Operando Ambient Pressure X-ray Photoelectron Spectroscopy Studies of Sodium–Oxygen Redox Reactions

Lower charge overpotential of sodium–oxygen (Na–O2) batteries makes them a promising electrical storage technology. However, they have an undesirable discharge product, sodium carbonate (Na2CO3), which has widely been found in many previous studies. Whether and how the carbon components in the cathode are involved in the formation of Na2CO3 is still not well understood. Herein, an all solid-state Na–O2 battery was constructed and its charge and discharge cycles were studied using ambient pressure X-ray photoelectron spectroscopy. The operando XPS results clearly demonstrate the formation of Na2CO3 on the cathode during the discharge cycle. A fraction of the carbonate formed can be cycled while charging the battery. Transformation of the carbon-based cathode to Na2CO3 is a potential cause of capacity fading of the Na–O2 battery.