DOE OSTI2020
Li2TiV3O8 is Spinel-derived structured and crystallizes in the monoclinic P2_1 space group. The structure is three-dimensional. there are four inequivalent Li1+ sites. In the first Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share corners with three TiO6 octahedra and corners with nine VO6 octahedra. The corner-sharing octahedra tilt angles range from 56–63°. There are a spread of Li–O bond distances ranging from 1.99–2.02 Å. In the second Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share corners with three TiO6 octahedra and corners with nine VO6 octahedra. The corner-sharing octahedra tilt angles range from 54–63°. There are two shorter (2.00 Å) and two longer (2.02 Å) Li–O bond lengths. In the third Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share corners with three TiO6 octahedra and corners with nine VO6 octahedra. The corner-sharing octahedra tilt angles range from 56–63°. There are a spread of Li–O bond distances ranging from 1.99–2.03 Å. In the fourth Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share corners with three TiO6 octahedra and corners with nine VO6 octahedra. The corner-sharing octahedra tilt angles range from 55–62°. There are two shorter (2.00 Å) and two longer (2.02 Å) Li–O bond lengths. There are two inequivalent Ti4+ sites. In the first Ti4+ site, Ti4+ is bonded to six O2- atoms to form TiO6 octahedra that share corners with six LiO4 tetrahedra and edges with six VO6 octahedra. There are a spread of Ti–O bond distances ranging from 1.93–2.06 Å. In the second Ti4+ site, Ti4+ is bonded to six O2- atoms to form TiO6 octahedra that share corners with six LiO4 tetrahedra and edges with six VO6 octahedra. There are a spread of Ti–O bond distances ranging from 1.92–2.06 Å. There are six inequivalent V+3.33+ sites. In the first V+3.33+ site, V+3.33+ is bonded to six O2- atoms to form VO6 octahedra that share corners with six LiO4 tetrahedra, edges with two equivalent TiO6 octahedra, and edges with four VO6 octahedra. There are a spread of V–O bond distances ranging from 1.95–2.01 Å. In the second V+3.33+ site, V+3.33+ is bonded to six O2- atoms to form VO6 octahedra that share corners with six LiO4 tetrahedra, edges with two TiO6 octahedra, and edges with four VO6 octahedra. There are a spread of V–O bond distances ranging from 2.04–2.09 Å. In the third V+3.33+ site, V+3.33+ is bonded to six O2- atoms to form VO6 octahedra that share corners with six LiO4 tetrahedra, edges with two TiO6 octahedra, and edges with four VO6 octahedra. There are a spread of V–O bond distances ranging from 2.03–2.07 Å. In the fourth V+3.33+ site, V+3.33+ is bonded to six O2- atoms to form VO6 octahedra that share corners with six LiO4 tetrahedra, edges with two equivalent TiO6 octahedra, and edges with four VO6 octahedra. There are a spread of V–O bond distances ranging from 1.94–2.00 Å. In the fifth V+3.33+ site, V+3.33+ is bonded to six O2- atoms to form VO6 octahedra that share corners with six LiO4 tetrahedra, edges with two TiO6 octahedra, and edges with four VO6 octahedra. There are a spread of V–O bond distances ranging from 2.03–2.10 Å. In the sixth V+3.33+ site, V+3.33+ is bonded to six O2- atoms to form VO6 octahedra that share corners with six LiO4 tetrahedra, edges with two TiO6 octahedra, and edges with four VO6 octahedra. There are a spread of V–O bond distances ranging from 2.03–2.08 Å. There are sixteen inequivalent O2- sites. In the first O2- site, O2- is bonded to one Li1+, one Ti4+, and two V+3.33+ atoms to form distorted OLiTiV2 trigonal pyramids that share corners with six OLiV3 trigonal pyramids and an edgeedge with one OLiTiV2 trigonal pyramid. In the second O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Li1+, one Ti4+, and two V+3.33+ atoms. In the third O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Li1+ and three V+3.33+ atoms. In the fourth O2- site, O2- is bonded to one Li1+, one Ti4+, and two V+3.33+ atoms to form a mixture of distorted edge and corner-sharing OLiTiV2 trigonal pyramids. In the fifth O2- site, O2- is bonded to one Li1+, one Ti4+, and two V+3.33+ atoms to form a mixture of distorted edge and corner-sharing OLiTiV2 trigonal pyramids. In the sixth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Li1+ and three V+3.33+ atoms. In the seventh O2- site, O2- is bonded to one Li1+, one Ti4+, and two V+3.33+ atoms to form a mixture of distorted edge and corner-sharing OLiTiV2 trigonal pyramids. In the eighth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Li1+, one Ti4+, and two V+3.33+ atoms. In the ninth O2- site, O2- is bonded to one Li1+, one Ti4+, and two V+3.33+ atoms to form a mixture of distorted edge and corner-sharing OLiTiV2 trigonal pyramids. In the tenth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Li1+, one Ti4+, and two V+3.33+ atoms. In the eleventh O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Li1+ and three V+3.33+ atoms. In the twelfth O2- site, O2- is bonded to one Li1+, one Ti4+, and two V+3.33+ atoms to form distorted OLiTiV2 trigonal pyramids that share corners with five OLiTiV2 trigonal pyramids and edges with two OLiV3 trigonal pyramids. In the thirteenth O2- site, O2- is bonded to one Li1+, one Ti4+, and two V+3.33+ atoms to form a mixture of distorted edge and corner-sharing OLiTiV2 trigonal pyramids. In the fourteenth O2- site, O2- is bonded to one Li1+ and three V+3.33+ atoms to form a mixture of distorted edge and corner-sharing OLiV3 trigonal pyramids. In the fifteenth O2- site, O2- is bonded to one Li1+, one Ti4+, and two V+3.33+ atoms to form a mixture of distorted edge and corner-sharing OLiTiV2 trigonal pyramids. In the sixteenth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Li1+, one Ti4+, and two V+3.33+ atoms.