DOE OSTI2020
Li2FeV3O8 is Spinel-derived structured and crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are eight inequivalent Li1+ sites. In the first Li1+ site, Li1+ is bonded to six O2- atoms to form LiO6 octahedra that share corners with three LiO4 tetrahedra, corners with three FeO4 tetrahedra, and edges with six VO6 octahedra. There are a spread of Li–O bond distances ranging from 2.14–2.20 Å. In the second Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share corners with three LiO6 octahedra and corners with nine VO6 octahedra. The corner-sharing octahedra tilt angles range from 49–66°. There are a spread of Li–O bond distances ranging from 1.98–2.00 Å. In the third Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share corners with three LiO6 octahedra and corners with nine VO6 octahedra. The corner-sharing octahedra tilt angles range from 51–67°. All Li–O bond lengths are 1.98 Å. In the fourth Li1+ site, Li1+ is bonded to six O2- atoms to form LiO6 octahedra that share corners with three LiO4 tetrahedra, corners with three FeO4 tetrahedra, and edges with six VO6 octahedra. There are a spread of Li–O bond distances ranging from 2.12–2.19 Å. In the fifth Li1+ site, Li1+ is bonded to six O2- atoms to form LiO6 octahedra that share corners with three LiO4 tetrahedra, corners with three FeO4 tetrahedra, and edges with six VO6 octahedra. There are a spread of Li–O bond distances ranging from 2.14–2.19 Å. In the sixth Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share corners with three LiO6 octahedra and corners with nine VO6 octahedra. The corner-sharing octahedra tilt angles range from 49–66°. There are a spread of Li–O bond distances ranging from 1.98–2.00 Å. In the seventh Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share corners with three LiO6 octahedra and corners with nine VO6 octahedra. The corner-sharing octahedra tilt angles range from 51–67°. All Li–O bond lengths are 1.98 Å. In the eighth Li1+ site, Li1+ is bonded to six O2- atoms to form LiO6 octahedra that share corners with three LiO4 tetrahedra, corners with three FeO4 tetrahedra, and edges with six VO6 octahedra. There are a spread of Li–O bond distances ranging from 2.11–2.19 Å. There are twelve inequivalent V4+ sites. In the first V4+ site, V4+ is bonded to six O2- atoms to form VO6 octahedra that share corners with three LiO4 tetrahedra, corners with three FeO4 tetrahedra, edges with two LiO6 octahedra, and edges with four VO6 octahedra. There are a spread of V–O bond distances ranging from 1.80–2.09 Å. In the second V4+ site, V4+ is bonded to six O2- atoms to form VO6 octahedra that share corners with three LiO4 tetrahedra, corners with three FeO4 tetrahedra, edges with two LiO6 octahedra, and edges with four VO6 octahedra. There are a spread of V–O bond distances ranging from 1.81–2.10 Å. In the third V4+ site, V4+ is bonded to six O2- atoms to form VO6 octahedra that share corners with three LiO4 tetrahedra, corners with three FeO4 tetrahedra, edges with two LiO6 octahedra, and edges with four VO6 octahedra. There are a spread of V–O bond distances ranging from 1.79–2.10 Å. In the fourth V4+ site, V4+ is bonded to six O2- atoms to form VO6 octahedra that share corners with three LiO4 tetrahedra, corners with three FeO4 tetrahedra, edges with two LiO6 octahedra, and edges with four VO6 octahedra. There are a spread of V–O bond distances ranging from 2.00–2.08 Å. In the fifth V4+ site, V4+ is bonded to six O2- atoms to form VO6 octahedra that share corners with three LiO4 tetrahedra, corners with three FeO4 tetrahedra, edges with two LiO6 octahedra, and edges with four VO6 octahedra. There are a spread of V–O bond distances ranging from 2.01–2.07 Å. In the sixth V4+ site, V4+ is bonded to six O2- atoms to form VO6 octahedra that share corners with three LiO4 tetrahedra, corners with three FeO4 tetrahedra, edges with two LiO6 octahedra, and edges with four VO6 octahedra. There are a spread of V–O bond distances ranging from 1.82–2.09 Å. In the seventh V4+ site, V4+ is bonded to six O2- atoms to form VO6 octahedra that share corners with three LiO4 tetrahedra, corners with three FeO4 tetrahedra, edges with two LiO6 octahedra, and edges with four VO6 octahedra. There are a spread of V–O bond distances ranging from 1.80–2.09 Å. In the eighth V4+ site, V4+ is bonded to six O2- atoms to form VO6 octahedra that share corners with three LiO4 tetrahedra, corners with three FeO4 tetrahedra, edges with two LiO6 octahedra, and edges with four VO6 octahedra. There are a spread of V–O bond distances ranging from 1.81–2.10 Å. In the ninth V4+ site, V4+ is bonded to six O2- atoms to form VO6 octahedra that share corners with three LiO4 tetrahedra, corners with three FeO4 tetrahedra, edges with two LiO6 octahedra, and edges with four VO6 octahedra. There are a spread of V–O bond distances ranging from 1.79–2.10 Å. In the tenth V4+ site, V4+ is bonded to six O2- atoms to form VO6 octahedra that share corners with three LiO4 tetrahedra, corners with three FeO4 tetrahedra, edges with two LiO6 octahedra, and edges with four VO6 octahedra. There are a spread of V–O bond distances ranging from 2.00–2.08 Å. In the eleventh V4+ site, V4+ is bonded to six O2- atoms to form VO6 octahedra that share corners with three LiO4 tetrahedra, corners with three FeO4 tetrahedra, edges with two LiO6 octahedra, and edges with four VO6 octahedra. There are a spread of V–O bond distances ranging from 2.01–2.07 Å. In the twelfth V4+ site, V4+ is bonded to six O2- atoms to form VO6 octahedra that share corners with three LiO4 tetrahedra, corners with three FeO4 tetrahedra, edges with two LiO6 octahedra, and edges with four VO6 octahedra. There are a spread of V–O bond distances ranging from 1.82–2.09 Å. There are four inequivalent Fe2+ sites. In the first Fe2+ site, Fe2+ is bonded to four O2- atoms to form FeO4 tetrahedra that share corners with three LiO6 octahedra and corners with nine VO6 octahedra. The corner-sharing octahedra tilt angles range from 52–63°. There are a spread of Fe–O bond distances ranging from 1.92–1.96 Å. In the second Fe2+ site, Fe2+ is bonded to four O2- atoms to form FeO4 tetrahedra that share corners with three LiO6 octahedra and corners with nine VO6 octahedra. The corner-sharing octahedra tilt angles range from 54–63°. There are a spread of Fe–O bond distances ranging from 1.92–1.95 Å. In the third Fe2+ site, Fe2+ is bonded to four O2- atoms to form FeO4 tetrahedra that share corners with three LiO6 octahedra and corners with nine VO6 octahedra. The corner-sharing octahedra tilt angles range from 52–63°. There are a spread of Fe–O bond distances ranging from 1.92–1.96 Å. In the fourth Fe2+ site, Fe2+ is bonded to four O2- atoms to form FeO4 tetrahedra that share corners with three LiO6 octahedra and corners with nine VO6 octahedra. The corner-sharing octahedra tilt angles range from 54–64°. There are a spread of Fe–O bond distances ranging from 1.92–1.95 Å. There are thirty-two inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two Li1+ and two V4+ atoms. In the second O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Li1+ and two V4+ atoms. In the third O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Li1+ and three V4+ atoms. In the fourth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two Li1+ and two V4+ atoms. In the fifth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Li1+, two V4+, and one Fe2+ atom. In the sixth O2- site, O2- is bonded to three V4+ and one Fe2+ atom to form a mixture of distorted edge and corner-sharing OV3Fe trigonal pyramids. In the seventh O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Li1+, two V4+, and one Fe2+ atom. In the eighth O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Li1+, two V4+, and one Fe2+ atom. In the ninth O2- site, O2- is bonded to one Li1+, two V4+, and one Fe2+ atom to form a mixture of distorted edge and corner-sharing OLiV2Fe trigonal pyramids. In the tenth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Li1+, two V4+, and one Fe2+ atom. In the eleventh O2- site, O2- is bonded in a rectangular see-saw-like geometry to three V4+ and one Fe2+ atom. In the twelfth O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Li1+, two V4+, and one Fe2+ atom. In the thirteenth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two Li1+ and two V4+ atoms. In the fourteenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Li1+ and three V4+ atoms. In the fifteenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Li1+ and two V4+ atoms. In the sixteenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Li1+ and two V4+ atoms. In the seventeenth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two Li1+ and two V4+ atoms. In the eighteenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Li1+ and two V4+ atoms. In the nineteenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Li1+ and three V4+ atoms. In the twentieth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two Li1+ and two V4+ atoms. In the twenty-first O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Li1+, two V4+, and one Fe2+ atom. In the twenty-second O2- site, O2- is bonded to three V4+ and one Fe2+ atom to form a mixture of distorted edge and corner-sharing OV3Fe trigonal pyramids. In the twenty-third O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Li1+, two V4+, and one Fe2+ atom. In the twenty-fourth O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Li1+, two V4+, and one Fe2+ atom. In the twenty-fifth O2- site, O2- is bonded to one Li1+, two V4+, and one Fe2+ atom to form a mixture of distorted edge and corner-sharing OLiV2Fe trigonal pyramids. In the twenty-sixth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Li1+, two V4+, and one Fe2+ atom. In the twenty-seventh O2- site, O2- is bonded in a rectangular see-saw-like geometry to three V4+ and one Fe2+ atom. In the twenty-eighth O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Li1+, two V4+, and one Fe2+ atom. In the twenty-ninth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two Li1+ and two V4+ atoms. In the thirtieth O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Li1+ and three V4+ atoms. In the thirty-first O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Li1+ and two V4+ atoms. In the thirty-second O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Li1+ and two V4+ atoms.