LAUSR

When aprotic Li-O2 batteries recharge, the solid Li2O2 in the positive electrode is oxidized, which often exhibits a continuous or step increase in the charging potential as a function of the charging capacity, and its origin remains incompletely understood. Here, we report a model study of electro-oxidation of a Li2O2 film on an Au electrode using voltammetry coupled with in situ Raman spectroscopy. It was found that the charging reaction initializes at the positive electrode|Li2O2 interface, instead of the previously presumed Li2O2 surface, and consists of two temporally and spatially separated Li2O2 oxidation processes, accounting for the potential rise during charging of Li-O2 batteries. Moreover, the electrode surface-initialized oxidation can disintegrate the Li2O2 film resulting in a loss of Li2O2 into electrolyte solution, which drastically decreases the charging efficiency and highlights the importance of using soluble electro-catalyst for the complete charging of Li-O2 batteries.