文摘
O<sub>2sub> reduction in aprotic Na–O<sub>2sub> batteries results in the formation of NaO<sub>2sub>, which can be oxidized at small overpotentials (<200 mV) on charge. In this study, we investigated the NaO<sub>2sub> oxidation mechanism using rotating ring disk electrode (RRDE) measurements of Na−O<sub>2sub> reaction products and by tracking the morphological evolution of the NaO<sub>2sub> discharge product at different states of charge using scanning electron microscopy (SEM). The results show that negligible soluble species are formed during NaO<sub>2sub> oxidation, and that the oxidation occurs predominantly via charge transfer at the interface between NaO<sub>2sub> and carbon electrode fibers rather than uniformly from all NaO<sub>2sub> surfaces. X-ray absorption near edge structure (XANES), and X-ray photoelectron spectroscopy (XPS) measurements show that the band gap of NaO<sub>2sub> is smaller than that of Li<sub>2sub>O<sub>2sub> formed in Li–O<sub>2sub> batteries, in which charging overpotentials are much higher (∼1000 mV). These results emphasize the importance of discharge product electronic structure for rationalizing metal–air battery mechanisms and performance.