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. (© 2023 Wiley‐VCH GmbH)