Materials Data on Li4CoO4 by Materials Project

Abstract

Li4CoO4 crystallizes in the monoclinic Pc space group. The structure is three-dimensional. there are sixteen inequivalent Li1+ sites. In the first Li1+ site, Li1+ is bonded to four O2- atoms to form distorted LiO4 tetrahedra that share corners with two CoO4 tetrahedra, corners with five LiO4 tetrahedra, corners with three LiO4 trigonal pyramids, an edgeedge with one LiO4 tetrahedra, and an edgeedge with one CoO4 tetrahedra. There are a spread of Li–O bond distances ranging from 1.97–2.05 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 1.90–2.51 Å. In the third Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share corners with two CoO4 tetrahedra, corners with four LiO4 tetrahedra, corners with two LiO4 trigonal pyramids, an edgeedge with one CoO4 tetrahedra, edges with two LiO4 tetrahedra, and an edgeedge with one LiO4 trigonal pyramid. There are a spread of Li–O bond distances ranging from 1.91–2.04 Å. In the fourth Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share corners with four LiO4 tetrahedra, corners with four CoO4 tetrahedra, corners with three LiO4 trigonal pyramids, and edges with two LiO4 tetrahedra. There are a spread of Li–O bond distances ranging from 1.92–2.12 Å. In the fifth Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 trigonal pyramids that share corners with two CoO4 tetrahedra, corners with six LiO4 tetrahedra, a cornercorner with one LiO4 trigonal pyramid, an edgeedge with one LiO4 tetrahedra, and an edgeedge with one CoO4 tetrahedra. There are a spread of Li–O bond distances ranging from 1.91–2.28 Å. In the sixth Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share corners with two equivalent CoO4 tetrahedra, corners with four LiO4 tetrahedra, corners with two LiO4 trigonal pyramids, an edgeedge with one CoO4 tetrahedra, edges with two LiO4 tetrahedra, and an edgeedge with one LiO4 trigonal pyramid. There are a spread of Li–O bond distances ranging from 1.93–2.03 Å. In the seventh Li1+ site, Li1+ is bonded to four O2- atoms to form distorted LiO4 tetrahedra that share corners with two equivalent CoO4 tetrahedra, corners with four LiO4 tetrahedra, corners with six LiO4 trigonal pyramids, an edgeedge with one CoO4 tetrahedra, and edges with two LiO4 tetrahedra. There are a spread of Li–O bond distances ranging from 1.93–2.15 Å. In the eighth Li1+ site, Li1+ is bonded to four O2- atoms to form distorted LiO4 trigonal pyramids that share corners with two CoO4 tetrahedra, corners with eight LiO4 tetrahedra, a cornercorner with one LiO4 trigonal pyramid, an edgeedge with one LiO4 tetrahedra, an edgeedge with one CoO4 tetrahedra, and edges with two LiO4 trigonal pyramids. There are a spread of Li–O bond distances ranging from 1.95–2.18 Å. In the ninth Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share corners with four LiO4 tetrahedra, corners with four CoO4 tetrahedra, corners with three LiO4 trigonal pyramids, edges with two LiO4 tetrahedra, and edges with two LiO4 trigonal pyramids. There are a spread of Li–O bond distances ranging from 1.99–2.05 Å. In the tenth Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share corners with two CoO4 tetrahedra, corners with three LiO4 tetrahedra, corners with six LiO4 trigonal pyramids, an edgeedge with one CoO4 tetrahedra, edges with two LiO4 tetrahedra, and an edgeedge with one LiO4 trigonal pyramid. There are a spread of Li–O bond distances ranging from 1.96–2.04 Å. In the eleventh Li1+ site, Li1+ is bonded to four O2- atoms to form distorted LiO4 trigonal pyramids that share corners with two CoO4 tetrahedra, corners with seven LiO4 tetrahedra, corners with three LiO4 trigonal pyramids, an edgeedge with one CoO4 tetrahedra, edges with two LiO4 tetrahedra, and an edgeedge with one LiO4 trigonal pyramid. There are a spread of Li–O bond distances ranging from 1.97–2.07 Å. In the twelfth Li1+ site, Li1+ is bonded to four O2- atoms to form distorted LiO4 trigonal pyramids that share corners with two CoO4 tetrahedra, corners with six LiO4 tetrahedra, a cornercorner with one LiO4 trigonal pyramid, an edgeedge with one CoO4 tetrahedra, and edges with two LiO4 trigonal pyramids. There are a spread of Li–O bond distances ranging from 1.92–2.28 Å. In the thirteenth Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share corners with two CoO4 tetrahedra, corners with three LiO4 tetrahedra, corners with six LiO4 trigonal pyramids, an edgeedge with one LiO4 tetrahedra, an edgeedge with one CoO4 tetrahedra, and an edgeedge with one LiO4 trigonal pyramid. There are a spread of Li–O bond distances ranging from 1.95–2.08 Å. In the fourteenth Li1+ site, Li1+ is bonded to four O2- atoms to form distorted LiO4 trigonal pyramids that share corners with four LiO4 tetrahedra, corners with four CoO4 tetrahedra, a cornercorner with one LiO4 trigonal pyramid, edges with two LiO4 tetrahedra, and edges with two LiO4 trigonal pyramids. There are a spread of Li–O bond distances ranging from 1.92–2.09 Å. In the fifteenth Li1+ site, Li1+ is bonded to four O2- atoms to form distorted LiO4 trigonal pyramids that share corners with two CoO4 tetrahedra, corners with six LiO4 tetrahedra, a cornercorner with one LiO4 trigonal pyramid, an edgeedge with one LiO4 tetrahedra, an edgeedge with one CoO4 tetrahedra, and an edgeedge with one LiO4 trigonal pyramid. There are a spread of Li–O bond distances ranging from 1.89–2.31 Å. In the sixteenth Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share a cornercorner with one LiO4 tetrahedra, corners with two equivalent CoO4 tetrahedra, corners with six LiO4 trigonal pyramids, an edgeedge with one CoO4 tetrahedra, edges with two LiO4 tetrahedra, and an edgeedge with one LiO4 trigonal pyramid. There are a spread of Li–O bond distances ranging from 1.88–2.04 Å. There are four inequivalent Co4+ sites. In the first Co4+ site, Co4+ is bonded to four O2- atoms to form CoO4 tetrahedra that share corners with seven LiO4 tetrahedra, corners with two LiO4 trigonal pyramids, and edges with two LiO4 tetrahedra. There are a spread of Co–O bond distances ranging from 1.79–1.84 Å. In the second Co4+ site, Co4+ is bonded to four O2- atoms to form CoO4 tetrahedra that share corners with six LiO4 tetrahedra, corners with two LiO4 trigonal pyramids, an edgeedge with one LiO4 tetrahedra, and an edgeedge with one LiO4 trigonal pyramid. There are a spread of Co–O bond distances ranging from 1.72–1.86 Å. In the third Co4+ site, Co4+ is bonded to four O2- atoms to form CoO4 tetrahedra that share corners with six LiO4 tetrahedra, corners with six LiO4 trigonal pyramids, edges with two LiO4 tetrahedra, and edges with two LiO4 trigonal pyramids. There are a spread of Co–O bond distances ranging from 1.82–1.93 Å. In the fourth Co4+ site, Co4+ is bonded to four O2- atoms to form CoO4 tetrahedra that share corners with three LiO4 tetrahedra, corners with four LiO4 trigonal pyramids, edges with two LiO4 tetrahedra, and edges with two LiO4 trigonal pyramids. There are a spread of Co–O bond distances ranging from 1.71–1.85 Å. There are sixteen inequivalent O2- sites. In the first O2- site, O2- is bonded to four Li1+ and one Co4+ atom to form distorted OLi4Co trigonal bipyramids that share a cornercorner with one OLi5Co octahedra, corners with two equivalent OLi4Co trigonal bipyramids, a cornercorner with one OLi3Co trigonal pyramid, and edges with two OLi5Co octahedra. The corner-sharing octahedral tilt angles are 55°. In the second O2- site, O2- is bonded in a distorted see-saw-like geometry to three Li1+ and one Co4+ atom. In the third O2- site, O2- is bonded to three Li1+ and one Co4+ atom to form OLi3Co trigonal pyramids that share a cornercorner with one OLi5Co octahedra, corners with two OLi4Co trigonal bipyramids, and an edgeedge with one OLi4Co trigonal bipyramid. The corner-sharing octahedral tilt angles are 49°. In the fourth O2- site, O2- is bonded to four Li1+ and one Co4+ atom to form distorted OLi4Co trigonal bipyramids that share a cornercorner with one OLi5Co octahedra, corners with two equivalent OLi4Co trigonal bipyramids, a cornercorner with one OLi3Co trigonal pyramid, and an edgeedge with one OLi3Co trigonal pyramid. The corner-sharing octahedral tilt angles are 61°. In the fifth O2- site, O2- is bonded in a distorted T-shaped geometry to two Li1+ and one Co4+ atom. In the sixth O2- site, O2- is bonded in a see-saw-like geometry to three Li1+ and one Co4+ atom. In the seventh O2- site, O2- is bonded in a 5-coordinate geometry to five Li1+ and one Co4+ atom. In the eighth O2- site, O2- is bonded in a 6-coordinate geometry to five Li1+ and one Co4+ atom. In the ninth O2- site, O2- is bonded in a 6-coordinate geometry to five Li1+ and one Co4+ atom. In the tenth O2- site, O2- is bonded to five Li1+ and one Co4+ atom to form distorted OLi5Co octahedra that share a cornercorner with one OLi4Co trigonal bipyramid, a cornercorner with one OLi3Co trigonal pyramid, and edges with three OLi5Co octahedra. In the eleventh O2- site, O2- is bonded to five Li1+ and one Co4+ atom to form distorted OLi5Co octahedra that share corners with two equivalent OLi5Co octahedra, edges with three OLi5Co octahedra, and an edgeedge with one OLi4Co trigonal bipyramid. The corner-sharing octahedra tilt angles range from 55–61°. In the twelfth O2- site, O2- is bonded to five Li1+ and one Co4+ atom to form OLi5Co octahedra that share a cornercorner with one OLi4Co trigonal bipyramid, edges with three OLi5Co octahedra, and an edgeedge with one OLi4Co trigonal bipyramid. In the thirteenth O2- site, O2- is bonded to five Li1+ and one Co4+ atom to form a mixture of distorted edge and corner-sharing OLi5Co octahedra. The corner-sharing octahedra tilt angles range from 55–61°. In the fourteenth O2- site, O2- is bonded in a 6-coordinate geometry to five Li1+ and one Co4+ atom. In the fifteenth O2- site, O2- is bonded in a distorted see-saw-like geometry to three Li1+ and one Co4+ atom. In the sixteenth O2- site, O2- is bonded in a distorted T-shaped geometry to two Li1+ and one Co4+ atom.