Recent Advances and Perspectives on the Promising High‐Voltage Cathode Material of Na3(VO)2(PO4)2F

Abstract Na 3 (VO) 2 (PO 4 ) 2 F (NVOPF) has emerged as one of the most promising cathode materials for sodium‐ion batteries (SIBs) attributed to its high specific capacity (130 mAh g −1 ), high operation voltage (>3.9 V vs Na + /Na), and excellent structural stability (<2% volume change). However, the comparatively low intrinsic electronic conductivity (≈10 −7 S cm −1 ) of NVOPF leads to unsatisfactory electrochemical performance, especially at high rates, limiting its practical applications. To improve the conductivity and enhance Na storage performance, many efforts have been devoted to designing NVOPF, including morphology optimization, hybridization with conductive materials, metal‐ion doping, Na‐site regulation, and F/O ratio adjustment. These attempts have shown some encouraging achievements and shed light on the practical application of NVOPF cathodes. This work aims to provide a general introduction, synthetic methods, and rational design of NVOPF to give a deeper understanding of the recent progress. Additionally, the unique microstructure of NVOPF and its relationship with Na storage properties are also described in detail. The current status, as well as the advances and limitations of such SIB cathode material, are reported. Finally, future perspectives and guidance for advancing high‐performance NVOPF cathodes toward practical applications are presented.