An Ab Initio and Kinetic Monte Carlo Simulation Study of Lithium Ion Diffusion on Graphene.

The Li⁺ diffusion coefficients in Li⁺-adsorbed graphene systems were determined by combining first-principle calculations based on density functional theory with Kinetic Monte Carlo simulations. The calculated results indicate that the interactions between Li ions have a very important influence on lithium diffusion. Based on energy barriers directly obtained from first-principle calculations for single-Li⁺ and two-Li⁺ adsorbed systems, a new equation predicting energy barriers with more than two Li ions was deduced. Furthermore, it is found that the temperature dependence of Li⁺ diffusion coefficients fits well to the Arrhenius equation, rather than meeting the equation from electrochemical impedance spectroscopy applied to estimate experimental diffusion coefficients. Moreover, the calculated results also reveal that Li⁺ concentration dependence of diffusion coefficients roughly fits to the equation from electrochemical impedance spectroscopy in a low concentration region; however, it seriously deviates from the equation in a high concentration region. So, the equation from electrochemical impedance spectroscopy technique could not be simply used to estimate the Li⁺ diffusion coefficient for all Li⁺-adsorbed graphene systems with various Li⁺ concentrations. Our work suggests that interactions between Li ions, and among Li ion and host atoms will influence the Li⁺ diffusion, which determines that the Li⁺ intercalation dependence of Li⁺ diffusion coefficient should be changed and complex.