Materials Data on Li5BiS4 by Materials Project

Abstract

Li5BiS4 crystallizes in the tetragonal P4_2/nmc space group. The structure is three-dimensional. there are six inequivalent Li1+ sites. In the first Li1+ site, Li1+ is bonded to four equivalent S2- atoms to form LiS4 tetrahedra that share corners with four equivalent BiS4 tetrahedra, corners with six LiS4 tetrahedra, and edges with five LiS4 tetrahedra. There are two shorter (2.42 Å) and two longer (2.46 Å) Li–S bond lengths. In the second Li1+ site, Li1+ is bonded to four S2- atoms to form LiS4 tetrahedra that share corners with two equivalent BiS4 tetrahedra, corners with ten LiS4 tetrahedra, an edgeedge with one BiS4 tetrahedra, and edges with four LiS4 tetrahedra. There are a spread of Li–S bond distances ranging from 2.43–2.66 Å. In the third Li1+ site, Li1+ is bonded to four S2- atoms to form LiS4 tetrahedra that share corners with four equivalent BiS4 tetrahedra, corners with ten LiS4 tetrahedra, and edges with two LiS4 tetrahedra. There are two shorter (2.52 Å) and two longer (2.55 Å) Li–S bond lengths. In the fourth Li1+ site, Li1+ is bonded to four equivalent S2- atoms to form LiS4 tetrahedra that share corners with four equivalent BiS4 tetrahedra, corners with eight equivalent LiS4 tetrahedra, and edges with six LiS4 tetrahedra. All Li–S bond lengths are 2.46 Å. In the fifth Li1+ site, Li1+ is bonded to four equivalent S2- atoms to form LiS4 tetrahedra that share corners with four equivalent BiS4 tetrahedra, corners with eight equivalent LiS4 tetrahedra, and edges with two equivalent LiS4 tetrahedra. All Li–S bond lengths are 2.55 Å. In the sixth Li1+ site, Li1+ is bonded to four equivalent S2- atoms to form LiS4 tetrahedra that share corners with four equivalent BiS4 tetrahedra and edges with six LiS4 tetrahedra. All Li–S bond lengths are 2.38 Å. Bi3+ is bonded to four S2- atoms to form BiS4 tetrahedra that share corners with sixteen LiS4 tetrahedra and edges with two equivalent LiS4 tetrahedra. There are a spread of Bi–S bond distances ranging from 2.64–2.75 Å. There are three inequivalent S2- sites. In the first S2- site, S2- is bonded to five Li1+ and one Bi3+ atom to form a mixture of distorted edge and corner-sharing SLi5Bi octahedra. The corner-sharing octahedra tilt angles range from 49–68°. In the second S2- site, S2- is bonded in a 7-coordinate geometry to six Li1+ and one Bi3+ atom. In the third S2- site, S2- is bonded in a 5-coordinate geometry to four Li1+ and one Bi3+ atom.