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Herein, a facile catalyst\/solvent\u2010free multicomponent reaction involving alcohols\/amines\/thiols, dimethyl phosphite, and benzaldehyde was developed to simultaneously address these drawbacks. The terminal phosphite groups endow intrinsic flame retardancy, while intermolecular interactions enhanced by P\u2550O bonds transform the material into a viscous\u2010to\u2010solid state above its melting point, eliminating leakage. Notably, the reaction proceeds smoothly with quantitative yield under fully catalyst\u2010free conditions as nucleophilicity increases from alcohols to thiols. Battery thermal management tests show the intrinsic flame\u2010retardant solid\u2010solid phase change materials extend the safe operation of lithium\u2010ion batteries by 140%. Cone calorimeter tests reveal a 14 s ignition delay, and 37.6%, 29.8%, and 27.3% reductions in average heat release rate, total heat release, and total oxygen consumption compared to raw materials, confirming excellent flame retardancy. The material exhibits a maximum latent heat of 133.87 J\/g, ensuring favorable thermal energy storage performance.<\/jats:p>","DOI":"10.1002\/advs.77157","type":"journal-article","created":{"date-parts":[[2026,8,13]],"date-time":"2026-08-13T15:43:36Z","timestamp":1786635816000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Hydrogen\u2010Bond Enabled Phosphite Based Intrinsic Flame\u2010Retardant Solid\u2010Solid Phase Change Materials Using Catalyst\/Solvent\u2010Free Multi\u2010Component Reaction for Battery Thermal Management"],"prefix":"10.1002","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-8265-7302","authenticated-orcid":false,"given":"Changhui","family":"Liu","sequence":"first","affiliation":[{"name":"School of Low\u2010carbon Energy and Power Engineering China University of Mining and Technology  Xuzhou Jiangsu 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