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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 conc
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