DOE OSTI2020
Li9Nb7V12O48 crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are nine inequivalent Li1+ sites. In the first Li1+ site, Li1+ is bonded to six O2- atoms to form LiO6 octahedra that share corners with six VO4 tetrahedra and faces with two equivalent NbO6 octahedra. There are a spread of Li–O bond distances ranging from 2.05–2.17 Å. In the second Li1+ site, Li1+ is bonded to six O2- atoms to form LiO6 octahedra that share a cornercorner with one NbO6 octahedra, a cornercorner with one LiO6 pentagonal pyramid, corners with six VO4 tetrahedra, and edges with two equivalent NbO6 octahedra. The corner-sharing octahedral tilt angles are 61°. There are a spread of Li–O bond distances ranging from 2.05–2.31 Å. In the third Li1+ site, Li1+ is bonded to six O2- atoms to form distorted LiO6 octahedra that share a cornercorner with one LiO6 octahedra, a cornercorner with one NbO6 pentagonal pyramid, corners with six VO4 tetrahedra, and edges with two equivalent NbO6 octahedra. The corner-sharing octahedral tilt angles are 66°. There are a spread of Li–O bond distances ranging from 2.10–2.36 Å. In the fourth Li1+ site, Li1+ is bonded to six O2- atoms to form distorted LiO6 octahedra that share a cornercorner with one LiO6 octahedra, a cornercorner with one NbO6 pentagonal pyramid, corners with six VO4 tetrahedra, and edges with two equivalent NbO6 octahedra. The corner-sharing octahedral tilt angles are 66°. There are a spread of Li–O bond distances ranging from 2.10–2.34 Å. In the fifth Li1+ site, Li1+ is bonded to six O2- atoms to form distorted LiO6 pentagonal pyramids that share a cornercorner with one LiO6 octahedra, a cornercorner with one NbO6 octahedra, corners with six VO4 tetrahedra, and edges with two equivalent LiO6 pentagonal pyramids. The corner-sharing octahedra tilt angles range from 62–70°. There are a spread of Li–O bond distances ranging from 2.08–2.32 Å. In the sixth Li1+ site, Li1+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Li–O bond distances ranging from 2.08–2.48 Å. In the seventh Li1+ site, Li1+ is bonded to six O2- atoms to form distorted LiO6 octahedra that share a cornercorner with one NbO6 octahedra, corners with six VO4 tetrahedra, and edges with two equivalent NbO6 octahedra. The corner-sharing octahedral tilt angles are 58°. There are a spread of Li–O bond distances ranging from 2.07–2.36 Å. In the eighth Li1+ site, Li1+ is bonded to six O2- atoms to form distorted LiO6 pentagonal pyramids that share corners with two NbO6 octahedra, corners with six VO4 tetrahedra, and edges with two equivalent LiO6 pentagonal pyramids. The corner-sharing octahedra tilt angles range from 59–61°. There are a spread of Li–O bond distances ranging from 2.08–2.31 Å. In the ninth Li1+ site, Li1+ is bonded to six O2- atoms to form LiO6 octahedra that share corners with six VO4 tetrahedra and faces with two equivalent NbO6 octahedra. There are a spread of Li–O bond distances ranging from 2.09–2.19 Å. There are seven inequivalent Nb5+ sites. In the first Nb5+ site, Nb5+ is bonded to six O2- atoms to form distorted NbO6 pentagonal pyramids that share corners with two LiO6 octahedra and corners with six VO4 tetrahedra. The corner-sharing octahedral tilt angles are 63°. There are a spread of Nb–O bond distances ranging from 1.96–2.13 Å. In the second Nb5+ site, Nb5+ is bonded to six O2- atoms to form NbO6 octahedra that share a cornercorner with one LiO6 octahedra, a cornercorner with one LiO6 pentagonal pyramid, corners with six VO4 tetrahedra, and edges with two equivalent LiO6 octahedra. The corner-sharing octahedral tilt angles are 61°. There are a spread of Nb–O bond distances ranging from 1.89–2.21 Å. In the third Nb5+ site, Nb5+ is bonded to six O2- atoms to form NbO6 octahedra that share corners with six VO4 tetrahedra and faces with two equivalent LiO6 octahedra. There are a spread of Nb–O bond distances ranging from 1.94–2.09 Å. In the fourth Nb5+ site, Nb5+ is bonded to six O2- atoms to form NbO6 octahedra that share corners with six VO4 tetrahedra and faces with two equivalent LiO6 octahedra. There are a spread of Nb–O bond distances ranging from 1.89–2.09 Å. In the fifth Nb5+ site, Nb5+ is bonded to six O2- atoms to form NbO6 octahedra that share a cornercorner with one NbO6 octahedra, a cornercorner with one LiO6 pentagonal pyramid, corners with six VO4 tetrahedra, and edges with two equivalent LiO6 octahedra. The corner-sharing octahedral tilt angles are 51°. There are a spread of Nb–O bond distances ranging from 1.89–2.11 Å. In the sixth Nb5+ site, Nb5+ is bonded to six O2- atoms to form NbO6 octahedra that share a cornercorner with one NbO6 octahedra, a cornercorner with one LiO6 pentagonal pyramid, corners with six VO4 tetrahedra, and edges with two equivalent LiO6 octahedra. The corner-sharing octahedral tilt angles are 51°. There are a spread of Nb–O bond distances ranging from 1.89–2.10 Å. In the seventh Nb5+ site, Nb5+ is bonded to six O2- atoms to form NbO6 octahedra that share a cornercorner with one LiO6 octahedra, corners with six VO4 tetrahedra, and edges with two equivalent LiO6 octahedra. The corner-sharing octahedral tilt angles are 58°. There are a spread of Nb–O bond distances ranging from 1.90–2.22 Å. There are twelve inequivalent V+4.33+ sites. In the first V+4.33+ site, V+4.33+ is bonded to four O2- atoms to form VO4 tetrahedra that share corners with four LiO6 octahedra and corners with four NbO6 octahedra. The corner-sharing octahedra tilt angles range from 31–64°. There are a spread of V–O bond distances ranging from 1.75–1.90 Å. In the second V+4.33+ site, V+4.33+ is bonded to four O2- atoms to form VO4 tetrahedra that share corners with two LiO6 octahedra, corners with three NbO6 octahedra, and corners with three LiO6 pentagonal pyramids. The corner-sharing octahedra tilt angles range from 32–61°. There are a spread of V–O bond distances ranging from 1.67–1.82 Å. In the third V+4.33+ site, V+4.33+ is bonded to four O2- atoms to form VO4 tetrahedra that share corners with two LiO6 octahedra, corners with three NbO6 octahedra, and corners with three LiO6 pentagonal pyramids. The corner-sharing octahedra tilt angles range from 33–60°. There are a spread of V–O bond distances ranging from 1.65–1.81 Å. In the fourth V+4.33+ site, V+4.33+ is bonded to four O2- atoms to form VO4 tetrahedra that share corners with two LiO6 octahedra, corners with three NbO6 octahedra, and a cornercorner with one NbO6 pentagonal pyramid. The corner-sharing octahedra tilt angles range from 23–62°. There are a spread of V–O bond distances ranging from 1.89–1.93 Å. In the fifth V+4.33+ site, V+4.33+ is bonded to four O2- atoms to form VO4 tetrahedra that share corners with two NbO6 octahedra, corners with three LiO6 octahedra, and a cornercorner with one NbO6 pentagonal pyramid. The corner-sharing octahedra tilt angles range from 21–56°. There are a spread of V–O bond distances ranging from 1.68–1.79 Å. In the sixth V+4.33+ site, V+4.33+ is bonded to four O2- atoms to form VO4 tetrahedra that share corners with three LiO6 octahedra and corners with five NbO6 octahedra. The corner-sharing octahedra tilt angles range from 23–68°. There are a spread of V–O bond distances ranging from 1.86–1.99 Å. In the seventh V+4.33+ site, V+4.33+ is bonded to four O2- atoms to form VO4 tetrahedra that share corners with three NbO6 octahedra and corners with five LiO6 octahedra. The corner-sharing octahedra tilt angles range from 20–58°. There are a spread of V–O bond distances ranging from 1.69–1.78 Å. In the eighth V+4.33+ site, V+4.33+ is bonded to four O2- atoms to form VO4 tetrahedra that share corners with two NbO6 octahedra, corners with three LiO6 octahedra, and corners with three LiO6 pentagonal pyramids. The corner-sharing octahedra tilt angles range from 25–57°. There are a spread of V–O bond distances ranging from 1.68–1.86 Å. In the ninth V+4.33+ site, V+4.33+ is bonded to four O2- atoms to form VO4 tetrahedra that share corners with two LiO6 octahedra, corners with three NbO6 octahedra, and corners with three LiO6 pentagonal pyramids. The corner-sharing octahedra tilt angles range from 27–60°. There are a spread of V–O bond distances ranging from 1.66–1.95 Å. In the tenth V+4.33+ site, V+4.33+ is bonded to four O2- atoms to form VO4 tetrahedra that share corners with two NbO6 octahedra, corners with three LiO6 octahedra, and corners with two equivalent NbO6 pentagonal pyramids. The corner-sharing octahedra tilt angles range from 31–59°. There are a spread of V–O bond distances ranging from 1.79–1.89 Å. In the eleventh V+4.33+ site, V+4.33+ is bonded to four O2- atoms to form VO4 tetrahedra that share corners with two NbO6 octahedra, corners with three LiO6 octahedra, and corners with two equivalent NbO6 pentagonal pyramids. The corner-sharing octahedra tilt angles range from 30–60°. There are a spread of V–O bond distances ranging from 1.78–1.90 Å. In the twelfth V+4.33+ site, V+4.33+ is bonded to four O2- atoms to form VO4 tetrahedra that share corners with four LiO6 octahedra and corners with four NbO6 octahedra. The corner-sharing octahedra tilt angles range from 28–64°. There are a spread of V–O bond distances ranging from 1.72–1.80 Å. There are forty-eight inequivalent O2- sites. In the first O2- site, O2- is bonded in a trigonal planar geometry to one Li1+, one Nb5+, and one V+4.33+ atom. In the second O2- site, O2- is bonded in a trigonal planar geometry to one Li1+, one Nb5+, and one V+4.33+ atom. In the third O2- site, O2- is bonded in a trigonal planar geometry to one Li1+, one Nb5+, and one V+4.33+ atom. In the fourth O2- site, O2- is bonded in a distorted trigonal planar geometry to one Li1+, one Nb5+, and one V+4.33+ atom. In the fifth O2- site, O2- is bonded in a 3-coordinate geometry to one Li1+, one Nb5+, and one V+4.33+ atom. In the sixth O2- site, O2- is bonded in a 3-coordinate geometry to one Li1+, one Nb5+, and one V+4.33+ atom. In the seventh O2- site, O2- is bonded in a 3-coordinate geometry to one Li1+, one Nb5+, and one V+4.33+ atom. In the eighth O2- site, O2- is bonded in a 3-coordinate geometry to one Li1+, one Nb5+, and one V+4.33+ atom. In the ninth O2- site, O2- is bonded in a distorted trigonal planar geometry to one Li1+, one Nb5+, and one V+4.33+ atom. In the tenth O2- site, O2- is bonded in a 3-coordinate geometry to one Li1+, one Nb5+, and one V+4.33+ atom. In the eleventh O2- site, O2- is bonded in a 3-coordinate geometry to one Li1+, one Nb5+, and one V+4.33+ atom. In the twelfth O2- site, O2- is bonded in a 3-coordinate geometry to one Li1+, one Nb5+, and one V+4.33+ atom. In the thirteenth O2- site, O2- is bonded in a 3-coordinate geometry to one Li1+, one Nb5+, and one V+4.33+ atom. In the fourteenth O2- site, O2- is bonded in a 3-coordinate geometry to one Li1+, one Nb5+, and one V+4.33+ atom. In the fifteenth O2- site, O2- is bonded in a 3-coordinate geometry to one Li1+, one Nb5+, and one V+4.33+ atom. In the sixteenth O2- site, O2- is bonded in a 3-coordinate geometry to one Li1+, one Nb5+, and one V+4.33+ atom. In the seventeenth O2- site, O2- is bonded in a 3-coordinate geometry to one Li1+, one Nb5+, and one V+4.33+ atom. In the eighteenth O2- site, O2- is bonded in a trigonal planar geometry to one Li1+, one Nb5+, and one V+4.33+ atom. In the nineteenth O2- site, O2- is bonded in a 3-coordinate geometry to one Li1+, one Nb5+, and one V+4.33+ atom. In the twentieth O2- site, O2- is bonded in a 3-coordinate geometry to two Li1+ and one V+4.33+ atom. In the twenty-first O2- site, O2- is bonded in a 3-coordinate geometry to two Li1+ and one V+4.33+ atom. In the twenty-second O2- site, O2- is bonded in a distorted trigonal planar geometry to one Li1+, one Nb5+, and one V+4.33+ atom. In the twenty-third O2- site, O2- is bonded in a trigonal planar geometry to two Li1+ and one V+4.33+ atom. In the twenty-fourth O2- site, O2- is bonded in a tri