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Here, we present a spray\u2010assisted in situ assembly strategy to construct azolate hybrid frameworks (AHFs) directly on glass fiber substrates, followed by thermal polymerization to yield a chemically integrated QSSE. The heterocyclic AHF provides ordered lithium\u2010philic coordination sites and continuous ion\u2010transport pathways, enabling efficient Li\n                    <jats:sup>+<\/jats:sup>\n                    migration while maintaining high thermal robustness. As a result, the resulting LiFePO\n                    <jats:sub>4<\/jats:sub>\n                    |FP10v\u2010GF|Li cell sustains stable cycling for over 500 cycles at 25\u00b0C and 100 cycles at 60\u00b0C. Notably, the framework architecture enables molecular level confinement of triethyl phosphate (TEP) as a flame\u2010retardant component, establishing a nitrogen phosphorus synergistic flame\u2010retardant mechanism without compromising electrochemical compatibility. Consequently, high\u2010loading Li||LiFePO\n                    <jats:sub>4<\/jats:sub>\n                    cells exhibit stable cycling under practical conditions (E\/C = 0.56\u00a0g Ah\n                    <jats:sup>\u22121<\/jats:sup>\n                    , N\/p = 3.27) and successfully withstand accelerated rate calorimetry tests from 25\u00b0C to 300\u00b0C without thermal runaway. This work demonstrates how framework chemistry and molecular confinement can be synergistically integrated to decouple ionic conductivity from flammability, providing a general design principle for intrinsically safe, high\u2010energy quasi\u2010solid\u2010state lithium batteries.\n                  <\/jats:p>","DOI":"10.1002\/anie.1279221","type":"journal-article","created":{"date-parts":[[2026,6,24]],"date-time":"2026-06-24T13:04:28Z","timestamp":1782306268000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":2,"title":["Flame\u2010Retardant Quasi\u2010Solid\u2010State Electrolytes From Self\u2010Assembled Azolate Hybrid Frameworks for Highly Safe Lithium Batteries"],"prefix":"10.1002","volume":"65","author":[{"given":"Shun","family":"Wang","sequence":"first","affiliation":[{"name":"Key Laboratory of Chemical Additives for China National Light Industry College of Chemistry and Chemical Engineering Shaanxi University of Science and Technology  Xi'an People's Republic of China"},{"name":"College of Chemistry and Chemical Engineering Flexible Energy Storage and Interfacial Chemistry Key Laboratory of Shaanxi University Shaanxi University of Science and Technology  Xi'an People's Republic of China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Qimin","family":"Zhu","sequence":"additional","affiliation":[{"name":"Key Laboratory of Chemical Additives for China National Light Industry College of Chemistry and Chemical Engineering Shaanxi University of Science and Technology  Xi'an People's Republic of China"},{"name":"College of Chemistry and Chemical Engineering Flexible Energy Storage and Interfacial Chemistry Key Laboratory of Shaanxi University Shaanxi University of Science and Technology  Xi'an People's Republic of China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yuanyuan","family":"Tian","sequence":"additional","affiliation":[{"name":"Key Laboratory of Chemical Additives for China National Light Industry College of Chemistry and Chemical Engineering Shaanxi University of Science and Technology  Xi'an People's Republic of China"},{"name":"College of Chemistry and Chemical Engineering Flexible Energy Storage and Interfacial Chemistry Key Laboratory of Shaanxi University Shaanxi University of Science and Technology  Xi'an People's Republic of China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Peiyu","family":"Cui","sequence":"additional","affiliation":[{"name":"Key Laboratory of Chemical Additives for China National Light Industry College of Chemistry and Chemical Engineering Shaanxi University of Science and Technology  Xi'an People's Republic of China"},{"name":"College of Chemistry and Chemical Engineering Flexible Energy Storage and Interfacial Chemistry Key Laboratory of Shaanxi University Shaanxi University of Science and Technology  Xi'an People's Republic of China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Qing","family":"Ji","sequence":"additional","affiliation":[{"name":"Department of Mechanical Engineering Vehicle Energy and Safety Laboratory Ningbo University of Technology  Ningbo People's Republic of China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Tian","family":"Xie","sequence":"additional","affiliation":[{"name":"Key Laboratory of Chemical Additives for China National Light Industry College of Chemistry and Chemical Engineering Shaanxi University of Science and Technology  Xi'an People's Republic of China"},{"name":"College of Chemistry and Chemical Engineering Flexible Energy Storage and Interfacial Chemistry Key Laboratory of Shaanxi University Shaanxi University of Science and Technology  Xi'an People's Republic of China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hong","family":"Wang","sequence":"additional","affiliation":[{"name":"Shanghai Lingfang Energy Co. 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