High‐Capacity and Stable Li‐O₂ Batteries Enabled by a Trifunctional Soluble Redox Mediator

Li-O₂ batteries with ultrahigh theoretical energy densities usually suffer from low practical discharge capacities and inferior cycling stability owing to the cathode passivation caused by insulating discharge products and by-products. Here, a trifunctional ether-based redox mediator, 2,5-di-tert-butyl-1,4-dimethoxybenzene (DBDMB), is introduced into the electrolyte to capture reactive O₂ ⁻ and alleviate the rigorous oxidative environment of Li-O₂ batteries. Thanks to the strong solvation effect of DBDMB towards Li⁺ and O₂ ⁻ , it not only reduces the formation of by-products (a high Li₂ O₂ yield of 96.6 %), but also promotes the solution growth of large-sized Li₂ O₂ particles, avoiding the passivation of cathode as well as enabling a large discharge capacity. Moreover, DBDMB makes the oxidization of Li₂ O₂ and the decomposition of main by-products (Li₂ CO₃ and LiOH) proceed in a highly effective manner, prolonging the stability of Li-O₂ batteries (243 cycles at 1000 mAh g⁻¹ and 1000 mA g⁻¹ ).