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

Abstract

AbstractLi‐O2 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‐O2 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‐O2 battery with a limited Li anode (7 mAh cm−2). This work gains comprehensive insights into rational electrolyte design for Li‐O2 batteries.