Significance of Antisolvents on Solvation Structures Enhancing Interfacial Chemistry in Localized High-Concentration Electrolytes

[Image: see text] Localized high-concentration electrolytes (LHCEs) provide a new way to expand multifunctional electrolytes because of their unique physicochemical properties. LHCEs are generated when high-concentration electrolytes (HCEs) are diluted by antisolvents, while the effect of antisolvents on the lithium-ion solvation structure is negligible. Herein, using one-dimensional infrared spectroscopy and theoretical calculations, we explore the significance of antisolvents in the model electrolyte lithium bis(fluorosulfonyl)imide/dimethyl carbonate (LiFSI/DMC) with hydrofluoroether. We clarify that the role of antisolvent is more than dilution; it is also the formation of a low-dielectric environment and intensification of the inductive effect on the C=O moiety of DMC caused by the antisolvent, which decrease the binding energy of the Li(+)···solvent and Li(+)···anion interactions. It also has beneficial effects on interfacial ion desolvation and Li(+) transport. Furthermore, antisolvents also favor reducing the lowest unoccupied molecular orbital (LUMO) energy level of the solvated clusters, and FSI(–) anions show a decreased reduction stability. Consequently, the influence of antisolvents on the interfacial chemical and electrochemical activities of solvation structures cannot be ignored. This finding introduces a new way to improve battery performance.