We demonstrate an economical polytetrafluoroethylene-assisted fluorination method to synthesize three binary sodium-rich fluorides NaMVF (M = Mn, Fe, and Co). The optimal NaFeVF cathode delivers a high reversible capacity of 146.5 mA h g based on active Fe/Fe and V/V redox reactions in sodium-ion batteries. A steady cycling performance with a high capacity retention of 95% over 200 cycles is achieved owing to the negligible structural change during Na insertion/extraction.
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