Phenol‐Catalyzed Discharge in the Aprotic Lithium‐Oxygen Battery

Discharge in the lithium‐O(2) battery is known to occur either by a solution mechanism, which enables high capacity and rates, or a surface mechanism, which passivates the electrode surface and limits performance. The development of strategies to promote solution‐phase discharge in stable electrolyte solutions is a central challenge for development of the lithium‐O(2) battery. Here we show that the introduction of the protic additive phenol to ethers can promote a solution‐phase discharge mechanism. Phenol acts as a phase‐transfer catalyst, dissolving the product Li(2)O(2), avoiding electrode passivation and forming large particles of Li(2)O(2) product—vital requirements for high performance. As a result, we demonstrate capacities of over 9 mAh cm(−2) (areal), which is a 35‐fold increase in capacity compared to without phenol. We show that the critical requirement is the strength of the conjugate base such that an equilibrium exists between protonation of the base and protonation of Li(2)O(2).