Visible-Light-Controlled Thermal Energy Storage and Release: A Tetra-Ortho-Fluorinated Azobenzene-Doped Composite Phase Change Material

Organic phase change materials (OPCMs) offer high energy density for thermal storage but suffer from crystallization kinetics dependent on ambient temperature, leading to uncontrolled heat release and limited storage lifetime. Although doping OPCMs with azobenzene (Azo) derivatives enables optically controlled energy storage and release, existing systems require UV irradiation for <i>E</i>-to-<i>Z</i> isomerization. This UV dependency seriously hinders their development in practical solar applications. Herein, we develop a visible-light-responsive Azo@OPCM composite by doping <i>tetra</i>-<i>ortho</i>-fluorinated azobenzene into eicosane. Systematic characterization of composites with different dopant ratios via UV-visible spectroscopy and differential scanning calorimetry reveals that green-light irradiation drives <i>E</i>-to-<i>Z</i> isomerization, achieving 97-99% <i>Z</i>-isomer conversion. This photoisomerization could introduce supercooling through photo-responsive energy barriers generated by <i>Z</i>-isomer, allowing thermal energy storage at lower temperatures. Subsequent blue-light irradiation triggers <i>Z</i>-to-<i>E</i> reversion to eliminate supercooling and enable optically controlled heat release. Additionally, by regulating the molar ratios of dopant, the optimized composites achieved 280.76 J/g energy density at 20% molar doping ratio, which surpassed that of pure eicosane and the reported Azo-based photothermal energy storage system. This work establishes a complete visible-light-controlled energy harvesting-storage-release cycle with significant potential for near-room-temperature solar thermal storage applications.