The Mystery from Tetragonal NaVPO₄F to Monoclinic NaVPO₄F: Crystal Presentation, Phase Conversion, and Na‐Storage Kinetics

Abstract NaVPO₄F is regarded as one of the most competitive cathodes in high performance sodium ion batteries (SIBs). Two polymorphs with the tetragonal and monoclinic NaVPO₄F have been reported, while the true presentation of the fluorophosphates is still poorly understood. Herein, fluorophosphates with a molar ratio of 1:1:1:1 for Na, V, P, F are fabricated at different temperatures. The presentation of tetragonal and monoclinic NaVPO₄F is strikingly confirmed. For the first time, the accurate atomic arrangement in the crystal, and the irreversible phase transition from tetragonal to monoclinic with temperature variation are unveiled by combining series of advanced in/ex situ characterizations. From both the thermodynamic and kinetic perspectives, the sodium storage behavior and the electron/Na⁺ conduction, contributing to notably different electrochemical performance for the two fluorophosphates, are elaborately studied based on experimental and density functional theory calculations. The comprehensive expositions indicate that the tetragonal and monoclinic NaVPO₄F have the potential to be employed as high‐energy‐density and high‐power‐density cathodes, respectively. This research answers the question of the true state of the fluorophosphates and reveals some of their previously unexplored mysteries, which provides an instructive selection principle for NaVPO₄F compounds for serving in well‐defined application scenarios and is expected to become an accelerator for the next generation of high‐performance SIBs.