A phase field electro-chemo-mechanical formulation for predicting void evolution at the Li-electrolyte interface in all-solid-state batteries

Abstract: We present a mechanistic theory for predicting void evolution in the Li metal electrode during the charge and discharge of all-solid-state battery cells. A phase field formulation is developed to model vacancy annihilation and nucleation, and to enable the tracking of the void-Li metal interface. This is coupled with a viscoplastic description of Li deformation, to capture creep effects, and a mass transfer formulation accounting for substitutional (bulk and surface) Li diffusion and current-driven flux. Moreover, we incorporate the interaction between the electrode and the solid electrolyte, resolving the coupled electro-chemical-mechanical problem in both domains. This enables predicting the electrolyte current distribution and thus the emergence of local current 'hot spots', which act as precursors for dendrite formation and cell death. The theoretical framework is numerically implemented, and single and multiple void case studies are carried out to predict the evolution of voids and current hot spots as a function of the applied pressure, material properties and charge (magnitude and cycle history). For both plating and stripping, insight is gained into the interplay between bulk diffusion, Li dissolution and deposition, creep, and the nucleation and annihilation of vacancies. The model is shown to capture the main experimental observations, including not only key features of electrolyte current and void morphology but also the sensitivity to the applied current, the role of pressure in increasing the electrode-electrolyte contact area, and the dominance of creep over vacancy diffusion.