The application of phase change materials (PCMs) for thermal storage in construction can effectively reduce building energy consumption. However, high costs and vulnerability to leaks have hindered their application. The present study proposes two approaches for the synthesis of porous supporting matrices derived from rice husk, resulting in the formation of rice husk silica (RHS) and rice husk carbon (RHC). Then, n-octadecane and the porous materials were combined by vacuum impregnation, while the leakage resistance performance of the composite PCMs was enhanced by applying epoxy resin coating to create a shell-core structure. The results show that the n-octadecane/RHS and n-octadecane/RHC composite PCMs exhibit high latent heat potential of 106.5 J/g and 116.3 J/g, respectively. Both porous supporting structures provided the PCMs with robust structural stability and exceptional thermal conductivity. The thermal conductivity of the n-octadecane/RHS composite PCMs and n-octadecane/RHC composite PCMs reached 0.52 W/(m K) and 0.41 W/(m K), respectively. The thermal properties of the biogenic porous core/shell-based shape-stabilized PCMs were characterized by an analog T-history method, and the results demonstrated that the composite PCMs exhibited excellent and rapid heat storage and exothermic capabilities. After undergoing 300 complete heating and cooling cycles, the composite PCMs demonstrate exceptional thermal reliability and possess a high enthalpy capacity. Finally, the impact of the pore structure of RHS and RHC on the crystallization behavior of n-octadecane was discussed. Both composite PCMs can be regarded as environmentally friendly construction materials with promising thermal and acoustic properties.
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