Modeling How Interface Geometry and Mechanical Stress Affect Li Metal/Solid Electrolyte Current Distributions

We develop a coupled electrochemical-mechanical model to assess the current distributions at Li/single-ion conducting solid ceramic electrolyte interfaces containing a parameterized interfacial geometric asperity, and carefully distinguish between the thermodynamic and kinetic effects of interfacial mechanics on the current distribution. We find that with an elastic-perfectly plastic model for Li metal, and experimentally relevant mechanical initial and boundary conditions, the stress variations along the interface for experimentally relevant stack pressures and interfacial geometries are small (e.g., <1 MPa), resulting in a small or negligible influence of the interfacial mechanical state on the interfacial current distribution for both plating and stripping. However, we find that the current distribution is sensitive to interface geometry, with sharper (i.e., smaller tip radius of curvature) asperities experiencing greater current focusing. In addition, the effect on the current distribution of an identically sized lithium peak vs valley geometry is not the same. These interfacial geometry effects may lead to void formation on both stripping and plating and at both Li peaks and valleys. The presence of high-curvature interface geometry asperities provides an additional perspective on the superior cycling performance of flat, film-based separators (e.g., sputtered LiPON) versus particle-based separators (e.g., polycrystalline LLZO) in some conditions.