Detection of Electrochemical Reaction Products from the Sodium–Oxygen Cell with Solid-State ²³Na NMR Spectroscopy

²³Na MAS NMR spectra of sodium–oxygen (Na–O₂) cathodes reveals a combination of degradation species: newly observed sodium fluoride (NaF) and the expected sodium carbonate (Na₂CO₃), as well as the desired reaction product sodium peroxide (Na₂O₂). The initial reaction product, sodium superoxide (NaO₂), is not present in a measurable quantity in the ²³Na NMR spectra of the cycled electrodes. The reactivity of solid NaO₂ is probed further, and NaF is found to be formed through a reaction between the electrochemically generated NaO₂ and the electrode binder, polyvinylidene fluoride (PVDF). The instability of cell components in the presence of desired electrochemical reaction products is clearly problematic and bears further investigation

How to Control the Discharge Products in Na–O₂ Cells: Direct Evidence toward the Role of Functional Groups at the Air Electrode Surface

Sodium–oxygen batteries have received a significant amount of research attention as a low-overpotential alternative to lithium–oxygen. However, the critical factors governing the composition and morphology of the discharge products in Na–O₂ cells are not thoroughly understood. Here we show that oxygen containing functional groups at the air electrode surface have a substantial role in the electrochemical reaction mechanisms in Na–O₂ cells. Our results show that the presence of functional groups at the air–electrode surface conducts the growth mechanism of discharge products toward a surface-mediated mechanism, forming a conformal film of products at the electrode surface. In addition, oxygen reduction reaction at hydrophilic surfaces more likely passes through a peroxide pathway, which results in the formation of peroxide-based discharge products. Moreover, in-line X-ray diffraction combined with solid state ²³Na NMR results indicate the instability of discharge products against carbonaceous electrodes. The findings of this study help to explain the inconsistency among various reports on composition and morphology of the discharge products in Na–O₂ cells and allow the precise control over the discharge products