Robust Cross‐Linked Na₃V₂(PO₄)₂F₃ Full Sodium‐Ion Batteries

Sodium‐ion batteries (SIBs) have rapidly risen to the forefront of energy storage systems as a promising supplementary for Lithium‐ion batteries (LIBs). Na₃V₂(PO₄)₂F₃ (NVPF) as a common cathode of SIBs, features the merits of high operating voltage, small volume change and favorable specific energy density. However, it suffers from poor cycling stability and rate performance induced by its low intrinsic conductivity. Herein, we propose an ingenious strategy targeting superior SIBs through cross‐linked NVPF with multi‐dimensional nanocarbon frameworks composed of amorphous carbon and carbon nanotubes (NVPF@C@CNTs). This rational design ensures favorable particle size for shortened sodium ion transmission pathway as well as improved electronic transfer network, thus leading to enhanced charge transfer kinetics and superior cycling stability. Benefited from this unique structure, significantly improved electrochemical properties are obtained, including high specific capacity (126.9 mAh g⁻¹ at 1 C, 1 C = 128 mA g⁻¹) and remarkably improved long‐term cycling stability with 93.9% capacity retention after 1000 cycles at 20 C. The energy density of 286.8 Wh kg⁻¹ can be reached for full cells with hard carbon as anode (NVPF@C@CNTs//HC). Additionally, the electrochemical performance of the full cell at high temperature is also investigated (95.3 mAh g⁻¹ after 100 cycles at 1 C at 50 °C). Such nanoscale dual‐carbon networks engineering and thorough discussion of ion diffusion kinetics might make contributions to accelerating the process of phosphate cathodes in SIBs for large‐scale energy storages.