Solvent versus Anion Chemistry: Unveiling the Structure-Dependent Reactivity in Tailoring Electrochemical Interphases for Lithium-Metal Batteries

[Image: see text] Electrolytes are critical for the reversibility of various electrochemical energy storage systems. The recent development of electrolytes for high-voltage Li-metal batteries has been counting on the salt anion chemistry for building stable interphases. Herein, we investigate the effect of the solvent structure on the interfacial reactivity and discover profound solvent chemistry of designed monofluoro-ether in anion-enriched solvation structures, which enables enhanced stabilization of both high-voltage cathodes and Li-metal anodes. Systematic comparison of different molecular derivatives provides an atomic-scale understanding of the unique solvent structure-dependent reactivity. The interaction between Li(+) and the monofluoro (−CH(2)F) group significantly influences the electrolyte solvation structure and promotes the monofluoro-ether-based interfacial reactions over the anion chemistry. With in-depth analyses of the compositions, charge transfer, and ion transport at interfaces, we demonstrated the essential role of the monofluoro-ether solvent chemistry in tailoring highly protective and conductive interphases (with enriched LiF at full depths) on both electrodes, as opposed to the anion-derived ones in typical concentrated electrolytes. As a result, the solvent-dominant electrolyte chemistry enables a high Li Coulombic efficiency (∼99.4%) and stable Li anode cycling at a high rate (10 mA cm(–2)), together with greatly improved cycling stability of 4.7 V-class nickel-rich cathodes. This work illustrates the underlying mechanism of the competitive solvent and anion interfacial reaction schemes in Li-metal batteries and offers fundamental insights into the rational design of electrolytes for future high-energy batteries.