In this work, we present and apply schemes to determine from first-principles calculations the relevant effective parameters used in phase field theory simulations of battery compounds. In particular, we derive that a consistent free energy density can be obtained by mean-field sampling, which is especially suited for materials with different configurations on a lattice, such as alloys or Li intercalation batteries. In addition, it is demonstrated that mean-field sampling can be performed very effectively with the use of special quasi random structures and that experimentally determined free energy density parameters for LiFePO4 are reproduced by density functional theory calculations. The additional computation of interfacial and strain energy parameters allows us to present a consistent phase field parametrization of Li2FeSiO4 without relying on experimental data.
Kangning Zhao, Yuehui Li, Rui Xia, Liping Zhong