Reaction Mechanism and Surface Film Formation of Conversion Materials for Lithium- and Sodium-Ion Batteries: An XPS Case Study on Sputtered Copper Oxide (CuO) Thin Film Model Electrodes

Charge storage based on conversion reactions is a promising concept to store electrical energy. Many studies have been devoted to conversion reactions with lithium; however, still many scientific questions remain due to the complexity of the reaction mechanism combined with surface film formation. Replacing lithium by sodium is an attractive approach to widen the scope of conversion reactions and to study whether the increase in ion size changes the reaction mechanisms and whether the cell performance benefits or worsens. In this study, we use thin film electrodes as a additive-free model system to study the conversion reaction of CuO with sodium (CuO/Na) by means of electrochemical methods, microscopy, and X-ray photoelectron spectroscopy. The reaction mechanism and film formation are being discussed. Some important differences to the analogue lithium-based system (CuO/Li) are found. Whereas CuO has been reported as charge product in CuO/Li cells, charging is incomplete in the case of CuO/Na and only Cu₂O is formed. As an important finding, oxygen appears to be redox active and Na₂O₂ forms during charging from Na₂O. Moreover, surface film formation due to electrolyte decomposition is much more severe as compared to CuO/Li. Depth profiling is used to probe the inner composition of the surface film, revealing a much thicker surface film with more inorganic components as compared to the lithium system. It is also found that the surface film disappears to a large extent during charging