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Na3+yV2-yMgy(PO4)3 (0 ≤ y ≤ 1) NASICON compounds, thanks to their relative simplicity and the presence of a single redox-active species, are of interest for understanding the function and limitations of more complex, mixed transition metal NASICON-type Na-ion cathodes. Partial Mg substitution for V in Na3+yV2-yMgy(PO4)3 leads to a gradual transition from a two-phase to a solid solution Na (de)intercalation mechanism during electrochemical cycling. When cycled over a narrow voltage window (3.8 – 2.75 V vs. Na+/Na0), these cathodes exhibit good structural and electrochemical reversibility, leading to a high capacity retention. Yet, when the upper cutoff voltage is increased from 3.8 V to 4.2 V, significant irreversibilities arise, accompanied by a notable evolution of the electrochemical profiles during the first cycle. We focus here on the y = 0.5 and 1 compounds and use a combination of electrochemical testing, advanced characterization, and first principles density functional theory calculations to investigate the redox and structural processes taking place at high potentials. In-situ and ex-situ X-ray diffraction, and 23Na and 31P solid-state NMR reveal bulk structural rearrangements, at least partly caused by Na extraction from Na(1) sites. For the y = 1 cathode, an irreversible phase transition leads to a change in the symmetry of the crystal structure from rhombohedral to monoclinic. For both compounds, substantial distortions of the VO6 octahedra and irreversible changes to the local structure are observed using X-ray absorption spectroscopy during high voltage cycling, but our 51V NMR results show no evidence for V migration. Instead, first principles nudged elastic band calculations suggest low energy migration pathways for Mg2+ into vacant face-sharing Na(1) sites at high states of charge. These findings are consistent with the significant evolution of the electrochemical profile during the first cycle, voltage hysteresis, and subsequent rapid capacity decay. More broadly, these results could suggest similar structural rearrangements (e.g., Mn migration) in related V- and Mn-containing NASICON cathodes, which also show poor reversibility when cycled up to high potentials. 

Of the few weberite-type Na-ion cathodes explored to date, Na₂Fe₂F₇ exhibits the best performance, with capacities up to 184 mAh/g and energy densities up to 550 Wh/kg reported for this material. However, the development of robust structure-property relationships for this material is complicated by its tendency to form as a mixture of metastable polymorphs, and transform to a lower-energy NayFeF3 perovskite compound during electrochemical cycling. Our first principles-guided exploration of Fe-based weberite solid solutions with redox-inactive Mg2+ and Al3+ predicts an enhanced thermodynamic stability of Na2MgxFe2−x F7 as the Mg content is increased, and the x = 0.125 composition is selected for further exploration. We demonstrate that the monoclinic polymorph (space group C2/c) of Na2Fe2F7 (Mg0) and of a new Mg-substituted weberite composition, Na2Mg0.125Fe1.875F7 (Mg0.125), can be isolated using an optimized synthesis protocol. The impact of Mg substitution on the stability of the weberite phase during electrochemical cycling, and on the extent and rate of Na (de)intercalation, is examined. Irrespective of the Mg content, we find that the weberite phase is retained when cycling over a narrow voltage window (2.8– 4.0 V vs. Na/Na+). Over a wider voltage range (1.9–4.0 V), Mg0 shows steady capacity fade due to its transformation to the NayFeF₃ perovskite phase, while Mg0.125 displays more reversible cycling and a reduced phase transformation. Yet, Mg incorporation also leads to kinetically limited Na extraction, and a reduced overall capacity. These findings highlight the need for the continued compositional optimization of weberite cathodes to improve their structural stability while maximizing their energy density. 

Weberite-type sodium transition metal fluorides (Na2M2+Mʹ3+F7) have emerged as potential high performance sodium intercalation cathodes, with predicted energy densities in the 600-800 Wh/kg range and fast Na-ion transport. One of the few weberites that has been electrochemically tested is Na2Fe2F7, 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 Na2Fe2F7 weberite polymorphs, as well as their predicted (de)intercalation behavior. We find that as-prepared Na2Fe2F7 samples inevitably contain a mixture of polymorphs, with local probes such as solid-state nuclear magnetic resonance and Mössbauer spectroscopy providing unique insights into the distribution of Na and Fe local environments. Polymorphic Na2Fe2F7 exhibits a respectable initial capacity yet steady capacity fade, a consequence of the transformation of the Na2Fe2F7 weberite phases to the more stable perovskite-type NaFeF3 phase upon cycling, as revealed by ex situ 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.