DOE OSTI2020
Li3VS4 crystallizes in the orthorhombic Fdd2 space group. The structure is three-dimensional. there are seven inequivalent Li1+ sites. In the first Li1+ site, Li1+ is bonded to six S2- atoms to form distorted LiS6 octahedra that share corners with two equivalent VS4 tetrahedra, edges with six LiS6 octahedra, and edges with two equivalent VS4 tetrahedra. There are a spread of Li–S bond distances ranging from 2.56–3.05 Å. In the second Li1+ site, Li1+ is bonded to six S2- atoms to form distorted LiS6 octahedra that share corners with two equivalent VS4 tetrahedra, edges with six LiS6 octahedra, and edges with two equivalent VS4 tetrahedra. There are a spread of Li–S bond distances ranging from 2.53–3.03 Å. In the third Li1+ site, Li1+ is bonded to six S2- atoms to form distorted LiS6 octahedra that share corners with two equivalent LiS6 octahedra, corners with four VS4 tetrahedra, edges with four LiS6 octahedra, an edgeedge with one VS4 tetrahedra, and a faceface with one LiS6 octahedra. The corner-sharing octahedra tilt angles range from 29–58°. There are a spread of Li–S bond distances ranging from 2.53–2.99 Å. In the fourth Li1+ site, Li1+ is bonded to six S2- atoms to form LiS6 octahedra that share corners with four equivalent LiS6 octahedra, corners with four VS4 tetrahedra, edges with four LiS6 octahedra, and an edgeedge with one VS4 tetrahedra. The corner-sharing octahedra tilt angles range from 28–35°. There are a spread of Li–S bond distances ranging from 2.62–2.67 Å. In the fifth Li1+ site, Li1+ is bonded in a 6-coordinate geometry to six S2- atoms. There are a spread of Li–S bond distances ranging from 2.60–3.22 Å. In the sixth Li1+ site, Li1+ is bonded in a 6-coordinate geometry to six S2- atoms. There are a spread of Li–S bond distances ranging from 2.62–3.13 Å. In the seventh Li1+ site, Li1+ is bonded to six S2- atoms to form LiS6 octahedra that share corners with six LiS6 octahedra, corners with four VS4 tetrahedra, edges with two LiS6 octahedra, an edgeedge with one VS4 tetrahedra, and a faceface with one LiS6 octahedra. The corner-sharing octahedra tilt angles range from 28–58°. There are a spread of Li–S bond distances ranging from 2.53–2.81 Å. There are two inequivalent V5+ sites. In the first V5+ site, V5+ is bonded to four S2- atoms to form VS4 tetrahedra that share corners with seven LiS6 octahedra and edges with two LiS6 octahedra. The corner-sharing octahedra tilt angles range from 9–77°. There are a spread of V–S bond distances ranging from 2.14–2.17 Å. In the second V5+ site, V5+ is bonded to four S2- atoms to form VS4 tetrahedra that share corners with seven LiS6 octahedra and edges with three LiS6 octahedra. The corner-sharing octahedra tilt angles range from 9–78°. There are three shorter (2.16 Å) and one longer (2.17 Å) V–S bond lengths. There are eight inequivalent S2- sites. In the first S2- site, S2- is bonded to four Li1+ and one V5+ atom to form a mixture of distorted corner and edge-sharing SLi4V trigonal bipyramids. In the second S2- site, S2- is bonded in a 5-coordinate geometry to five Li1+ and one V5+ atom. In the third S2- site, S2- is bonded to four Li1+ and one V5+ atom to form a mixture of corner and edge-sharing SLi4V square pyramids. In the fourth S2- site, S2- is bonded to four Li1+ and one V5+ atom to form a mixture of distorted corner and edge-sharing SLi4V square pyramids. In the fifth S2- site, S2- is bonded in a 6-coordinate geometry to five Li1+ and one V5+ atom. In the sixth S2- site, S2- is bonded in a 5-coordinate geometry to four Li1+ and one V5+ atom. In the seventh S2- site, S2- is bonded in a 6-coordinate geometry to five Li1+ and one V5+ atom. In the eighth S2- site, S2- is bonded in a 6-coordinate geometry to five Li1+ and one V5+ atom.