DOE OSTI2020
Li3V5O10 crystallizes in the triclinic P-1 space group. The structure is three-dimensional. there are two inequivalent Li1+ sites. In the first Li1+ site, Li1+ is bonded to six O2- atoms to form LiO6 octahedra that share a cornercorner with one LiO6 octahedra, corners with five VO6 octahedra, edges with four LiO6 octahedra, and edges with five VO6 octahedra. The corner-sharing octahedra tilt angles range from 7–20°. There are a spread of Li–O bond distances ranging from 2.09–2.36 Å. In the second Li1+ site, Li1+ is bonded to six O2- atoms to form distorted LiO6 octahedra that share corners with two equivalent LiO6 octahedra, corners with two equivalent VO6 octahedra, edges with four equivalent LiO6 octahedra, and edges with six VO6 octahedra. The corner-sharing octahedra tilt angles range from 11–14°. There are a spread of Li–O bond distances ranging from 1.98–2.43 Å. There are three inequivalent V+3.40+ sites. In the first V+3.40+ site, V+3.40+ is bonded to six O2- atoms to form VO6 octahedra that share a cornercorner with one VO6 octahedra, corners with two equivalent LiO6 octahedra, edges with five LiO6 octahedra, and edges with five VO6 octahedra. The corner-sharing octahedra tilt angles range from 11–15°. There are a spread of V–O bond distances ranging from 1.81–2.10 Å. In the second V+3.40+ site, V+3.40+ is bonded to six O2- atoms to form VO6 octahedra that share corners with two equivalent LiO6 octahedra, corners with four VO6 octahedra, edges with two equivalent LiO6 octahedra, and edges with six VO6 octahedra. The corner-sharing octahedra tilt angles range from 11–16°. There are four shorter (2.04 Å) and two longer (2.10 Å) V–O bond lengths. In the third V+3.40+ site, V+3.40+ is bonded to six O2- atoms to form VO6 octahedra that share a cornercorner with one VO6 octahedra, corners with three equivalent LiO6 octahedra, edges with two LiO6 octahedra, and edges with seven VO6 octahedra. The corner-sharing octahedra tilt angles range from 7–20°. There are a spread of V–O bond distances ranging from 1.98–2.16 Å. There are five inequivalent O2- sites. In the first O2- site, O2- is bonded to one Li1+ and four V+3.40+ atoms to form a mixture of edge and corner-sharing OLiV4 square pyramids. In the second O2- site, O2- is bonded to three Li1+ and two equivalent V+3.40+ atoms to form a mixture of edge and corner-sharing OLi3V2 square pyramids. In the third O2- site, O2- is bonded in a rectangular see-saw-like geometry to four V+3.40+ atoms. In the fourth O2- site, O2- is bonded to two Li1+ and three V+3.40+ atoms to form distorted OLi2V3 square pyramids that share corners with six OLi3V2 square pyramids and edges with seven OLiV4 square pyramids. In the fifth O2- site, O2- is bonded to three Li1+ and two V+3.40+ atoms to form a mixture of distorted edge and corner-sharing OLi3V2 square pyramids.