DOE OSTI2020
Li4Co5Sb3O16 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 SbO6 octahedra and corners with eight CoO6 octahedra. The corner-sharing octahedra tilt angles range from 54–65°. There are a spread of Li–O bond distances ranging from 1.98–2.13 Å. In the second Li1+ site, Li1+ is bonded in a distorted rectangular see-saw-like geometry to four O2- atoms. There are a spread of Li–O bond distances ranging from 1.77–2.12 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 1.80–1.95 Å. In the fourth Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share corners with five SbO6 octahedra and corners with seven CoO6 octahedra. The corner-sharing octahedra tilt angles range from 58–65°. There are a spread of Li–O bond distances ranging from 1.98–2.05 Å. There are four inequivalent Co+2.60+ sites. In the first Co+2.60+ site, Co+2.60+ is bonded to six O2- atoms to form distorted CoO6 octahedra that share corners with two equivalent SbO6 octahedra, corners with four equivalent CoO6 octahedra, corners with three equivalent LiO4 tetrahedra, an edgeedge with one CoO6 octahedra, and edges with two equivalent SbO6 octahedra. The corner-sharing octahedra tilt angles range from 52–57°. There are a spread of Co–O bond distances ranging from 2.04–2.33 Å. In the second Co+2.60+ site, Co+2.60+ is bonded to six O2- atoms to form CoO6 octahedra that share corners with two equivalent CoO6 octahedra, corners with three LiO4 tetrahedra, an edgeedge with one CoO6 octahedra, and edges with four equivalent SbO6 octahedra. The corner-sharing octahedral tilt angles are 50°. There are a spread of Co–O bond distances ranging from 2.05–2.13 Å. In the third Co+2.60+ site, Co+2.60+ is bonded to six O2- atoms to form CoO6 octahedra that share corners with two equivalent CoO6 octahedra, corners with four equivalent SbO6 octahedra, corners with three equivalent LiO4 tetrahedra, an edgeedge with one SbO6 octahedra, and edges with two equivalent CoO6 octahedra. The corner-sharing octahedra tilt angles range from 50–54°. There are a spread of Co–O bond distances ranging from 2.09–2.30 Å. In the fourth Co+2.60+ site, Co+2.60+ is bonded to six O2- atoms to form CoO6 octahedra that share corners with two equivalent CoO6 octahedra, corners with three LiO4 tetrahedra, edges with two equivalent SbO6 octahedra, and edges with three CoO6 octahedra. The corner-sharing octahedra tilt angles range from 52–54°. There are a spread of Co–O bond distances ranging from 1.92–1.99 Å. There are two inequivalent Sb5+ sites. In the first Sb5+ site, Sb5+ is bonded to six O2- atoms to form SbO6 octahedra that share corners with two equivalent CoO6 octahedra, corners with three LiO4 tetrahedra, edges with two equivalent SbO6 octahedra, and edges with three CoO6 octahedra. The corner-sharing octahedra tilt angles range from 53–54°. There are a spread of Sb–O bond distances ranging from 1.97–2.04 Å. In the second Sb5+ site, Sb5+ is bonded to six O2- atoms to form SbO6 octahedra that share corners with two equivalent CoO6 octahedra, corners with three LiO4 tetrahedra, and edges with five CoO6 octahedra. The corner-sharing octahedral tilt angles are 57°. There are a spread of Sb–O bond distances ranging from 2.02–2.04 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+, two Co+2.60+, and one Sb5+ atom. In the second O2- site, O2- is bonded in a 4-coordinate geometry to one Li1+, one Co+2.60+, and two equivalent Sb5+ atoms. In the third O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Li1+, one Co+2.60+, and two equivalent Sb5+ atoms. In the fourth O2- site, O2- is bonded to one Li1+, one Co+2.60+, and two equivalent Sb5+ atoms to form distorted OLiCoSb2 trigonal pyramids that share corners with four equivalent OLiCo2Sb tetrahedra and a cornercorner with one OLiCo3 trigonal pyramid. In the fifth O2- site, O2- is bonded to one Li1+, two equivalent Co+2.60+, and one Sb5+ atom to form a mixture of distorted edge and corner-sharing OLiCo2Sb tetrahedra. In the sixth O2- site, O2- is bonded to one Li1+, two Co+2.60+, and one Sb5+ atom to form distorted OLiCo2Sb tetrahedra that share a cornercorner with one OLiCo2Sb tetrahedra, corners with three OLiCo3 trigonal pyramids, and an edgeedge with one OLiCo2Sb tetrahedra. In the seventh O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Li1+, one Co+2.60+, and two equivalent Sb5+ atoms. In the eighth O2- site, O2- is bonded to one Li1+ and three Co+2.60+ atoms to form distorted OLiCo3 trigonal pyramids that share corners with four OLiCo3 tetrahedra, a cornercorner with one OLiCoSb2 trigonal pyramid, and an edgeedge with one OLiCo2Sb tetrahedra. In the ninth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Li1+, two Co+2.60+, and one Sb5+ atom. In the tenth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Li1+, two equivalent Co+2.60+, and one Sb5+ atom. In the eleventh O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Li1+, two Co+2.60+, and one Sb5+ atom. In the twelfth O2- site, O2- is bonded to one Li1+ and three Co+2.60+ atoms to form distorted OLiCo3 tetrahedra that share corners with two equivalent OLiCo2Sb tetrahedra and corners with two equivalent OLiCo3 trigonal pyramids.