Materials Data on Li4Mn2Nb3V3O16 by Materials Project

Abstract

Li4Nb3V3Mn2O16 is Spinel-derived structured and crystallizes in the monoclinic Cm 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 four VO6 octahedra and corners with five NbO6 octahedra. The corner-sharing octahedra tilt angles range from 51–59°. There are a spread of Li–O bond distances ranging from 1.99–2.07 Å. In the second Li1+ site, Li1+ is bonded in a rectangular see-saw-like geometry to four O2- atoms. There are a spread of Li–O bond distances ranging from 1.86–1.96 Å. In the third Li1+ site, Li1+ is bonded in a rectangular see-saw-like geometry to four O2- atoms. There are a spread of Li–O bond distances ranging from 1.80–2.07 Å. In the fourth Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share corners with three equivalent MnO6 octahedra, corners with four NbO6 octahedra, and corners with five VO6 octahedra. The corner-sharing octahedra tilt angles range from 55–63°. There are a spread of Li–O bond distances ranging from 2.00–2.18 Å. There are two inequivalent Nb5+ sites. In the first Nb5+ site, Nb5+ is bonded to six O2- atoms to form NbO6 octahedra that share corners with three LiO4 tetrahedra, an edgeedge with one MnO6 octahedra, and edges with four equivalent VO6 octahedra. There are a spread of Nb–O bond distances ranging from 2.00–2.08 Å. In the second Nb5+ site, Nb5+ is bonded to six O2- atoms to form NbO6 octahedra that share corners with two equivalent MnO6 octahedra, corners with three LiO4 tetrahedra, edges with two equivalent NbO6 octahedra, and edges with two equivalent VO6 octahedra. The corner-sharing octahedral tilt angles are 54°. There are a spread of Nb–O bond distances ranging from 1.97–2.06 Å. There are two inequivalent V3+ sites. In the first V3+ site, V3+ is bonded to six O2- atoms to form VO6 octahedra that share corners with three LiO4 tetrahedra, an edgeedge with one MnO6 octahedra, edges with two equivalent NbO6 octahedra, and edges with two equivalent VO6 octahedra. There are a spread of V–O bond distances ranging from 2.00–2.11 Å. In the second V3+ site, V3+ is bonded to six O2- atoms to form VO6 octahedra that share corners with two equivalent MnO6 octahedra, corners with three LiO4 tetrahedra, and edges with four equivalent NbO6 octahedra. The corner-sharing octahedral tilt angles are 52°. There are a spread of V–O bond distances ranging from 2.02–2.13 Å. There are two inequivalent Mn2+ sites. In the first Mn2+ site, Mn2+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with two equivalent VO6 octahedra, corners with four equivalent NbO6 octahedra, corners with three equivalent LiO4 tetrahedra, an edgeedge with one NbO6 octahedra, and edges with two equivalent VO6 octahedra. The corner-sharing octahedra tilt angles range from 52–54°. There are a spread of Mn–O bond distances ranging from 2.19–2.28 Å. In the second Mn2+ site, Mn2+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Mn–O bond distances ranging from 2.09–2.50 Å. There are twelve inequivalent O2- sites. In the first O2- site, O2- is bonded to one Li1+, one Nb5+, one V3+, and one Mn2+ atom to form a mixture of distorted edge and corner-sharing OLiMnNbV trigonal pyramids. In the second O2- site, O2- is bonded to one Li1+, two equivalent V3+, and one Mn2+ atom to form distorted OLiMnV2 tetrahedra that share corners with two equivalent OLiNbV2 tetrahedra, corners with six OLiMnV2 trigonal pyramids, and edges with two equivalent OLiMnNbV trigonal pyramids. In the third O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Li1+, one Nb5+, and two equivalent V3+ atoms. In the fourth O2- site, O2- is bonded to one Li1+, one Nb5+, and two equivalent V3+ atoms to form distorted OLiNbV2 tetrahedra that share corners with two equivalent OLiMnV2 tetrahedra, corners with six OLiMnNbV trigonal pyramids, and an edgeedge with one OLiMnV2 trigonal pyramid. In the fifth O2- site, O2- is bonded to one Li1+, two equivalent Nb5+, and one V3+ atom to form distorted OLiNb2V trigonal pyramids that share corners with four equivalent OLiMnNbV tetrahedra, a cornercorner with one OLiMnV2 trigonal pyramid, and edges with two equivalent OLiMnNbV trigonal pyramids. In the sixth O2- site, O2- is bonded to one Li1+, one Nb5+, one V3+, and one Mn2+ atom to form distorted OLiMnNbV trigonal pyramids that share corners with three OLiMnV2 tetrahedra, corners with four OLiMnV2 trigonal pyramids, an edgeedge with one OLiMnV2 tetrahedra, and an edgeedge with one OLiMnNbV trigonal pyramid. In the seventh O2- site, O2- is bonded to one Li1+, two equivalent V3+, and one Mn2+ atom to form distorted OLiMnV2 trigonal pyramids that share corners with four OLiMnNbV tetrahedra, corners with three OLiNb2V trigonal pyramids, and an edgeedge with one OLiNbV2 tetrahedra. In the eighth O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Li1+, two equivalent Nb5+, and one Mn2+ atom. In the ninth O2- site, O2- is bonded to one Li1+, one Nb5+, one V3+, and one Mn2+ atom to form distorted OLiMnNbV tetrahedra that share a cornercorner with one OLiMnNbV tetrahedra, corners with six OLiMnV2 trigonal pyramids, and an edgeedge with one OLiMnNbV tetrahedra. In the tenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Li1+, two equivalent Nb5+, and one V3+ atom. In the eleventh O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Li1+, one Nb5+, one V3+, and one Mn2+ atom. In the twelfth O2- site, O2- is bonded in a 4-coordinate geometry to one Li1+, two equivalent Nb5+, and one Mn2+ atom.