DOE OSTI2020
Li4Cr2Ni3Sb3O16 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 trigonal pyramids that share corners with three equivalent CrO6 octahedra, corners with four SbO6 octahedra, and corners with five NiO6 octahedra. The corner-sharing octahedra tilt angles range from 47–66°. There are a spread of Li–O bond distances ranging from 1.96–2.14 Å. In the second Li1+ site, Li1+ is bonded to four O2- atoms to form distorted LiO4 trigonal pyramids that share a cornercorner with one SbO6 octahedra, corners with two equivalent NiO6 octahedra, corners with three equivalent CrO6 octahedra, an edgeedge with one NiO6 octahedra, and edges with two equivalent SbO6 octahedra. The corner-sharing octahedra tilt angles range from 56–70°. There are a spread of Li–O bond distances ranging from 1.77–2.18 Å. In the third Li1+ site, Li1+ is bonded to four O2- atoms to form distorted LiO4 tetrahedra that share a cornercorner with one NiO6 octahedra, corners with two equivalent SbO6 octahedra, corners with three equivalent CrO6 octahedra, an edgeedge with one SbO6 octahedra, and edges with two equivalent NiO6 octahedra. The corner-sharing octahedra tilt angles range from 54–68°. There are a spread of Li–O bond distances ranging from 1.83–2.00 Å. In the fourth Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share corners with three equivalent CrO6 octahedra, corners with four NiO6 octahedra, and corners with five SbO6 octahedra. The corner-sharing octahedra tilt angles range from 58–62°. There are a spread of Li–O bond distances ranging from 1.94–2.08 Å. There are two inequivalent Cr+4.50+ sites. In the first Cr+4.50+ site, Cr+4.50+ is bonded to six O2- atoms to form distorted CrO6 octahedra that share corners with two equivalent SbO6 octahedra, corners with four equivalent NiO6 octahedra, corners with six LiO4 tetrahedra, an edgeedge with one NiO6 octahedra, and edges with two equivalent SbO6 octahedra. The corner-sharing octahedra tilt angles range from 51–53°. There are a spread of Cr–O bond distances ranging from 1.92–2.21 Å. In the second Cr+4.50+ site, Cr+4.50+ is bonded to six O2- atoms to form CrO6 octahedra that share corners with two equivalent NiO6 octahedra, corners with four equivalent SbO6 octahedra, corners with six LiO4 trigonal pyramids, an edgeedge with one SbO6 octahedra, and edges with two equivalent NiO6 octahedra. The corner-sharing octahedra tilt angles range from 51–52°. There are a spread of Cr–O bond distances ranging from 1.93–2.33 Å. There are two inequivalent Ni2+ sites. In the first Ni2+ site, Ni2+ is bonded to six O2- atoms to form NiO6 octahedra that share corners with two equivalent CrO6 octahedra, corners with three LiO4 tetrahedra, a cornercorner with one LiO4 trigonal pyramid, an edgeedge with one CrO6 octahedra, edges with four equivalent SbO6 octahedra, and an edgeedge with one LiO4 trigonal pyramid. The corner-sharing octahedral tilt angles are 51°. There are a spread of Ni–O bond distances ranging from 2.04–2.12 Å. In the second Ni2+ site, Ni2+ is bonded to six O2- atoms to form NiO6 octahedra that share corners with two equivalent CrO6 octahedra, a cornercorner with one LiO4 tetrahedra, corners with three LiO4 trigonal pyramids, an edgeedge with one CrO6 octahedra, edges with two equivalent NiO6 octahedra, edges with two equivalent SbO6 octahedra, and an edgeedge with one LiO4 tetrahedra. The corner-sharing octahedra tilt angles range from 52–53°. There are a spread of Ni–O bond distances ranging from 1.97–2.16 Å. There are two inequivalent Sb+4.33+ sites. In the first Sb+4.33+ site, Sb+4.33+ is bonded to six O2- atoms to form SbO6 octahedra that share corners with two equivalent CrO6 octahedra, corners with three LiO4 tetrahedra, a cornercorner with one LiO4 trigonal pyramid, an edgeedge with one CrO6 octahedra, edges with two equivalent NiO6 octahedra, edges with two equivalent SbO6 octahedra, and an edgeedge with one LiO4 trigonal pyramid. The corner-sharing octahedra tilt angles range from 51–52°. There are a spread of Sb–O bond distances ranging from 1.97–2.06 Å. In the second Sb+4.33+ site, Sb+4.33+ is bonded to six O2- atoms to form SbO6 octahedra that share corners with two equivalent CrO6 octahedra, a cornercorner with one LiO4 tetrahedra, corners with three LiO4 trigonal pyramids, an edgeedge with one CrO6 octahedra, edges with four equivalent NiO6 octahedra, and an edgeedge with one LiO4 tetrahedra. The corner-sharing octahedral tilt angles are 51°. There are a spread of Sb–O bond distances ranging from 1.99–2.03 Å. There are twelve inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Li1+, one Cr+4.50+, one Ni2+, and one Sb+4.33+ atom. In the second O2- site, O2- is bonded to one Li1+, one Cr+4.50+, and two equivalent Sb+4.33+ atoms to form distorted OLiCrSb2 trigonal pyramids that share corners with four OLiNiSb2 tetrahedra, a cornercorner with one OLiNi2Sb trigonal pyramid, and edges with two equivalent OLiCrNiSb tetrahedra. In the third O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Li1+, one Ni2+, and two equivalent Sb+4.33+ atoms. In the fourth O2- site, O2- is bonded to one Li1+, one Ni2+, and two equivalent Sb+4.33+ atoms to form distorted OLiNiSb2 tetrahedra that share corners with four equivalent OLiCrNiSb tetrahedra and corners with two equivalent OLiCrSb2 trigonal pyramids. In the fifth O2- site, O2- is bonded to one Li1+, two equivalent Ni2+, and one Sb+4.33+ atom to form distorted OLiNi2Sb tetrahedra that share corners with two equivalent OLiCrNi2 tetrahedra and corners with three equivalent OLiNi2Sb trigonal pyramids. In the sixth O2- site, O2- is bonded to one Li1+, one Cr+4.50+, one Ni2+, and one Sb+4.33+ atom to form distorted OLiCrNiSb tetrahedra that share corners with three OLiNiSb2 tetrahedra, corners with two OLiNi2Sb trigonal pyramids, an edgeedge with one OLiCrNiSb tetrahedra, and an edgeedge with one OLiCrSb2 trigonal pyramid. In the seventh O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Li1+, one Cr+4.50+, and two equivalent Sb+4.33+ atoms. In the eighth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Li1+, one Cr+4.50+, and two equivalent Ni2+ atoms. In the ninth O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Li1+, one Cr+4.50+, one Ni2+, and one Sb+4.33+ atom. In the tenth O2- site, O2- is bonded to one Li1+, two equivalent Ni2+, and one Sb+4.33+ atom to form distorted OLiNi2Sb trigonal pyramids that share corners with five OLiNi2Sb tetrahedra, a cornercorner with one OLiCrSb2 trigonal pyramid, and an edgeedge with one OLiCrNi2 tetrahedra. In the eleventh O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Li1+, one Cr+4.50+, one Ni2+, and one Sb+4.33+ atom. In the twelfth O2- site, O2- is bonded to one Li1+, one Cr+4.50+, and two equivalent Ni2+ atoms to form a mixture of distorted corner and edge-sharing OLiCrNi2 tetrahedra.