MgCr₂O₄-Modified CuO/Cu₂O for High-Temperature Thermochemical Energy Storage with High Redox Activity and Sintering...

Metal oxides as high-temperature thermochemical energy storage systems with high energy density based on the gas-solid reaction are a critical demand for the future development of concentrated solar power plants. A copper-based system has high enthalpy change and low cost, but its serious sintering leads to poor reactivity. In this study, MgCr₂O₄ is decorated on the CuO/Cu₂O surface to effectively increase the sintering temperature and alleviate the sintering problem. The re-oxidation degree is increased from 46 to 99.9%, and the reaction time is shortened by 3.7 times. The thermochemical energy density of storage and release reach -818.23 and 812.90 kJ/kg, respectively. After 600 cycles, the oxidation activity remains 98.77%. Material characterization elucidates that nanosized MgCr₂O₄ is uniformly loaded on the surface of CuO/Cu₂O during the reversible reaction, and there is a strong interaction between metal oxides and prompter. Density functional theory (DFT) calculation further confirms that CuO/Cu₂O-MgCr₂O₄ has large binding energy and the formation energy of copper vacancy increases, which can effectively inhibit sintering. The modification mechanism of CuO/Cu₂O by MgCr₂O₄ is revealed, which can provide guidance for the reasonable design of thermochemical energy storage materials with sintering resistance and redox activity.