LAUSR

The chemical potential of lithium in LixFePO4 active cathode nanoparticles and the surface free energy between LixFePO4 and electrolyte were determined with the novel thermodynamically consistent application of the regular solution theory. Innovative consideration of crystal anisotropy accounts for the consistent determination of the dependency of the chemical potential on the mechanistically derived enthalpy of mixing and the phase boundary gradient penalty. This enabled the analytic, thermodynamically consistent determination of the phase boundary thickness between LiFePO4 and FePO4, which is in good agreement with experimental observations. The obtained explicit functional dependency of the surface free energy on the lithium concentration enables adequate simulation of the initiation of the phase transition from FePO4 to LiFePO4 at the surface of active cathode particles. To validate the plausibility of the newly developed approaches, lithium intercalation into the LixFePO4 nanoparticles from electrolyte was modeled by solving the Cahn-Hilliard equation in a quasi-two-dimensional domain.