Molecular Unravelling of the Structural Effect of Quinone Redox Mediators on Oxygen Reduction Reaction in Aprotic Lithium–Oxygen Batteries

Redox mediators (RMs) provide tantalizing solutions to unlock the energy capabilities of aprotic lithium-oxygen (Li-O₂) batteries by driving solution-mediated Li₂O₂ growth. However, the structural effect of RMs on the catalytic efficiency of the oxygen reduction reaction remains incompletely understood. Herein, we present the interplay between the structure of RMs and their discharge capabilities by a comparative study of model quinone (Q)-based RMs. Specifically, at low current densities, incorporating electron-withdrawing groups onto the Q ring can positively move the discharge potential and deliver larger discharge capacity by extending the lifespan of the LiQO₂ intermediate and allowing for Li₂O₂ growth into deeper electrolyte regions. Conversely, at high current densities, the absence of electron-withdrawing groups facilitates homogeneous reaction kinetics from LiQ to regenerate Q (i.e., decreased lifespan of LiQO₂), mitigating electrode potential polarization and preserving catalytic activity of Q for higher discharge capacity. The work establishes structure-property relationships that guide the rational design of RMs toward next-generation Li-O₂ batteries.