Rationally Designed Sodium Chromium Vanadium Phosphate Cathodes with Multi-Electron Reaction for Fast-Charging Sodium-Ion Batteries

Authors：Zhang, Wei; Wu, Yulun; Xu, Zhenming^*; Li, Huangxu; Xu, Ming; Li, Jianwei; Dai, Yuhang; Zong, Wei; Chen, Ruwei; He, Liang; Zhang, Zhian^*; Brett, Dan J. L.; He, Guanjie^*; Lai, Yanqing^*; Parkin, Ivan P.

Source：Advanced Energy Materials, 2022, 12(25): 2201065.

DOI：10.1002/aenm.202201065

• fast-charging
• multielectron reaction
• NASICON
• Sodium-ion batteries

Sodium super-ionic conductor (NASICON)-structured phosphates are emerging as rising stars as cathodes for sodium-ion batteries. However, they usually suffer from a relatively low capacity due to the limited activated redox couples and low intrinsic electronic conductivity. Herein, a reduced graphene oxide supported NASICON Na3Cr0.5V1.5(PO4)(3) cathode (VC/C-G) is designed, which displays ultrafast (up to 50 C) and ultrastable (1 000 cycles at 20 C) Na+ storage properties. The VC/C-G can reach a high energy density of approximate to 470 W h kg(-1) at 0.2 C with a specific capacity of 176 mAh g(-1) (equivalent to the theoretical value); this corresponds to a three-electron transfer reaction based on fully activated V5+/V4+, V4+/V3+, V3+/V2+ couples. In situ X-ray diffraction (XRD) results disclose a combination of solid-solution reaction and biphasic reaction mechanisms upon cycling. Density functional theory calculations reveal a narrow forbidden-band gap of 1.41 eV and a low Na+ diffusion energy barrier of 0.194 eV. Furthermore, VC/C-G shows excellent fast-charging performance by only taking approximate to 11 min to reach 80% state of charge. The work provides a widely applicable strategy for realizing multi-electron cathode design for high-performance SIBs.

• Institution
  南京航空航天大学; 1; 西安交通大学