, we introduce a NaCl\u2010based SE reinforced by mesoporous \u03b1\u2010AlF\n                    <jats:sub>3<\/jats:sub>\n                    (denoted as HS\u2010AlF\n                    <jats:sub>3<\/jats:sub>\n                    ), leading to a heterostructure halide architecture, designated as NHxy (where x\/y represents the mass ratio of NaCl to HS\u2010AlF\n                    <jats:sub>3<\/jats:sub>\n                    ). The high dispersion of NaCl and HS\u2010AlF\n                    <jats:sub>3<\/jats:sub>\n                    during mechanochemical process enables the generation of defective and amorphous structures and nanodomains in NHxy along with F\u2010Cl anion substitution effect at grain boundaries. These factors collectively promote Na ion transport in NHxy, especially along the NaCl based heterostructures with AlF\n                    <jats:sub>3<\/jats:sub>\n                    and NaF. This class of SEs achieves the high ionic conductivity approaching 10\n                    <jats:sup>\u22124<\/jats:sup>\n                    S cm\n                    <jats:sup>\u22121<\/jats:sup>\n                    at 30\u00a0\u00b0C. Specifically, NH54 exhibits excellent long\u2010term air stability at 35% relative humidity, maintaining high ion conductivity without degradation. The raw material cost of this Na\u2010based electrolyte is less than $10 USD kg\n                    <jats:sup>\u22121<\/jats:sup>\n                    when considering the production in a large scale. The corresponding Na\/\/Na symmetric cells demonstrate the stable cycling for at least 1000\u00a0h at 0.1\u00a0mA cm\n                    <jats:sup>\u2212<\/jats:sup>\n                    <jats:sup>2<\/jats:sup>\n                    . The Na\/\/Na\n                    <jats:sub>3<\/jats:sub>\n                    V\n                    <jats:sub>2<\/jats:sub>\n                    (PO\n                    <jats:sub>4<\/jats:sub>\n                    )\n                    <jats:sub>3<\/jats:sub>\n                    cells assembled with the NH54 after air exposure exhibit the remarkable longevity, sustaining over 400 cycles at 60\u00a0\u00b0C. The conversion\u2010type Na\/NH54\/FeF\n                    <jats:sub>3<\/jats:sub>\n                    cells deliver a high capacity of 500 mAh g\n                    <jats:sup>\u22121<\/jats:sup>\n                    . This work opens the new pathways for inorganic SEs with enhanced economic value, ion conductivity, air stability and suitability for energy\u2010dense conversion reaction batteries.\n                  <\/jats:p>","DOI":"10.1002\/anie.202425503","type":"journal-article","created":{"date-parts":[[2025,4,21]],"date-time":"2025-04-21T05:41:27Z","timestamp":1745214087000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":18,"title":["Mesoporous Enhanced Heterostructured Halide Solid Electrolytes with High Air Stability and High Abundance for Sustainable Sodium Metal Batteries"],"prefix":"10.1002","volume":"64","author":[{"given":"Qijie","family":"Yu","sequence":"first","affiliation":[{"name":"State Key Laboratory of High Performance Ceramics and Superfine Microstructure Shanghai Institute of Ceramics Chinese Academy of Sciences  585 He Shuo Road Shanghai 201899 China"},{"name":"Center of Materials Science and Optoelectronics Engineering University of Chinese Academy of Sciences  Beijing 100049 China"},{"name":"CAS Key Laboratory of Materials for Energy Conversion, Shanghai Institute of Ceramics Chinese Academy of Sciences  Shanghai 201899 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jiulin","family":"Hu","sequence":"additional","affiliation":[{"name":"State Key Laboratory of High Performance Ceramics and Superfine Microstructure Shanghai Institute of Ceramics Chinese Academy of Sciences  585 He Shuo Road Shanghai 201899 China"},{"name":"Center of Materials Science and Optoelectronics Engineering University of Chinese Academy of Sciences  Beijing 100049 China"},{"name":"CAS Key Laboratory of Materials for Energy Conversion, Shanghai Institute of Ceramics Chinese Academy of Sciences  Shanghai 201899 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yi","family":"Xu","sequence":"additional","affiliation":[{"name":"Department of Chemical Engineering, School of Environmental and Chemical Engineering Shanghai University  Shangda Road 99 Shanghai 200444 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Runyuan","family":"Cao","sequence":"additional","affiliation":[{"name":"State Key Laboratory of High Performance Ceramics and Superfine Microstructure Shanghai Institute of Ceramics Chinese Academy of Sciences  585 He Shuo Road Shanghai 201899 China"},{"name":"Center of Materials Science and Optoelectronics Engineering University of Chinese Academy of Sciences  Beijing 100049 China"},{"name":"CAS Key Laboratory of Materials for Energy Conversion, Shanghai Institute of Ceramics Chinese Academy of Sciences  Shanghai 201899 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Shuangqiang","family":"Chen","sequence":"additional","affiliation":[{"name":"Institute for Carbon Neutralization College of Chemistry and Materials Engineering Wenzhou University  Wenzhou 325035 China"},{"name":"Department of Chemical 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