Abstract: Niobium-based oxide negative electrode materials have attracted much attention because of their excellent lithium-ion diffusion rate, but their poor electrical conductivity severely limits their large-scale application. In this study, the effects of different cationic doping on the bandgap of H-Nb₂O₅ state density were calculated by using the VASP software package and Hubbard modified generalized gradient approximation (GGA + U). The results show that Ni, Co and Ag can improve the electronic structure of H-Nb₂O₅ and reduce the band gap compared to pure phase H-Nb₂O₅ from 0.35 eV to 0, 0.13 and 0.17 eV, respectively. On this basis, H-Nb₂O₅ doped with Ni, Co and Ag was prepared using the solid phase method, and its structure and electrochemical lithium storage mechanism were studied, respectively. The experimental results show that Ni-doped H-Nb₂O₅ exhibits the best electrochemical performance among the doped H-Nb₂O₅ anodes. The specific discharge capacity reaches 203 mAh/g at 2.5 C. The capacity remains at 89 mAh/g at 50 C. The capacity loss rate per 3000 cycles is only 0.002 1% under the 25 C condition. The calculation results show that the migration barrier of Ni-doped H-Nb₂O₅ is 0.674 eV, much lower than 0.847 eV of pure H-Nb₂O₅.