Li Han, Lin Jinfeng, Wu Jianze, Wang Jiashun, Wang Pengzhao, Kang Guojian, Huang Shuping, Fu Mingkai, Wei Jinjia, Ding Zhengxin, Long Jinlin
State Key Lab of Photocatalysis on Energy and Environment, Fuzhou University, Fuzhou, 350116, P. R. China.
College of Chemistry, Fuzhou University, Fuzhou, 350116, P. R. China.
Adv Sci (Weinh). 2025 Feb;12(6):e2412082. doi: 10.1002/advs.202412082. Epub 2024 Dec 16.
Developing high-performance Ca-based materials that can work for long-term heat transfer and storage in concentrated solar power plants is crucial to achieve the large-scale conversion of solar photon fluxes to dispatchable electricity. This work demonstrates that a series of Mn, Zr co-doped CaCO nanomaterials with the 3D ordered macroporous (3DOM) skeletons are successfully prepared by a novel strategy of templated metal salt co-precipitation. The characterization results indicate that a majority of Zr and Mn are atomically dispersed into the highly-crystallized CaCO framework, whereas a minor amount of Mn is present in the form of CaMnO nanoparticles (NPs). The optimal 3DOM material made by templating with PS microspheres with a diameter of ≈350 nm, 3DOM-Ca80Mn10Zr10, shows a solar light absorptance of ≈74.1% and an initial energy storage density of 1706.4 kJ kg. Importantly, it gives an impressive energy storage density loss of < 6.0% and maintains above 1600 kJ kg after 125 cycles. The density functional theory calculations reveal that the co-doping of Mn and Zr into the CaO crystal lattice offers a strong affinity to [CaO] clusters, as a result, the anti-sintering of CaO NPs is significantly enhanced under high temperature.
开发能够在聚光太阳能发电厂中长期用于传热和储能的高性能钙基材料，对于实现将太阳光子通量大规模转换为可调度电力至关重要。这项工作表明，通过一种新颖的模板金属盐共沉淀策略，成功制备了一系列具有三维有序大孔（3DOM）骨架的锰、锆共掺杂碳酸钙纳米材料。表征结果表明，大部分锆和锰以原子方式分散在高度结晶的碳酸钙骨架中，而少量锰以CaMnO纳米颗粒（NPs）的形式存在。通过用直径约为350nm的聚苯乙烯微球作为模板制备的最佳3DOM材料3DOM-Ca80Mn10Zr10，显示出约74.1%的太阳光吸收率和1706.4kJ kg的初始储能密度。重要的是，它的储能密度损失令人印象深刻，小于6.0%，并且在125次循环后保持在1600kJ kg以上。密度泛函理论计算表明，锰和锆共掺杂到氧化钙晶格中对[CaO]团簇具有很强的亲和力，因此，氧化钙纳米颗粒在高温下的抗烧结性能显著增强。
