New Reaction Pathway of Superoxide Disproportionation Induced by a Soluble Catalyst in Li-O₂ Batteries

Aprotic Li-O₂ battery has attracted considerable interest for high theoretical energy density, however the disproportionation of the intermediate of superoxide (O₂ ^- ) during discharge and charge leads to slow reaction kinetics and large voltage hysteresis. Herein, the chemically stable ruthenium tris(bipyridine) (RB) cations are employed as a soluble catalyst to alternate the pathway of O₂ ^- disproportionation and its kinetics in both the discharge and charge processes. RB captures O₂ ^- dimer and promotes their intramolecular charge transfer, and it decreases the energy barrier of the disproportionation reaction from 7.70 to 0.70 kcal mol^-1 . This facilitates the discharge and charge processes and simultaneously mitigates O₂ ^- and singlet oxygen related side reactions. These endow the Li-O₂ battery with reduced discharge/charge voltage gap of 0.72 V and prolonged lifespan for over 230 cycles when coupled with RuO₂ catalyst. This work highlights the vital role of superoxide disproportionation for Li-O₂ battery.