Bi-phasic lithiation/delithiation dynamics in Li-ion batteries: application of the Smoothed Boundary Method in the phase field model

Abstract: An appropriate description of the lithiation/delithiation dynamics in bi-phasic primary cathode particles of Li-ion batteries requires an accurate treatment of the conditions holding at the interface between the particle and the surrounding liquid electrolyte. We propose a phase field model based on the Allen-Cahn approach within which the particle-electrolyte interface is smooth (Smoothed Boundary Method - SBM), in order to simulate arbitrarily shaped particles. Surface terms are added to the evolution equations, and SBM calculations are compared with benchmark simulations for which the boundary conditions are explicitly imposed at the borders of the calculation domain. We find that strengthening factors for the surface terms are needed in order to achieve the desired conditions for the phase and elastic fields, and to correctly reproduce the level of stress within the particle. This reveals crucial in the context of Li-ion batteries for an accurate prediction of the Li insertion/extraction rate and the Li diffusion behavior. We perform also a simulation under potentio-static conditions with a full coupling of the different physical processes at play. It illustrates the applicability of our approach and demonstrates the capabilities of the SBM for a simulation of lithiation/delithiation dynamics with coupled electrochemistry and mechanics.