Structural and electronic properties of V₂O₅ and their tuning by doping with 3d elements - modelling using the DFT+U...

New electrode materials for alkaline-ion batteries are a timely topic. Among many promising candidates, V2O5 is one of the most interesting cathode materials. While having very high theoretical capacity, in practice, its performance is hindered by its low stability and poor conductivity. As regards the theoretical descriptions of V2O5, common DFT-GGA calculations fail to reproduce both the electronic and crystal structures. While the band gap is underestimated, the interlayer spacing is overestimated as weak dispersion interactions are not properly described within GGA. Here we show that the combination of the DFT+U method and semi-empirical D2 correction can compensate for the drawbacks of the GGA when it comes to the modelling of V2O5. When compared to common PBE calculations, with a modest increase in the computational cost, PBE+U+D2 fully reproduced the experimental band gap of V2O5, while the errors in the lattice parameters are only a few percent. Using the proposed PBE+U+D2 methodology we studied the doping of V2O5 with 3d elements (from Sc to Zn). We show that both the structural and electronic parameters are affected by doping. Most importantly, a significant increase in conductivity is expected upon doping, which is of great importance for the application of V2O5 in metal-ion batteries.