First-Order or Second-Order? Disproportionation of Lithium Superoxide in Li–O2 Batteries

The disproportionation of LiO2 to Li2O2 is a key step in Li–O2 batteries, and it is regarded as a second-order reaction. However, its mechanism is not well addressed, and its kinetics is rarely studied due to the difficulties of quantifying the rate constants, particularly for high concentrations of superoxide (>10 mM). Here, we quantified the kinetic rate constant by a microkinetic model using a microelectrode tip with a thin diffusion layer and fast response. We report that the reaction order of LiO2 transitions from 1 at high concentrations of superoxide (∼20 mM) to 2 at low concentrations of superoxide (∼1 mM). LiO2 is chemically reduced by free superoxides to form Li2O2 and O2, instead of reacting with another LiO2 via a disproportionation step. This chemical-reduction mechanism explained the change of reaction order and the kinetics profile. As a rate-determining step, this step restricts the overall kinetics of the discharging process and should be the focus of future catalyst design.