Cation−Solvent, Cation−Anion, and Solvent−Solvent Interactions with Electrolyte Solvation in Lithium Batteries

Abstract Electrolyte solvation is a fundamental issue that regulates the lithium (Li) ion solvation sheath structure, the formation of cathode/anode−electrolyte interphase, and the plating/stripping behavior of Li ions in working Li batteries. Herein, we probe the cation‐solvent, cation‐anion, and solvent‐solvent interactions under both vacuum and electrolyte conditions through density functional theory calculations. The solvation effects can significantly weaken the aforementioned interactions in electrolytes as well as increase the Li−O/F distances in Li + ‐containing complexes. The dissolution behaviour of Li salts in electrolytes was further explored and experimentally validated by dissolving lithium nitrate in different solvents. This work affords a mechanistic understanding of electrolyte microstructure and highlights the significant role of electrolyte solvation in regulating battery performance, affording fruitful insights into emerging electrolyte design for high‐performance batteries.