Mn-Zr promoted CaCO3 porous microspheres for enhanced performance direct solar-driven calcium looping

The Calcium looping thermochemical reaction directly driven by solar energy effectively addresses the problem of efficient energy storage of concentrated solar power plants (CSP) by shortening the energy conversion path. But new requirements are put forward for energy storage materials, including high solar radiation absorption, high cycling stability and fast kinetics. To meet these challenges, we have designed porous microsphere structures for the purpose of enhancing mass transfer and the capture of solar radiation. Additionally, Zr and Mn oxides with elevated Tammann temperatures were incorporated to stabilize the morphology and prevent sintering. The synthesized porous microspheres retained abundant mesoporous channels on the surface even after undergoing 20 cycles. The addition of Mn oxide significantly enhances solar spectral absorptivity, achieving an impressive 82.88 % absorbance. The incorporation of Mn and Zr oxides increased the sintering resistance, specific surface area and porosity of CaO/CaCO3, especially in the 10-100 nm range, which accelerated the CO2 transport during carbonation. These enhancements significantly improve the chemical control stage of the carbonation reaction, as further supported by kinetic models. After 50 cycle experiments at 800 degrees C, the energy storage density of the sample remains at 1074 kJ/kg, which is 1.86 times that of the undoped CaCO3. This study provides a new way to design CaCO3 materials suitable for CSP applications.