Understanding the NaMnO₂ System: A Thermodynamics and XPS Approach

The NaMnO₂ system is an important class of materials with potential applications in rechargeable batteries, supercapacitors, catalysts, and gas sensors. This work reports the synthesis of NaMnO₂ (x = 0.39, 0.44, 0.48, 0.66, and 0.70) compounds and their characterization by powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and impedance spectroscopy (IS) techniques. The compounds in this series exhibit a significant variation in their structures with the extent of Na-content. The change in the nature of bonding with increasing Na content was investigated, and its effect on material stability as well as electrotransport properties was investigated. A detailed thermodynamic evaluation of these materials was carried out employing calorimetric techniques, and the data were correlated with changes in the chemical environment around the Na ion. This analysis is crucial for predicting the thermodynamic stability of NaMnO₂ compounds under different environments for their applications in Na-ion batteries.