Insights into Electrochemical Oxidation of NaO2 in Na-O2 Batteries via Rotating Ring Disk and Spectroscopic Measurements.

O2 reduction in aprotic Na-O2 batteries results in the formation of NaO2, which can be oxidized at small overpotentials (<200 mV) on charge. In this study, we investigated the NaO2 oxidation mechanism using rotating ring disk electrode (RRDE) measurements of Na-O2 reaction products and by tracking the morphological evolution of the NaO2 discharge product at different states of charge using scanning electron microscopy (SEM). The results show that negligible soluble species are formed during NaO2 oxidation, and that the oxidation occurs predominantly via charge transfer at the interface between NaO2 and carbon electrode fibers rather than uniformly from all NaO2 surfaces. X-ray absorption near edge structure (XANES), and X-ray photoelectron spectroscopy (XPS) measurements show that the band gap of NaO2 is smaller than that of Li2O2 formed in Li-O2 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.