Materials Data on LiMn2O4 by Materials Project

Abstract

LiMn2O4 crystallizes in the monoclinic Cc space group. The structure is three-dimensional. there are three inequivalent Li1+ sites. In the first Li1+ site, Li1+ is bonded to six O2- atoms to form LiO6 octahedra that share corners with five MnO6 octahedra, an edgeedge with one LiO6 octahedra, edges with five MnO6 octahedra, and a faceface with one MnO6 octahedra. The corner-sharing octahedra tilt angles range from 7–47°. There are a spread of Li–O bond distances ranging from 1.96–2.27 Å. In the second 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 1.90–2.46 Å. In the third Li1+ site, Li1+ is bonded to six O2- atoms to form LiO6 octahedra that share corners with five MnO6 octahedra, an edgeedge with one LiO6 octahedra, edges with five MnO6 octahedra, and a faceface with one MnO6 octahedra. The corner-sharing octahedra tilt angles range from 7–51°. There are a spread of Li–O bond distances ranging from 1.97–2.22 Å. There are six inequivalent Mn+3.50+ sites. In the first Mn+3.50+ site, Mn+3.50+ is bonded to six O2- atoms to form distorted MnO6 octahedra that share corners with two equivalent LiO6 octahedra, corners with eight MnO6 octahedra, edges with two equivalent MnO6 octahedra, and a faceface with one LiO6 octahedra. The corner-sharing octahedra tilt angles range from 49–53°. There are a spread of Mn–O bond distances ranging from 1.95–2.46 Å. In the second Mn+3.50+ site, Mn+3.50+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with two equivalent LiO6 octahedra, corners with eight MnO6 octahedra, edges with two equivalent MnO6 octahedra, and a faceface with one LiO6 octahedra. The corner-sharing octahedra tilt angles range from 46–54°. There are a spread of Mn–O bond distances ranging from 1.94–2.25 Å. In the third Mn+3.50+ site, Mn+3.50+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with four MnO6 octahedra, edges with three LiO6 octahedra, and edges with four MnO6 octahedra. The corner-sharing octahedra tilt angles range from 50–54°. There are a spread of Mn–O bond distances ranging from 1.91–2.01 Å. In the fourth Mn+3.50+ site, Mn+3.50+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with three equivalent LiO6 octahedra, corners with four MnO6 octahedra, edges with two equivalent LiO6 octahedra, and edges with four MnO6 octahedra. The corner-sharing octahedra tilt angles range from 7–53°. There are a spread of Mn–O bond distances ranging from 1.90–2.03 Å. In the fifth Mn+3.50+ site, Mn+3.50+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with four MnO6 octahedra, edges with three LiO6 octahedra, and edges with four MnO6 octahedra. The corner-sharing octahedra tilt angles range from 51–53°. There are a spread of Mn–O bond distances ranging from 1.91–2.15 Å. In the sixth Mn+3.50+ site, Mn+3.50+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with three equivalent LiO6 octahedra, corners with four MnO6 octahedra, edges with two equivalent LiO6 octahedra, and edges with four MnO6 octahedra. The corner-sharing octahedra tilt angles range from 7–52°. There are a spread of Mn–O bond distances ranging from 1.89–2.08 Å. There are twelve inequivalent O2- sites. In the first O2- site, O2- is bonded to one Li1+ and three Mn+3.50+ atoms to form distorted OLiMn3 trigonal pyramids that share corners with two OLi2Mn3 square pyramids, corners with two equivalent OLi2Mn3 trigonal bipyramids, corners with two OLiMn3 trigonal pyramids, an edgeedge with one OLi3Mn3 octahedra, and an edgeedge with one OLiMn3 trigonal pyramid. In the second O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Li1+ and three Mn+3.50+ atoms. In the third O2- site, O2- is bonded in a 5-coordinate geometry to two Li1+ and three Mn+3.50+ atoms. In the fourth O2- site, O2- is bonded in a 5-coordinate geometry to two Li1+ and three Mn+3.50+ atoms. In the fifth O2- site, O2- is bonded to one Li1+ and three Mn+3.50+ atoms to form distorted OLiMn3 trigonal pyramids that share corners with three equivalent OLi3Mn3 octahedra, corners with two OLiMn3 trigonal pyramids, edges with two OLi2Mn3 square pyramids, an edgeedge with one OLi2Mn3 trigonal bipyramid, and an edgeedge with one OLiMn3 trigonal pyramid. The corner-sharing octahedra tilt angles range from 9–12°. In the sixth O2- site, O2- is bonded in a distorted trigonal planar geometry to three Mn+3.50+ atoms. In the seventh O2- site, O2- is bonded in a 4-coordinate geometry to one Li1+ and three Mn+3.50+ atoms. In the eighth O2- site, O2- is bonded to one Li1+ and three Mn+3.50+ atoms to form distorted OLiMn3 trigonal pyramids that share corners with three equivalent OLi2Mn3 trigonal bipyramids, corners with two OLiMn3 trigonal pyramids, an edgeedge with one OLi3Mn3 octahedra, and edges with two OLi2Mn3 square pyramids. In the ninth O2- site, O2- is bonded to two Li1+ and three Mn+3.50+ atoms to form OLi2Mn3 square pyramids that share a cornercorner with one OLi2Mn3 square pyramid, a cornercorner with one OLi2Mn3 trigonal bipyramid, a cornercorner with one OLiMn3 trigonal pyramid, edges with two equivalent OLi3Mn3 octahedra, an edgeedge with one OLi2Mn3 square pyramid, an edgeedge with one OLi2Mn3 trigonal bipyramid, and edges with two OLiMn3 trigonal pyramids. In the tenth O2- site, O2- is bonded to three Li1+ and three Mn+3.50+ atoms to form OLi3Mn3 octahedra that share corners with three equivalent OLiMn3 trigonal pyramids, edges with four OLi2Mn3 square pyramids, edges with two equivalent OLi2Mn3 trigonal bipyramids, and edges with two OLiMn3 trigonal pyramids. In the eleventh O2- site, O2- is bonded to two Li1+ and three Mn+3.50+ atoms to form distorted OLi2Mn3 trigonal bipyramids that share corners with two OLi2Mn3 square pyramids, corners with five OLiMn3 trigonal pyramids, edges with two equivalent OLi3Mn3 octahedra, edges with two OLi2Mn3 square pyramids, and an edgeedge with one OLiMn3 trigonal pyramid. In the twelfth O2- site, O2- is bonded to two Li1+ and three Mn+3.50+ atoms to form OLi2Mn3 square pyramids that share a cornercorner with one OLi2Mn3 square pyramid, a cornercorner with one OLi2Mn3 trigonal bipyramid, a cornercorner with one OLiMn3 trigonal pyramid, edges with two equivalent OLi3Mn3 octahedra, an edgeedge with one OLi2Mn3 square pyramid, an edgeedge with one OLi2Mn3 trigonal bipyramid, and edges with two OLiMn3 trigonal pyramids.