Mass transfer is the key characteristic that affects the charging and discharging performance of the porous materials used in thermochemical heat storage systems. Therefore, an algorithm is required to simulate the transport process within heat storage materials and to accurately evaluate the effective diffusion coefficient. This study is about porous calcium oxide, which is widely used in CaO-Ca(OH)(2) or CaO-CaCO3 heat storage systems. In this paper, the fractal porous media that resemble real heat storage materials are reconstructed by a random walk method. Furthermore, the gas diffusion process through complicated porous microstructures within fractal porous media is simulated by an efficient lattice Boltzmann method. Results indicate that thermochemical heat storage materials have great fractal characteristic and materials with larger fractal dimension have more diffusion resistance. The effective gas diffusion coefficients of CaO and Ca(OH)(2) are obtained from the ratios of effective gas diffusion coefficient and bulk gas diffusion coefficient that are 0.228 and 0.188 for CaO and Ca(OH)(2), respectively. Additionally, it is found that calcium oxide samples prepared at higher temperatures have the poorer exothermic performance because of the poorer gas diffusion. Moreover, the correlation between the effective diffusion coefficients and the porosity of porous materials is numerically predicted and evaluated. The fractal model-LBM method developed in this paper may serve as a great tool for easy estimation of effective diffusion coefficients and mass transfer. (C) 2019 Elsevier Ltd. All rights reserved.