Light-triggered self-healing form-stable phase change materials (FSPCMs) can not only store and release thermal energy, but can also realize self-healing performance under light, showing important practical values. In this article, we provided a new strategy for the preparation of FSPCMs with light-triggered self-healing ability and high thermal energy storage density. Azobenzene side chain liquid crystal polymer was synthesized and used as gelator to blend with paraffin, and then the mixture was heated and dissolved to form transparent solutions. FSPCMs could be obtained after natural cooling to room temperature. The thermal stability, energy storage capacity and rheological property of the prepared FSPCMs were studied in detail. With the increase of gelator content, the thermal stability and storage modulus of FSPCMs enhanced, while the energy storage density decreased. When the gelator content is 6.0 wt%, the gel-sol phase transition temperature (TGS) of the FSPCM was 127 °C, the storage modulus could achieve 2.3 × 103 Pa at 70 °C, and the phase change enthalpy was 193.1 J g−1, showing excellent self-supporting performance and higher energy storage density. More interestingly, the FSPCMs also showed excellent light-triggered self-healing ability. When the FSPCMs were damaged, the materials could quickly repair the damage under the sequential irradiation of 365 nm and 470 nm light.
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