High‐Performance Lithium‐Oxygen Battery Electrolyte Derived from Optimum Combination of Solvent and Lithium Salt

To fabricate a sustainable lithium‐oxygen (Li‐O(2)) battery, it is crucial to identify an optimum electrolyte. Herein, it is found that tetramethylene sulfone (TMS) and lithium nitrate (LiNO(3)) form the optimum electrolyte, which greatly reduces the overpotential at charge, exhibits superior oxygen efficiency, and allows stable cycling for 100 cycles. Linear sweep voltammetry (LSV) and differential electrochemical mass spectrometry (DEMS) analyses reveal that neat TMS is stable to oxidative decomposition and exhibit good compatibility with a lithium metal. But, when TMS is combined with typical lithium salts, its performance is far from satisfactory. However, the TMS electrolyte containing LiNO(3) exhibits a very low overpotential, which minimizes the side reactions and shows high oxygen efficiency. LSV‐DEMS study confirms that the TMS‐LiNO(3) electrolyte efficiently produces NO(2) (−), which initiates a redox shuttle reaction. Interestingly, this NO(2) (−)/NO(2) redox reaction derived from the LiNO(3) salt is not very effective in solvents other than TMS. Compared with other common Li‐O(2) solvents, TMS seems optimum solvent for the efficient use of LiNO(3) salt. Good compatibility with lithium metal, high dielectric constant, and low donicity of TMS are considered to be highly favorable to an efficient NO(2) (−)/NO(2) redox reaction, which results in a high‐performance Li‐O(2) battery.