DOE OSTI2020
Li3CrO4 is Caswellsilverite-like structured and crystallizes in the monoclinic P2 space group. The structure is three-dimensional. there are twelve inequivalent Li1+ sites. In the first Li1+ site, Li1+ is bonded to six O2- atoms to form LiO6 octahedra that share corners with two equivalent LiO6 octahedra, corners with four equivalent CrO6 octahedra, edges with two equivalent CrO6 octahedra, and edges with ten LiO6 octahedra. The corner-sharing octahedra tilt angles range from 3–13°. There are a spread of Li–O bond distances ranging from 2.01–2.30 Å. In the second Li1+ site, Li1+ is bonded to six O2- atoms to form LiO6 octahedra that share corners with six LiO6 octahedra, edges with four CrO6 octahedra, and edges with eight LiO6 octahedra. The corner-sharing octahedra tilt angles range from 10–12°. There are four shorter (2.08 Å) and two longer (2.11 Å) Li–O bond lengths. In the third Li1+ site, Li1+ is bonded to six O2- atoms to form LiO6 octahedra that share corners with two equivalent LiO6 octahedra, corners with four equivalent CrO6 octahedra, edges with two equivalent CrO6 octahedra, and edges with ten LiO6 octahedra. The corner-sharing octahedra tilt angles range from 5–10°. There are a spread of Li–O bond distances ranging from 2.01–2.25 Å. In the fourth Li1+ site, Li1+ is bonded to six O2- atoms to form LiO6 octahedra that share corners with six LiO6 octahedra, edges with four CrO6 octahedra, and edges with eight LiO6 octahedra. The corner-sharing octahedra tilt angles range from 11–12°. There are a spread of Li–O bond distances ranging from 2.06–2.12 Å. In the fifth Li1+ site, Li1+ is bonded to six O2- atoms to form LiO6 octahedra that share corners with two LiO6 octahedra, corners with four equivalent CrO6 octahedra, edges with two CrO6 octahedra, and edges with ten LiO6 octahedra. The corner-sharing octahedra tilt angles range from 5–12°. There are a spread of Li–O bond distances ranging from 2.00–2.28 Å. In the sixth Li1+ site, Li1+ is bonded to six O2- atoms to form LiO6 octahedra that share a cornercorner with one CrO6 octahedra, corners with five LiO6 octahedra, edges with four CrO6 octahedra, and edges with eight LiO6 octahedra. The corner-sharing octahedra tilt angles range from 8–13°. There are a spread of Li–O bond distances ranging from 2.00–2.21 Å. In the seventh Li1+ site, Li1+ is bonded to six O2- atoms to form LiO6 octahedra that share a cornercorner with one CrO6 octahedra, corners with five LiO6 octahedra, edges with four CrO6 octahedra, and edges with eight LiO6 octahedra. The corner-sharing octahedra tilt angles range from 10–13°. There are a spread of Li–O bond distances ranging from 2.03–2.21 Å. In the eighth Li1+ site, Li1+ is bonded to six O2- atoms to form LiO6 octahedra that share corners with two LiO6 octahedra, corners with four equivalent CrO6 octahedra, edges with two CrO6 octahedra, and edges with ten LiO6 octahedra. The corner-sharing octahedra tilt angles range from 4–11°. There are a spread of Li–O bond distances ranging from 2.01–2.26 Å. In the ninth Li1+ site, Li1+ is bonded to six O2- atoms to form LiO6 octahedra that share corners with two equivalent CrO6 octahedra, corners with four equivalent LiO6 octahedra, edges with four CrO6 octahedra, and edges with eight LiO6 octahedra. The corner-sharing octahedra tilt angles range from 10–12°. There are a spread of Li–O bond distances ranging from 2.01–2.23 Å. In the tenth Li1+ site, Li1+ is bonded to six O2- atoms to form LiO6 octahedra that share a cornercorner with one CrO6 octahedra, corners with five LiO6 octahedra, edges with four CrO6 octahedra, and edges with eight LiO6 octahedra. The corner-sharing octahedra tilt angles range from 10–13°. There are a spread of Li–O bond distances ranging from 1.98–2.18 Å. In the eleventh Li1+ site, Li1+ is bonded to six O2- atoms to form LiO6 octahedra that share a cornercorner with one CrO6 octahedra, corners with five LiO6 octahedra, edges with four CrO6 octahedra, and edges with eight LiO6 octahedra. The corner-sharing octahedra tilt angles range from 8–14°. There are a spread of Li–O bond distances ranging from 2.04–2.19 Å. In the twelfth Li1+ site, Li1+ is bonded to six O2- atoms to form LiO6 octahedra that share corners with two equivalent CrO6 octahedra, corners with four equivalent LiO6 octahedra, edges with four CrO6 octahedra, and edges with eight LiO6 octahedra. The corner-sharing octahedral tilt angles are 11°. There are a spread of Li–O bond distances ranging from 2.01–2.23 Å. There are four inequivalent Cr5+ sites. In the first Cr5+ site, Cr5+ is bonded to six O2- atoms to form CrO6 octahedra that share corners with six LiO6 octahedra, edges with two CrO6 octahedra, and edges with ten LiO6 octahedra. The corner-sharing octahedra tilt angles range from 4–11°. There are a spread of Cr–O bond distances ranging from 1.74–2.06 Å. In the second Cr5+ site, Cr5+ is bonded to six O2- atoms to form CrO6 octahedra that share corners with six LiO6 octahedra, edges with two equivalent CrO6 octahedra, and edges with ten LiO6 octahedra. The corner-sharing octahedra tilt angles range from 3–13°. There are a spread of Cr–O bond distances ranging from 1.78–2.04 Å. In the third Cr5+ site, Cr5+ is bonded to six O2- atoms to form CrO6 octahedra that share corners with six LiO6 octahedra, edges with two CrO6 octahedra, and edges with ten LiO6 octahedra. The corner-sharing octahedra tilt angles range from 5–12°. There are a spread of Cr–O bond distances ranging from 1.75–2.06 Å. In the fourth Cr5+ site, Cr5+ is bonded to six O2- atoms to form CrO6 octahedra that share corners with six LiO6 octahedra, edges with two equivalent CrO6 octahedra, and edges with ten LiO6 octahedra. The corner-sharing octahedra tilt angles range from 5–14°. There are a spread of Cr–O bond distances ranging from 1.78–2.04 Å. There are twelve inequivalent O2- sites. In the first O2- site, O2- is bonded to five Li1+ and one Cr5+ atom to form OLi5Cr octahedra that share corners with six OLi5Cr octahedra and edges with twelve OLi4Cr2 octahedra. The corner-sharing octahedra tilt angles range from 6–10°. In the second O2- site, O2- is bonded to five Li1+ and one Cr5+ atom to form OLi5Cr octahedra that share corners with six OLi5Cr octahedra and edges with twelve OLi4Cr2 octahedra. The corner-sharing octahedra tilt angles range from 6–10°. In the third O2- site, O2- is bonded to five Li1+ and one Cr5+ atom to form a mixture of edge and corner-sharing OLi5Cr octahedra. The corner-sharing octahedra tilt angles range from 3–11°. In the fourth O2- site, O2- is bonded to four Li1+ and two Cr5+ atoms to form a mixture of edge and corner-sharing OLi4Cr2 octahedra. The corner-sharing octahedra tilt angles range from 3–16°. In the fifth O2- site, O2- is bonded to five Li1+ and one Cr5+ atom to form a mixture of edge and corner-sharing OLi5Cr octahedra. The corner-sharing octahedra tilt angles range from 4–12°. In the sixth O2- site, O2- is bonded to five Li1+ and one Cr5+ atom to form a mixture of edge and corner-sharing OLi5Cr octahedra. The corner-sharing octahedra tilt angles range from 4–11°. In the seventh O2- site, O2- is bonded to four Li1+ and two Cr5+ atoms to form OLi4Cr2 octahedra that share corners with six OLi5Cr octahedra and edges with twelve OLi4Cr2 octahedra. The corner-sharing octahedra tilt angles range from 3–16°. In the eighth O2- site, O2- is bonded to five Li1+ and one Cr5+ atom to form a mixture of edge and corner-sharing OLi5Cr octahedra. The corner-sharing octahedra tilt angles range from 3–16°. In the ninth O2- site, O2- is bonded to four Li1+ and two Cr5+ atoms to form a mixture of edge and corner-sharing OLi4Cr2 octahedra. The corner-sharing octahedra tilt angles range from 6–16°. In the tenth O2- site, O2- is bonded to four Li1+ and two Cr5+ atoms to form OLi4Cr2 octahedra that share corners with six OLi5Cr octahedra and edges with twelve OLi4Cr2 octahedra. The corner-sharing octahedra tilt angles range from 5–17°. In the eleventh O2- site, O2- is bonded to four Li1+ and two Cr5+ atoms to form OLi4Cr2 octahedra that share corners with six OLi5Cr octahedra and edges with twelve OLi4Cr2 octahedra. The corner-sharing octahedra tilt angles range from 3–16°. In the twelfth O2- site, O2- is bonded to four Li1+ and two Cr5+ atoms to form OLi4Cr2 octahedra that share corners with six OLi5Cr octahedra and edges with twelve OLi4Cr2 octahedra. The corner-sharing octahedra tilt angles range from 3–17°.