Electronic Structures of LixV2O5 (x=0.5 and 1): A Theoretical Study

The electronic properties of α‐Li_xV₂O₅ (x=0.5 and 1) are investigated using first principle calculations based on density functional theory with local density approximation. Different intercalation sites for Li in the V₂O₅ lattices are considered, showing different influences on the electronic structures of Li_xV₂O₅. The lowest total energy is found when Li is only intercalated along the c axis between two bridging oxygen ions of sequential V₂O₅ layers. The intercalation of Li into V₂O₅ does not change the electron transition property of V₂O₅, which is an indirect band gap semiconductor, but leads to a reduction of vanadium ions and an increase of the Fermi level of Li_xV₂O₅ arising from the electron transfer from the Li 2 s orbital to the initially empty conduction band of the V₂O₅ host.