Unraveling the modified mechanism of ruthenium substitution on Na3V2(PO4)3 with superior rate capability and ultralong cyclic performance

Abstract

Na3V2(PO4)3(NVP) is an ideal cathode material for sodium ion battery due to its stable three-dimensional frame structure and high operating voltage. However, the low intrinsic conductivity and serious structural collapse limit its further application. In this work, a simultaneous optimized Na3V1.96Ru0.04(PO4)3/C@CNTs cathode material is synthesized by a simple sol–gel method. Specifically, the ionic radius of Ru3+ is slightly larger than that of V3+ (0.68 Å vs 0.64 Å), which not only ensures the feasibility of Ru3+ replacing V3+ site, but also appropriately expands the migration channel of sodium ions in NVP and stabilizes the structure, effectively improving the diffusion efficiency of sodium ions. Moreover, CNTs construct a three-dimensional conductive network between the grains, reducing the impedance at the interface and effectively improving the electronic conductivity. Ex-situ XRD analysis at different SOC were performed to determine the change in the crystal structure of Ru3+doped Na3V2(PO4)3, and the refinement results simultaneously demonstrate the relatively low volume shrinkage value of less than 3 % during the de-intercalation process, further verifying the stabilized crystal construction after Ru3+ substitution. Furthermore, the ex-situ XRD/SEM/CV/EIS after cycling indicate the significantly improved kinetic characteristics and enhanced structural stability. Notably, the modified Na3V1.96Ru0.04(PO4)3/C@CNTs reveals superior rate capability and ultralong cyclic performance. It submits high capacities of 82.3/80.9 mAh g−1 at 80/120C and maintains 71.3/59.6 mAh g−1 after 14800/6250 cycles, indicating excellent retention ratios of 86.6 % and 73.6 %, respectively. This work provides a multi-modification strategy for the realization of high-performance cathode materials, which can be widely applied in the optimization of various materials.