Agglomeration inhibition mechanism of SiO2 in the Ca(OH)2/CaO thermochemical heat storage process: A reactive molecular dynamics study

As a promising thermochemical heat storage material, the Ca(OH)2/CaO can be agglomerated after repeated heat storage cycles, which will affect its performance severely. Experimental evidence indicated that the dopant of SiO2 particles alleviated the agglomeration phenomenon of Ca(OH)2/CaO. However, the mechanisms have not been clarified in theory, including the agglomeration of Ca(OH)2/CaO and the agglomeration inhibition of SiO2. Investigating these mechanisms is important for the broad application of Ca(OH)2/CaO thermochemical heat storage technology. In this paper, reactive molecular dynamics is employed to simulate and quantify the agglomeration of Ca(OH)2 and the inhibition by SiO2 during the heat storage process. Then, the agglomeration phenomena under the two processes are quantitatively described. The mechanisms are analyzed by using the parameters of kinetics and thermodynamics. From the phenomenological analysis, smaller size changes, larger mass center distances, and smaller atomic displacements indicate that SiO2 doping reduces the tendency of nanoparticles to agglomerate into a larger cluster. From the kinetic perspective, the diffusion of pure Ca(OH)2 clusters conforms to viscous flow, while the diffusion of the SiO2-doped clusters is close to surface diffusion. The dopant of SiO2 increases the activation energy of the diffusion process, which would increase the atomic mobility resistance and thus inhibit the agglomeration. From the thermodynamic perspective, cluster agglomeration is mainly caused by the work done by van der Waals forces, which leads to a decrease in potential energy, especially surface potential energy. By doping SiO2, the interatomic van der Waals forces are increased, which lowers the stable potential energy surface of the clusters, thereby obtaining a more stable structure to inhibit agglomeration.