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.

Controlling Solution-Mediated Reaction Mechanisms of Oxygen Reduction Using Potential and Solvent for Aprotic Lithium-Oxygen Batteries.

Fundamental understanding of growth mechanisms of Li2O2 in Li-O2 cells is critical for implementing batteries with high gravimetric energies. Li2O2 growth can occur first by 1e(-) transfer to O2, forming Li(+)-O2(-) and then either chemical disproportionation of Li(+)-O2(-), or a second electron transfer to Li(+)-O2(-). We demonstrate that Li2O2 growth is governed primarily by disproportionation of Li(+)-O2(-) at low overpotential, and surface-mediated electron transfer at high overpotential. We obtain evidence supporting this trend using the rotating ring disk electrode (RRDE) technique, which shows that the fraction of oxygen reduction reaction charge attributable to soluble Li(+)-O2(-)-based intermediates increases as the discharge overpotential reduces. Electrochemical quartz crystal microbalance (EQCM) measurements of oxygen reduction support this picture, and show that the dependence of the reaction mechanism on the applied potential explains the difference in Li2O2 morphologies observed at different discharge overpotentials: formation of large (∼250 nm-1 µm) toroids, and conformal coatings (<50 nm) at higher overpotentials. These results highlight that RRDE and EQCM can be used as complementary tools to gain new insights into the role of soluble and solid reaction intermediates in the growth of reaction products in metal-O2 batteries.

Low-temperature electrodeposition approach leading to robust mesoscopic anatase TiO2 films.

Anatase TiO2, a wide bandgap semiconductor, likely the most worldwide studied inorganic material for many practical applications, offers unequal characteristics for applications in photocatalysis and sun energy conversion. However, the lack of controllable, cost-effective methods for scalable fabrication of homogeneous thin films of anatase TiO2 at low temperatures (ie. < 100 °C) renders up-to-date deposition processes unsuited to flexible plastic supports or to smart textile fibres, thus limiting these wearable and easy-to-integrate emerging technologies. Here, we present a very versatile template-free method for producing robust mesoporous films of nanocrystalline anatase TiO2 at temperatures of/or below 80 °C. The individual assembly of the mesoscopic particles forming ever-demonstrated high optical quality beads of TiO2 affords, with this simple methodology, efficient light capture and confinement into the photo-anode, which in flexible dye-sensitized solar cell technology translates into a remarkable power conversion efficiency of 7.2% under A.M.1.5G conditions.