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Here, a dual\u2010layer thermo\u2010responsive smart window (DLTS) is reported that integrates optical regulation with solar heat storage, transforming smart windows from passive light modulators into active energy management systems. DLTS comprises a thermochromic poly(N\u2010isopropyl acrylamide) (PNIPAM) layer and a controllable supercooled calcium chloride hexahydrate (CCH) phase\u2010change layer. By use of dimethylacetamide (DMA) and tartaric acid (TA), the thermo\u2010responsive temperature (\n                    <jats:italic>T<\/jats:italic>\n                    <jats:sub>r<\/jats:sub>\n                    ) of PNIPAM can be adjusted up or down successively from 7 to 70\u00a0\u00b0C, which is the broadest range reported. Simultaneously, depending on ethanol and urea, the\n                    <jats:italic>T<\/jats:italic>\n                    <jats:sub>r<\/jats:sub>\n                    of CCH can be tuned facilely from 9 to 31\u00a0\u00b0C, first\u2010time covering the seasonal temperature change. More importantly, the supercooling degree of 50\u00a0\u00b0C allows the smart windows to remain transparent across the wide ambient temperature variation, while their stored high latent heat of 199 J\u00a0g\n                    <jats:sup>\u22121<\/jats:sup>\n                    can be released upon triggering to provide indoor heating. The correlated dual\u2010layer with well\u2010matched\n                    <jats:italic>T<\/jats:italic>\n                    <jats:sub>r<\/jats:sub>\n                    points endows the DLTS with a remarkable solar modulation (\u0394\n                    <jats:italic>T<\/jats:italic>\n                    <jats:sub>sol<\/jats:sub>\n                    = 70.1%). Compared to normal glass, DLTS can achieve more than 20% annual energy savings in heating, ventilation, and air conditioning (HVAC) systems in typical worldwide cities.\n                  <\/jats:p>","DOI":"10.1002\/smll.202510952","type":"journal-article","created":{"date-parts":[[2025,12,8]],"date-time":"2025-12-08T10:59:32Z","timestamp":1765191572000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":3,"title":["Thermo\u2010Responsive Smart Window Coupled with Heat Storage Effect"],"prefix":"10.1002","volume":"22","author":[{"given":"Tianle","family":"Cheng","sequence":"first","affiliation":[{"name":"Department of Materials Science and Engineering Shenzhen Key Laboratory of Full Spectral Solar Electricity Generation (FSSEG) Southern University of Science and Technology (SUSTech)  No. 1088, Xueyuan Rd. Shenzhen Guangdong 518055 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xusheng","family":"Zhang","sequence":"additional","affiliation":[{"name":"Department of Materials Science and Engineering Shenzhen Key Laboratory of Full Spectral Solar Electricity Generation (FSSEG) Southern University of Science and Technology (SUSTech)  No. 1088, Xueyuan Rd. Shenzhen Guangdong 518055 China"},{"name":"Birmingham Centre of Energy Storage (BCES) School of Chemical Engineering University of Birmingham  Edgbaston Birmingham B15 2TT UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Zeyu","family":"Niu","sequence":"additional","affiliation":[{"name":"Department of Materials Science and Engineering Shenzhen Key Laboratory of Full Spectral Solar Electricity Generation (FSSEG) Southern University of Science and Technology (SUSTech)  No. 1088, Xueyuan Rd. 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