Mechanistic Study on Oxygen Reduction Reaction in High-Concentrated Electrolytes for Aprotic Lithium–Oxygen Batteries

Highly concentrated electrolytes (HCEs) have energized the development of high-energy-density lithium metal batteries by facilitating the formation of robust inorganic-derived solid electrolyte interfaces on the lithium anode. However, the oxygen reduction reaction (ORR) occurring on the cathode side remains ambiguous in HCE-based lithium–oxygen (Li–O₂) batteries. Herein, we investigate the ORR mechanism in a highly concentrated LiTFSI-CH₃CN electrolyte using ultra-microelectrode voltammetry coupled with in situ spectroscopies. It is found that, compared to the dilute electrolyte, the HCE prolongs the lifespan of superoxide intermediates and decelerates their migration rate to the bulk solution, resulting in a change in growth mode for the discharge product of Li₂O₂ from traditional two-dimensional film growth to surface three-dimensional expansion growth. This alteration reduces the cathode passivation and thus delivers the enhanced discharge capacity. Additionally, the HCE also increases the reaction energy barrier between superoxide and solvent molecules, thereby minimizing parasitic reactions and improving the cycle performance of Li–O₂ batteries. Our study reveals the intricate interplay between electrolytes and oxygen intermediates and provides important insights into electrolyte chemistries for better Li–O₂ batteries.