DOE OSTI2020
Li5V5Cl16 is beta indium sulfide-derived structured and crystallizes in the orthorhombic Aem2 space group. The structure is three-dimensional. there are four inequivalent Li1+ sites. In the first Li1+ site, Li1+ is bonded to four Cl1- atoms to form LiCl4 tetrahedra that share corners with five LiCl6 octahedra and corners with seven VCl6 octahedra. The corner-sharing octahedra tilt angles range from 56–61°. There are a spread of Li–Cl bond distances ranging from 2.34–2.57 Å. In the second Li1+ site, Li1+ is bonded to six Cl1- atoms to form LiCl6 octahedra that share corners with three LiCl4 tetrahedra and edges with six VCl6 octahedra. There are a spread of Li–Cl bond distances ranging from 2.52–2.63 Å. In the third Li1+ site, Li1+ is bonded to six Cl1- atoms to form LiCl6 octahedra that share corners with three LiCl4 tetrahedra, edges with two equivalent LiCl6 octahedra, and edges with four VCl6 octahedra. There are a spread of Li–Cl bond distances ranging from 2.48–2.68 Å. In the fourth Li1+ site, Li1+ is bonded to four Cl1- atoms to form LiCl4 tetrahedra that share corners with four LiCl6 octahedra and corners with eight VCl6 octahedra. The corner-sharing octahedra tilt angles range from 56–62°. All Li–Cl bond lengths are 2.41 Å. There are three inequivalent V+2.20+ sites. In the first V+2.20+ site, V+2.20+ is bonded to six Cl1- atoms to form VCl6 octahedra that share corners with three LiCl4 tetrahedra, edges with three LiCl6 octahedra, and edges with three VCl6 octahedra. There are a spread of V–Cl bond distances ranging from 2.44–2.52 Å. In the second V+2.20+ site, V+2.20+ is bonded to six Cl1- atoms to form VCl6 octahedra that share corners with three LiCl4 tetrahedra, edges with two equivalent LiCl6 octahedra, and edges with four VCl6 octahedra. There are a spread of V–Cl bond distances ranging from 2.44–2.53 Å. In the third V+2.20+ site, V+2.20+ is bonded to six Cl1- atoms to form VCl6 octahedra that share corners with three LiCl4 tetrahedra, edges with three LiCl6 octahedra, and edges with three VCl6 octahedra. There are a spread of V–Cl bond distances ranging from 2.38–2.57 Å. There are ten inequivalent Cl1- sites. In the first Cl1- site, Cl1- is bonded in a distorted T-shaped geometry to one Li1+ and two equivalent V+2.20+ atoms. In the second Cl1- site, Cl1- is bonded in a distorted T-shaped geometry to one Li1+ and two V+2.20+ atoms. In the third Cl1- site, Cl1- is bonded in a distorted T-shaped geometry to three V+2.20+ atoms. In the fourth Cl1- site, Cl1- is bonded to one Li1+ and three V+2.20+ atoms to form distorted ClLiV3 trigonal pyramids that share corners with two equivalent ClLi3V tetrahedra, a cornercorner with one ClLi2V2 trigonal pyramid, and edges with three ClLi2V2 trigonal pyramids. In the fifth Cl1- site, Cl1- is bonded in a distorted T-shaped geometry to one Li1+ and two equivalent V+2.20+ atoms. In the sixth Cl1- site, Cl1- is bonded to two Li1+ and two V+2.20+ atoms to form distorted ClLi2V2 trigonal pyramids that share a cornercorner with one ClLi2V2 trigonal pyramid and edges with three ClLiV3 trigonal pyramids. In the seventh Cl1- site, Cl1- is bonded in a distorted T-shaped geometry to two equivalent Li1+ and one V+2.20+ atom. In the eighth Cl1- site, Cl1- is bonded to two Li1+ and two equivalent V+2.20+ atoms to form distorted ClLi2V2 trigonal pyramids that share corners with two equivalent ClLi3V tetrahedra, a cornercorner with one ClLiV3 trigonal pyramid, and edges with three ClLiV3 trigonal pyramids. In the ninth Cl1- site, Cl1- is bonded in a rectangular see-saw-like geometry to two Li1+ and two equivalent V+2.20+ atoms. In the tenth Cl1- site, Cl1- is bonded to three Li1+ and one V+2.20+ atom to form distorted ClLi3V tetrahedra that share a cornercorner with one ClLi3V tetrahedra, corners with two ClLiV3 trigonal pyramids, and an edgeedge with one ClLi3V tetrahedra.