Defect Thermodynamics in Nonstoichiometric Alluaudite-Based Polyanionic Materials for Na-Ion Batteries.

Sodium iron sulfate in the form of alluaudite NaFe(SO) (or NFS) has emerged as one of the most promising cathodes for Na-ion batteries due to its highest Fe redox potential, low cost, sustainability, and high rate capability. Unlike most of the other cathodes, NFS generally crystalizes in its nonstoichiometric form with partial Na substitution for Fe sites and contains a small amount of impurities. However, profound explanations behind this inherent behavior including others, like phase stability, configurational structure, and defect formation are still ambiguous. We therefore performed first-principles calculations combined with a random swapping method to determine the minimum energy configurations of NFS (with = 0, 0.25, and 0.5) and find a correlation between the Na distribution pattern and energetics in which the site preference for Na ion is in a sequence of Na4 > Na1 > Na2 > Na3. Our result points out that the nonstoichiometry cannot be properly described under the framework of primitive structures. Moreover, we investigated phase stability diagrams and defect formations based on thermodynamic criteria. Our predicted phase diagrams can explain the inevitable impurity precipitation, which can be reduced as diminishes. Defect formation analysis indicates an unlikely formation of channel blockage and identifies the dominant formation of Fe + and Na + Na complexes. While the former can become spontaneous in a Na-deficient environment, the latter occurs mainly in NFS0 and accommodates the presence of nonstoichiometry.