Polymorphism in Weberite NaFeF and its Effects on Electrochemical Properties as a Na-Ion Cathode.

Weberite-type sodium transition metal fluorides (Na'F) have emerged as potential high-performance sodium intercalation cathodes, with predicted energy densities in the 600-800 W h/kg range and fast Na-ion transport. One of the few weberites that have been electrochemically tested is NaFeF, yet inconsistencies in its reported structure and electrochemical properties have hampered the establishment of clear structure-property relationships. In this study, we reconcile structural characteristics and electrochemical behavior using a combined experimental-computational approach. First-principles calculations reveal the inherent metastability of weberite-type phases, the close energetics of several NaFeF weberite polymorphs, and their predicted (de)intercalation behavior. We find that the as-prepared NaFeF samples inevitably contain a mixture of polymorphs, with local probes such as solid-state nuclear magnetic resonance (NMR) and Mössbauer spectroscopy providing unique insights into the distribution of Na and Fe local environments. Polymorphic NaFeF exhibits a respectable initial capacity yet steady capacity fade, a consequence of the transformation of the NaFeF weberite phases to the more stable perovskite-type NaFeF phase upon cycling, as revealed by synchrotron X-ray diffraction and solid-state NMR. Overall, these findings highlight the need for greater control over weberite polymorphism and phase stability through compositional tuning and synthesis optimization.