DOE OSTI2020
LiTi2O4 crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are three inequivalent Li1+ sites. In the first Li1+ site, Li1+ is bonded to five O2- atoms to form LiO5 trigonal bipyramids that share corners with three TiO6 octahedra, corners with four LiO5 trigonal bipyramids, and edges with six TiO6 octahedra. The corner-sharing octahedra tilt angles range from 2–71°. There are a spread of Li–O bond distances ranging from 1.99–2.06 Å. In the second Li1+ site, Li1+ is bonded to five O2- atoms to form LiO5 trigonal bipyramids that share corners with three TiO6 octahedra, corners with four LiO5 trigonal bipyramids, and edges with six TiO6 octahedra. The corner-sharing octahedra tilt angles range from 2–71°. There are a spread of Li–O bond distances ranging from 1.99–2.05 Å. In the third Li1+ site, Li1+ is bonded to five O2- atoms to form LiO5 trigonal bipyramids that share corners with three TiO6 octahedra, corners with four LiO5 trigonal bipyramids, and edges with six TiO6 octahedra. The corner-sharing octahedra tilt angles range from 0–74°. There are a spread of Li–O bond distances ranging from 1.97–2.04 Å. There are six inequivalent Ti+3.50+ sites. In the first Ti+3.50+ site, Ti+3.50+ is bonded to six O2- atoms to form TiO6 octahedra that share corners with four TiO6 octahedra, corners with two LiO5 trigonal bipyramids, edges with four TiO6 octahedra, and edges with two LiO5 trigonal bipyramids. The corner-sharing octahedra tilt angles range from 4–24°. There are a spread of Ti–O bond distances ranging from 1.94–2.12 Å. In the second Ti+3.50+ site, Ti+3.50+ is bonded to six O2- atoms to form TiO6 octahedra that share corners with four TiO6 octahedra, a cornercorner with one LiO5 trigonal bipyramid, edges with four TiO6 octahedra, and edges with four LiO5 trigonal bipyramids. The corner-sharing octahedra tilt angles range from 1–24°. There are a spread of Ti–O bond distances ranging from 1.95–2.14 Å. In the third Ti+3.50+ site, Ti+3.50+ is bonded to six O2- atoms to form TiO6 octahedra that share corners with four TiO6 octahedra, corners with two LiO5 trigonal bipyramids, edges with four TiO6 octahedra, and edges with two LiO5 trigonal bipyramids. The corner-sharing octahedra tilt angles range from 1–24°. There are a spread of Ti–O bond distances ranging from 1.95–2.14 Å. In the fourth Ti+3.50+ site, Ti+3.50+ is bonded to six O2- atoms to form TiO6 octahedra that share corners with four TiO6 octahedra, a cornercorner with one LiO5 trigonal bipyramid, edges with four TiO6 octahedra, and edges with four LiO5 trigonal bipyramids. The corner-sharing octahedra tilt angles range from 1–24°. There are a spread of Ti–O bond distances ranging from 1.95–2.11 Å. In the fifth Ti+3.50+ site, Ti+3.50+ is bonded to six O2- atoms to form TiO6 octahedra that share corners with four TiO6 octahedra, corners with two LiO5 trigonal bipyramids, edges with four TiO6 octahedra, and edges with two LiO5 trigonal bipyramids. The corner-sharing octahedra tilt angles range from 1–23°. There are a spread of Ti–O bond distances ranging from 1.93–2.15 Å. In the sixth Ti+3.50+ site, Ti+3.50+ is bonded to six O2- atoms to form TiO6 octahedra that share corners with four TiO6 octahedra, a cornercorner with one LiO5 trigonal bipyramid, edges with four TiO6 octahedra, and edges with four LiO5 trigonal bipyramids. The corner-sharing octahedra tilt angles range from 1–24°. There are a spread of Ti–O bond distances ranging from 1.96–2.21 Å. There are twelve inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted T-shaped geometry to three Ti+3.50+ atoms. In the second O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Li1+ and three Ti+3.50+ atoms. In the third O2- site, O2- is bonded to two Li1+ and three Ti+3.50+ atoms to form a mixture of corner and edge-sharing OLi2Ti3 trigonal bipyramids. In the fourth O2- site, O2- is bonded in a distorted T-shaped geometry to three Ti+3.50+ atoms. In the fifth O2- site, O2- is bonded to two Li1+ and three Ti+3.50+ atoms to form a mixture of corner and edge-sharing OLi2Ti3 trigonal bipyramids. In the sixth O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Li1+ and three Ti+3.50+ atoms. In the seventh O2- site, O2- is bonded to two Li1+ and three Ti+3.50+ atoms to form a mixture of corner and edge-sharing OLi2Ti3 trigonal bipyramids. In the eighth O2- site, O2- is bonded in a distorted T-shaped geometry to three Ti+3.50+ atoms. In the ninth O2- site, O2- is bonded to two Li1+ and three Ti+3.50+ atoms to form a mixture of corner and edge-sharing OLi2Ti3 trigonal bipyramids. In the tenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Li1+ and three Ti+3.50+ atoms. In the eleventh O2- site, O2- is bonded to two Li1+ and three Ti+3.50+ atoms to form a mixture of corner and edge-sharing OLi2Ti3 trigonal bipyramids. In the twelfth O2- site, O2- is bonded to two Li1+ and three Ti+3.50+ atoms to form a mixture of corner and edge-sharing OLi2Ti3 trigonal bipyramids.