Solvent Anchored Electrolytes for Lithium‐Ion Batteries Working at High Voltage and Wide Temperature

Lithium‐ion batteries (LIBs) suffer from severe performance fading under coupled conditions of high voltage and wide temperature because cold retards Li + migration and desolvation kinetics while heat or high voltage exacerbates parasitic reactions and electrode destabilization. Herein, we propose a solvent‐anchored paradigm for electrolyte design via electrostatic potential matching to enable stable battery operation across the demanding voltage‐temperature matrix. The fine‐tuned electrolyte, which is composed of well‐matched dimethyltrifluoroacetamide solvent and fluorotoluene diluent, features a site‐specific solvation structure with anion‐dominated inner shell and solvent‐anchored outer cluster. This unique configuration facilitates fast Li + desolvation and robust interphase formation on both the lithium/graphite anode and LiCoO 2 cathode. Remarkably, the formulated electrolyte enables stable operation of graphite||LiCoO 2 full cells up to a charging voltage of 4.5 V from −60°C to 80°C, indicating its promising applicability to fortify LIB performance under harsh conditions.