Extended Data Fig. 9: Four representative configurations of Li₁₉V₁₃O₃₂ (equivalent to Li₃V₂O₅) with low energies and the most stable ordered structures of Li_3+xV₂O₅ (x = 0, 1, 2) after structure enumeration.

The configurations a to d are obtained from 2 × 2 × 2 supercells of the rock salt cubic conventional cell. Octahedral sites are fully occupied by Li/V atoms (green octahedra are LiO₆; red octahedra are VO₆). These representative configurations were used for NEB calculations at the start of discharge. e, LiO₄ tetrahedra and LiO₆ octahedra are shown as blue and green polyhedral, respectively, when red ones are for VO₆ octahedra. From the structure of Li₃V₂O₅ to Li₄V₂O₅, the majority of octahedral Li transfer to tetrahedral Li, which is consistent with site occupancy results in Fig. 2c. When Li continues to be inserted, the number of LiO₆ octahedra remain the same and LiO₄ tetrahedra keep increasing.