Surface Crystal Modification of Na₃V₂(PO₄)₃ to Cast Intermediate Na₂V₂(PO₄)₃ Phase toward High‐Rate Sodium Storage

Abstract The two‐phase reaction of Na₃V₂(PO₄)₃ – Na₁V₂(PO₄)₃ in Na₃V₂(PO₄)₃ (NVP) is hindered by low electronic and ionic conductivity. To address this problem, a surface‐N‐doped NVP encapsulating by N‐doped carbon nanocage (N‐NVP/N‐CN) is rationally constructed, wherein the nitrogen is doped in both the surface crystal structure of NVP and carbon layer. The surface crystal modification decreases the energy barrier of Na⁺ diffusion from bulk to electrolyte, enhances intrinsic electronic conductivity, and releases lattice stress. Meanwhile, the porous architecture provides more active sites for redox reactions and shortens the diffusion path of ion. Furthermore, the new interphase of Na₂V₂(PO₄)₃ is detected by in situ XRD and clarified by density functional theory (DFT) calculation with a lower energy barrier during the fast reversible electrochemical three‐phase reaction of Na₃V₂(PO₄)₃ – Na₂V₂(PO₄)₃ – Na₁V₂(PO₄)₃. Therefore, as cathode of sodium‐ion battery, the N‐NVP/N‐CN exhibited specific capacities of 119.7 and 75.3 mAh g⁻¹ at 1 C and even 200 C. Amazingly, high capacities of 89.0, 86.2, and 84.6 mAh g⁻¹ are achieved after overlong 10000 cycles at 20, 40, and 50 C, respectively. This approach provides a new idea for surface crystal modification to cast intermediate Na₂V₂(PO₄)₃ phase for achieving excellent cycling stability and rate capability.