Materials Data on Li4TiS4 by Materials Project
Li4TiS4 is Aluminum carbonitride-like structured and crystallizes in the orthorhombic Pnma space group. The structure is three-dimensional. there are three inequivalent Li1+ sites. In the first Li1+ site, Li1+ is bonded to six S2- atoms to form LiS6 octahedra that share corners with two equivalent LiS4 tetrahedra, corners with two equivalent TiS4 tetrahedra, corners with six equivalent LiS4 trigonal pyramids, edges with two equivalent LiS6 octahedra, edges with two equivalent LiS4 tetrahedra, edges with two equivalent TiS4 tetrahedra, and faces with two equivalent LiS4 trigonal pyramids. There are a spread of Li–S bond distances ranging from 2.61–2.90 Å. In the second Li1+ site, Li1+ is bonded to four S2- atoms to form LiS4 tetrahedra that share corners with two equivalent LiS6 octahedra, corners with two equivalent TiS4 tetrahedra, corners with eight equivalent LiS4 trigonal pyramids, edges with two equivalent LiS6 octahedra, and an edgeedge with one TiS4 tetrahedra. The corner-sharing octahedral tilt angles are 53°. There are a spread of Li–S bond distances ranging from 2.45–2.48 Å. In the third Li1+ site, Li1+ is bonded to four S2- atoms to form distorted LiS4 trigonal pyramids that share corners with three equivalent LiS6 octahedra, corners with four equivalent LiS4 tetrahedra, corners with four equivalent TiS4 tetrahedra, corners with four equivalent LiS4 trigonal pyramids, and a faceface with one LiS6 octahedra. The corner-sharing octahedra tilt angles range from 18–51°. There are a spread of Li–S bond distances ranging from 2.43–2.58 Å. Ti4+ is bonded to four S2- atoms to form TiS4 tetrahedra that share corners with two equivalent LiS6 octahedra, corners with two equivalent LiS4 tetrahedra, corners with eight equivalent LiS4 trigonal pyramids, edges with two equivalent LiS6 octahedra, and an edgeedge with one LiS4 tetrahedra. The corner-sharing octahedral tilt angles are 51°. There are a spread of Ti–S bond distances ranging from 2.27–2.29 Å. There are three inequivalent S2- sites. In the first S2- site, S2- is bonded in a 6-coordinate geometry to five Li1+ and one Ti4+ atom. In the second S2- site, S2- is bonded in a 6-coordinate geometry to five Li1+ and one Ti4+ atom. In the third S2- site, S2- is bonded in a 5-coordinate geometry to four Li1+ and one Ti4+ atom.