(577h) Solvation Effects on Lithium Ion Transport and Reaction on Lithium Metal Anodes

Chemistry and structure of electrolytes define characteristic behaviors on cation diffusion, desolvation, and deposition events that influence redox reactions at electrochemical interfaces. Here we discuss the effects of solvent properties such as reduction potential on the barriers for ion transport and their correlation to reorganization of molecules in the primary solvation shell during their journey from bulk to surface. Closer to the surface, we investigate the electron transfer effect on changing the solvation forces, thus transforming solvation into a desolvation process. We study these phenomena using constrained ab initio molecular dynamics within the Blue Moon ensemble along with separate density functional theory analysis of solvation thermodynamics. Our work is relevant to the ion diffusion and deposition on Li metal anodes, but also to many relevant electrochemical interfaces in electrochemical and bioelectrochemical processes.