Since 1994, Kinetic Monte Carlo (kMC) has been applied to the study of Li-ion batteries and has demonstrated to be a remarkable simulation tool to properly describe the physicochemical processes involved, on the atomistic scale and over long time scales. With the growth of computing power and the widespread use of lithium-based storage systems, more contributions from theoretical studies have been requested. This has led to a remarkable growth of theoretical publications on Li-ion batteries; kMC has been one of the preferred techniques to study these systems. Despite the advantages it presents, kMC has not yet been fully exploited in the field of lithium-ion batteries (LIBs) and its impact in this field is increasing exponentially. In this review, we summarize the most important applications of kMC to the study of LIBs and then comment on the state-of-the-art and prospects for the future of this technique, in the context of multi-scale modeling. We also briefly discuss the prospects for applying kMC to post lithium-ion chemistries such as lithium-sulfur and lithium-air.

Cell temperature of hard carbons is varied under open circuit conditions (entropy profiling) during sodiation. Features vary with pore size, revealing the nanopore filling onset. Sodium binding energy scales inversely with pore curvature radius.

The effect of temperature on the kinetics of electrochemical insertion/removal of lithium in graphite is analyzed by kinetic Monte Carlo methods. Different electrochemical techniques are simulated at different temperatures and responses are compared with experimental results. Simulated voltammograms show, similarly to experiment, how the behavior of the system becomes closer to equilibrium as temperature increases. Calculated chronoamperometric profiles show a different qualitative behavior in the current at different temperatures, especially in the Cottrell representation peaks, explained in terms of the relative importance of diffusive versus charge transfer processes at different temperatures. Results at room temperature are in good agreement with experiment, and we further evaluate trends at elevated temperature that have not yet been described in experimental or theoretical works. Exchange current densities for different degrees of lithium intercalation at different temperatures are predicted using potentiostatic simulations, showing an Arrhenius-type relationship. The dependence of the exchange current on electrolyte composition is simulated by investigating the effect of different activation energy barriers at different temperatures. The influence of temperature on diffusion coefficients as a function of lithiation fraction in graphite is simulated and related to Arrhenius plots, explaining the experimentally observed changes in diffusion phenomena with lithium composition and temperature.