Addressing Mass Conservation in Two-dimensional Modeling of Lithium Metal Batteries with Electrochemically Plated/Stripped Interfaces

Abstract

This work investigates convection in liquid electrolytes induced by the movement of the lithium metal surface, modeled as a moving boundary. The back-and-forth motion of the lithium metal surface during the plating and stripping of lithium introduces a weak fluid motion in the liquid electrolyte that should be incorporated in the model equations and corresponding boundary conditions. The results for the electrochemical signatures and morphology evolution thus obtained by solving a coupled fluid model are compared with the case where the velocity distribution in the liquid electrolyte is ignored. This work extends our previously reported perspective on the convective flux correction at moving boundaries in one-dimensional models to two dimensions. This careful implementation of the correct boundary conditions ensures the mass conservation of lithium in two-dimensional simulations for predicting the morphological evolution of lithium metal electrodes over cycles. Additionally, these relative fluxes at the moving and fixed boundaries are sometimes ignored by assuming a bulk concentration condition at the far end, especially at the cathode/separator interface. While it may not affect overpotential signatures at the anode, it leads to mass conservation issues with implications for the accuracy of cycling simulations. Two-dimensional model formulation for lithium metal anodes with liquid electrolytes Convection in liquid electrolytes is induced by movement of lithium metal surface Flux correction in boundary conditions at moving boundary ensures mass conservation Assuming bulk concentration boundary conditions lead to errors in mass conservation Solving for bulk fluid convection can be ignored to improve the simulation efficiency