Solvation Structure with Enhanced Anionic Coordination for Stable Anodes in Lithium‐Oxygen Batteries

Li‐O 2 batteries have garnered much attention due to their high theoretical energy density. However, the irreversible lithium plating/stripping on the anode limits their performance, which has been paid little attention. Herein, a solvation‐regulated strategy for stable lithium anodes in tetraethylene glycol dimethyl ether (G4) based electrolyte is attempted in Li‐O 2 batteries. Trifluoroacetate anions (TFA − ) with strong Li + affinity are incorporated into the lithium bis(fluorosulfonyl)imide (LiTFSI)/G4 electrolyte to attenuate the Li + ‐G4 interaction and form anion‐dominant solvates. The bisalt electrolyte with 0.5 M LiTFA and 0.5 M LiTFSI mitigates G4 decomposition and induces an inorganic‐rich solid electrolyte interphase (SEI). This contributes to decreased desolvation energy barrier from 58.20 to 46.31 kJ mol −1 , compared with 1.0 M LiTFSI/G4, for facile interfacial Li + diffusion and high efficiency. It yields extended lifespan of 120 cycles in Li‐O 2 battery with a limited Li anode (7 mAh cm −2 ). This work gains comprehensive insights into rational electrolyte design for Li‐O 2 batteries.