Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Be(CoO2)2”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

66 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Materials Data on Ca(CoO2)2 by Materials Project

CaCo2O4 is Spinel-like structured and crystallizes in the monoclinic Cm space group. The structure is three-dimensional. there are six inequivalent Ca2+ sites. In the first Ca2+ site, Ca2+ is bonded to four O2- atoms to form CaO4 tetrahedra that share corners with three CaO6 octahedra and corners with nine CoO6 octahedra. The corner-sharing octahedra tilt angles range from 54–73°. There are a spread of Ca–O bond distances ranging from 2.14–2.26 Å. In the second Ca2+ site, Ca2+ is bonded to six O2- atoms to form CaO6 octahedra that share corners with six CoO4 tetrahedra, edges with two CaO6 octahedra, and edges with four CoO6 octahedra. There are a spread of Ca–O bond distances ranging from 2.23–2.31 Å. In the third Ca2+ site, Ca2+ is bonded to six O2- atoms to form CaO6 octahedra that share corners with two equivalent CaO4 tetrahedra, corners with four CoO4 tetrahedra, an edgeedge with one CaO6 octahedra, and edges with five CoO6 octahedra. There are a spread of Ca–O bond distances ranging from 2.21–2.27 Å. In the fourth Ca2+ site, Ca2+ is bonded to six O2- atoms to form CaO6 octahedra that share corners with six CoO4 tetrahedra, edges with two CaO6 octahedra, and edges with four CoO6 octahedra. There are a spread of Ca–O bond distances ranging from 2.23–2.30 Å. In the fifth Ca2+ site, Ca2+ is bonded to six O2- atoms to form CaO6 octahedra that share corners with six CoO4 tetrahedra, edges with two CaO6 octahedra, and edges with four equivalent CoO6 octahedra. There are a spread of Ca–O bond distances ranging from 2.23–2.29 Å. In the sixth Ca2+ site, Ca2+ is bonded to six O2- atoms to form CaO6 octahedra that share a cornercorner with one CaO4 tetrahedra, corners with five CoO4 tetrahedra, an edgeedge with one CaO6 octahedra, and edges with five CoO6 octahedra. There are four shorter (2.24 Å) and two longer (2.25 Å) Ca–O bond lengths. There are nine inequivalent Co3+ sites. In the first Co3+ site, Co3+ is bonded to six O2- atoms to form CoO6 octahedra that share corners with two equivalent CaO4 tetrahedra, corners with four CoO4 tetrahedra, edges with three CaO6 octahedra, and edges with three CoO6 octahedra. There are a spread of Co–O bond distances ranging from 1.89–2.09 Å. In the second Co3+ site, Co3+ is bonded to four O2- atoms to form CoO4 tetrahedra that share corners with six CaO6 octahedra and corners with six CoO6 octahedra. The corner-sharing octahedra tilt angles range from 49–64°. There are a spread of Co–O bond distances ranging from 1.85–2.02 Å. In the third Co3+ site, Co3+ is bonded to six O2- atoms to form CoO6 octahedra that share corners with three equivalent CaO4 tetrahedra, corners with three equivalent CoO4 tetrahedra, edges with two CaO6 octahedra, and edges with four CoO6 octahedra. There are a spread of Co–O bond distances ranging from 1.85–2.00 Å. In the fourth Co3+ site, Co3+ is bonded to six O2- atoms to form CoO6 octahedra that share corners with six CoO4 tetrahedra, edges with two equivalent CoO6 octahedra, and edges with four CaO6 octahedra. There are a spread of Co–O bond distances ranging from 1.93–2.06 Å. In the fifth Co3+ site, Co3+ is bonded to four O2- atoms to form CoO4 tetrahedra that share corners with six CaO6 octahedra and corners with six CoO6 octahedra. The corner-sharing octahedra tilt angles range from 48–65°. There are a spread of Co–O bond distances ranging from 1.85–1.97 Å. In the sixth Co3+ site, Co3+ is bonded to six O2- atoms to form CoO6 octahedra that share a cornercorner with one CaO4 tetrahedra, corners with five CoO4 tetrahedra, edges with three CaO6 octahedra, and edges with three CoO6 octahedra. There are a spread of Co–O bond distances ranging from 1.93–2.12 Å. In the seventh Co3+ site, Co3+ is bonded to four O2- atoms to form CoO4 tetrahedra that share corners with six CaO6 octahedra and corners with six CoO6 octahedra. The corner-sharing octahedra tilt angles range from 48–64°. There are a spread of Co–O bond distances ranging from 1.86–2.00 Å. In the eighth Co3+ site, Co3+ is bonded to four O2- atoms to form CoO4 tetrahedra that share corners with six CaO6 octahedra and corners with six CoO6 octahedra. The corner-sharing octahedra tilt angles range from 49–63°. There are a spread of Co–O bond distances ranging from 1.86–2.04 Å. In the ninth Co3+ site, Co3+ is bonded to four O2- atoms to form CoO4 tetrahedra that share corners with three CaO6 octahedra and corners with nine CoO6 octahedra. The corner-sharing octahedra tilt angles range from 53–66°. There are a spread of Co–O bond distances ranging from 1.97–2.30 Å. There are eighteen inequivalent O2- sites. In the first O2- site, O2- is bonded to two Ca2+ and two Co3+ atoms to form distorted OCa2Co2 trigonal pyramids that share corners with two OCaCo3 tetrahedra, corners with six OCa2Co2 trigonal pyramids, an edgeedge with one OCaCo3 tetrahedra, and an edgeedge with one OCa2Co2 trigonal pyramid. In the second O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Ca2+ and three Co3+ atoms. In the third O2- site, O2- is bonded to one Ca2+ and three Co3+ atoms to form a mixture of distorted corner and edge-sharing OCaCo3 tetrahedra. In the fourth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Ca2+ and two Co3+ atoms. In the fifth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Ca2+ and three Co3+ atoms. In the sixth O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Ca2+ and three Co3+ atoms. In the seventh O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Ca2+ and two Co3+ atoms. In the eighth O2- site, O2- is bonded to one Ca2+ and three Co3+ atoms to form distorted OCaCo3 trigonal pyramids that share corners with two equivalent OCaCo3 tetrahedra and corners with seven OCa2Co2 trigonal pyramids. In the ninth O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Ca2+ and three Co3+ atoms. In the tenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Ca2+ and two Co3+ atoms. In the eleventh O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Ca2+ and three Co3+ atoms. In the twelfth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Ca2+ and two Co3+ atoms. In the thirteenth O2- site, O2- is bonded to two Ca2+ and two equivalent Co3+ atoms to form distorted OCa2Co2 tetrahedra that share a cornercorner with one OCaCo3 tetrahedra and corners with eight OCa2Co2 trigonal pyramids. In the fourteenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Ca2+ and three Co3+ atoms. In the fifteenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Ca2+ and three Co3+ atoms. In the sixteenth O2- site, O2- is bonded to four Co3+ atoms to form distorted OCo4 trigonal pyramids that share corners with three OCaCo3 tetrahedra, corners with five OCa2Co2 trigonal pyramids, and edges with two equivalent OCaCo3 trigonal pyramids. In the seventeenth O2- site, O2- is bonded to one Ca2+ and three Co3+ atoms to form distorted OCaCo3 trigonal pyramids that share corners with three OCaCo3 tetrahedra, corners with five OCa2Co2 trigonal pyramids, and edges with two OCo4 trigonal pyramids. In the eighteenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Ca2+ and three Co3+ atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Zn(CoO2)2 by Materials Project

ZnCo2O4 is Spinel-like structured and crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are twelve inequivalent Co3+ sites. In the first Co3+ site, Co3+ is bonded to six O2- atoms to form CoO6 octahedra that share corners with two equivalent ZnO4 tetrahedra, corners with four CoO4 tetrahedra, edges with three CoO6 octahedra, and edges with three ZnO6 octahedra. There are a spread of Co–O bond distances ranging from 1.91–1.96 Å. In the second Co3+ site, Co3+ is bonded to four O2- atoms to form CoO4 tetrahedra that share corners with six CoO6 octahedra and corners with six ZnO6 octahedra. The corner-sharing octahedra tilt angles range from 53–61°. There are a spread of Co–O bond distances ranging from 1.87–1.93 Å. In the third Co3+ site, Co3+ is bonded to six O2- atoms to form CoO6 octahedra that share corners with three equivalent CoO4 tetrahedra, corners with three equivalent ZnO4 tetrahedra, edges with two ZnO6 octahedra, and edges with four CoO6 octahedra. There are a spread of Co–O bond distances ranging from 1.89–1.98 Å. In the fourth Co3+ site, Co3+ is bonded to six O2- atoms to form CoO6 octahedra that share corners with two equivalent ZnO4 tetrahedra, corners with four CoO4 tetrahedra, edges with three CoO6 octahedra, and edges with three ZnO6 octahedra. There are a spread of Co–O bond distances ranging from 1.90–1.96 Å. In the fifth Co3+ site, Co3+ is bonded to six O2- atoms to form CoO6 octahedra that share corners with six CoO4 tetrahedra, edges with two equivalent CoO6 octahedra, and edges with four ZnO6 octahedra. There are a spread of Co–O bond distances ranging from 1.91–1.96 Å. In the sixth Co3+ site, Co3+ is bonded to four O2- atoms to form CoO4 tetrahedra that share corners with six CoO6 octahedra and corners with six ZnO6 octahedra. The corner-sharing octahedra tilt angles range from 52–61°. There are a spread of Co–O bond distances ranging from 1.87–1.93 Å. In the seventh Co3+ site, Co3+ is bonded to six O2- atoms to form CoO6 octahedra that share corners with six CoO4 tetrahedra, edges with two equivalent CoO6 octahedra, and edges with four ZnO6 octahedra. There are a spread of Co–O bond distances ranging from 1.91–1.96 Å. In the eighth Co3+ site, Co3+ is bonded to six O2- atoms to form CoO6 octahedra that share a cornercorner with one ZnO4 tetrahedra, corners with five CoO4 tetrahedra, edges with three CoO6 octahedra, and edges with three ZnO6 octahedra. There are a spread of Co–O bond distances ranging from 1.91–1.96 Å. In the ninth Co3+ site, Co3+ is bonded to four O2- atoms to form CoO4 tetrahedra that share corners with six CoO6 octahedra and corners with six ZnO6 octahedra. The corner-sharing octahedra tilt angles range from 53–60°. There are a spread of Co–O bond distances ranging from 1.86–1.94 Å. In the tenth Co3+ site, Co3+ is bonded to six O2- atoms to form CoO6 octahedra that share a cornercorner with one ZnO4 tetrahedra, corners with five CoO4 tetrahedra, edges with three CoO6 octahedra, and edges with three ZnO6 octahedra. There are a spread of Co–O bond distances ranging from 1.91–1.97 Å. In the eleventh Co3+ site, Co3+ is bonded to four O2- atoms to form CoO4 tetrahedra that share corners with six CoO6 octahedra and corners with six ZnO6 octahedra. The corner-sharing octahedra tilt angles range from 53–60°. There are a spread of Co–O bond distances ranging from 1.87–1.94 Å. In the twelfth Co3+ site, Co3+ is bonded to four O2- atoms to form CoO4 tetrahedra that share corners with three ZnO6 octahedra and corners with nine CoO6 octahedra. The corner-sharing octahedra tilt angles range from 56–63°. There are a spread of Co–O bond distances ranging from 1.89–2.00 Å. There are six inequivalent Zn2+ sites. In the first Zn2+ site, Zn2+ is bonded to four O2- atoms to form ZnO4 tetrahedra that share corners with three ZnO6 octahedra and corners with nine CoO6 octahedra. The corner-sharing octahedra tilt angles range from 57–62°. There are a spread of Zn–O bond distances ranging from 1.95–2.05 Å. In the second Zn2+ site, Zn2+ is bonded to six O2- atoms to form ZnO6 octahedra that share corners with six CoO4 tetrahedra, edges with two ZnO6 octahedra, and edges with four CoO6 octahedra. There are a spread of Zn–O bond distances ranging from 2.05–2.12 Å. In the third Zn2+ site, Zn2+ is bonded to six O2- atoms to form ZnO6 octahedra that share corners with two equivalent ZnO4 tetrahedra, corners with four CoO4 tetrahedra, an edgeedge with one ZnO6 octahedra, and edges with five CoO6 octahedra. There are a spread of Zn–O bond distances ranging from 2.03–2.14 Å. In the fourth Zn2+ site, Zn2+ is bonded to six O2- atoms to form ZnO6 octahedra that share corners with six CoO4 tetrahedra, edges with two ZnO6 octahedra, and edges with four CoO6 octahedra. There are a spread of Zn–O bond distances ranging from 2.05–2.12 Å. In the fifth Zn2+ site, Zn2+ is bonded to six O2- atoms to form ZnO6 octahedra that share corners with six CoO4 tetrahedra, edges with two ZnO6 octahedra, and edges with four CoO6 octahedra. There are a spread of Zn–O bond distances ranging from 2.04–2.12 Å. In the sixth Zn2+ site, Zn2+ is bonded to six O2- atoms to form ZnO6 octahedra that share a cornercorner with one ZnO4 tetrahedra, corners with five CoO4 tetrahedra, an edgeedge with one ZnO6 octahedra, and edges with five CoO6 octahedra. There are a spread of Zn–O bond distances ranging from 2.05–2.08 Å. There are twenty-four inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two Co3+ and two Zn2+ atoms. In the second O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Co3+ and one Zn2+ atom. In the third O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two Co3+ and two Zn2+ atoms. In the fourth O2- site, O2- is bonded to three Co3+ and one Zn2+ atom to form distorted corner-sharing OZnCo3 trigonal pyramids. In the fifth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Co3+ and two Zn2+ atoms. In the sixth O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Co3+ and one Zn2+ atom. In the seventh O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Co3+ and one Zn2+ atom. In the eighth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Co3+ and two Zn2+ atoms. In the ninth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Co3+ and two Zn2+ atoms. In the tenth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to three Co3+ and one Zn2+ atom. In the eleventh O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Co3+ and one Zn2+ atom. In the twelfth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Co3+ and two Zn2+ atoms. In the thirteenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Co3+ and two Zn2+ atoms. In the fourteenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Co3+ and one Zn2+ atom. In the fifteenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Co3+ and two Zn2+ atoms. In the sixteenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Co3+ and two Zn2+ atoms. In the seventeenth O2- site, O2- is bonded to two Co3+ and two Zn2+ atoms to form distorted corner-sharing OZn2Co2 trigonal pyramids. In the eighteenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Co3+ and one Zn2+ atom. In the nineteenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Co3+ and one Zn2+ atom. In the twentieth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Co3+ and two Zn2+ atoms. In the twenty-first O2- site, O2- is bonded to four Co3+ atoms to form distorted corner-sharing OCo4 trigonal pyramids. In the twenty-second O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Co3+ and one Zn2+ atom. In the twenty-third O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Co3+ and one Zn2+ atom. In the twenty-fourth O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Co3+ and one Zn2+ atom.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Mg(CoO2)2 by Materials Project

MgCo2O4 is Spinel-like structured and crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are six inequivalent Mg2+ sites. In the first Mg2+ site, Mg2+ is bonded to four O2- atoms to form MgO4 tetrahedra that share corners with three MgO6 octahedra and corners with nine CoO6 octahedra. The corner-sharing octahedra tilt angles range from 57–61°. There are a spread of Mg–O bond distances ranging from 1.94–2.05 Å. In the second Mg2+ site, Mg2+ is bonded to six O2- atoms to form MgO6 octahedra that share corners with six CoO4 tetrahedra, edges with two MgO6 octahedra, and edges with four CoO6 octahedra. There are a spread of Mg–O bond distances ranging from 2.04–2.08 Å. In the third Mg2+ site, Mg2+ is bonded to six O2- atoms to form MgO6 octahedra that share corners with two equivalent MgO4 tetrahedra, corners with four CoO4 tetrahedra, an edgeedge with one MgO6 octahedra, and edges with five CoO6 octahedra. There are a spread of Mg–O bond distances ranging from 2.00–2.10 Å. In the fourth Mg2+ site, Mg2+ is bonded to six O2- atoms to form MgO6 octahedra that share corners with six CoO4 tetrahedra, edges with two MgO6 octahedra, and edges with four CoO6 octahedra. There are a spread of Mg–O bond distances ranging from 2.03–2.08 Å. In the fifth Mg2+ site, Mg2+ is bonded to six O2- atoms to form MgO6 octahedra that share corners with six CoO4 tetrahedra, edges with two MgO6 octahedra, and edges with four CoO6 octahedra. There are a spread of Mg–O bond distances ranging from 2.03–2.08 Å. In the sixth Mg2+ site, Mg2+ is bonded to six O2- atoms to form MgO6 octahedra that share a cornercorner with one MgO4 tetrahedra, corners with five CoO4 tetrahedra, an edgeedge with one MgO6 octahedra, and edges with five CoO6 octahedra. There are a spread of Mg–O bond distances ranging from 2.02–2.06 Å. There are twelve inequivalent Co3+ sites. In the first Co3+ site, Co3+ is bonded to six O2- atoms to form CoO6 octahedra that share corners with two equivalent MgO4 tetrahedra, corners with four CoO4 tetrahedra, edges with three MgO6 octahedra, and edges with three CoO6 octahedra. There are a spread of Co–O bond distances ranging from 1.91–1.98 Å. In the second Co3+ site, Co3+ is bonded to four O2- atoms to form CoO4 tetrahedra that share corners with six MgO6 octahedra and corners with six CoO6 octahedra. The corner-sharing octahedra tilt angles range from 54–60°. There are a spread of Co–O bond distances ranging from 1.85–1.94 Å. In the third Co3+ site, Co3+ is bonded to six O2- atoms to form CoO6 octahedra that share corners with three equivalent MgO4 tetrahedra, corners with three equivalent CoO4 tetrahedra, edges with two MgO6 octahedra, and edges with four CoO6 octahedra. There are a spread of Co–O bond distances ranging from 1.89–1.98 Å. In the fourth Co3+ site, Co3+ is bonded to six O2- atoms to form CoO6 octahedra that share corners with two equivalent MgO4 tetrahedra, corners with four CoO4 tetrahedra, edges with three MgO6 octahedra, and edges with three CoO6 octahedra. There are a spread of Co–O bond distances ranging from 1.91–1.98 Å. In the fifth Co3+ site, Co3+ is bonded to six O2- atoms to form CoO6 octahedra that share corners with six CoO4 tetrahedra, edges with two equivalent CoO6 octahedra, and edges with four MgO6 octahedra. There are a spread of Co–O bond distances ranging from 1.92–1.97 Å. In the sixth Co3+ site, Co3+ is bonded to four O2- atoms to form CoO4 tetrahedra that share corners with six MgO6 octahedra and corners with six CoO6 octahedra. The corner-sharing octahedra tilt angles range from 54–60°. There are a spread of Co–O bond distances ranging from 1.85–1.93 Å. In the seventh Co3+ site, Co3+ is bonded to six O2- atoms to form CoO6 octahedra that share corners with six CoO4 tetrahedra, edges with two equivalent CoO6 octahedra, and edges with four MgO6 octahedra. There is two shorter (1.93 Å) and four longer (1.96 Å) Co–O bond length. In the eighth Co3+ site, Co3+ is bonded to six O2- atoms to form CoO6 octahedra that share a cornercorner with one MgO4 tetrahedra, corners with five CoO4 tetrahedra, edges with three MgO6 octahedra, and edges with three CoO6 octahedra. There are a spread of Co–O bond distances ranging from 1.92–1.98 Å. In the ninth Co3+ site, Co3+ is bonded to four O2- atoms to form CoO4 tetrahedra that share corners with six MgO6 octahedra and corners with six CoO6 octahedra. The corner-sharing octahedra tilt angles range from 55–60°. There is two shorter (1.85 Å) and two longer (1.94 Å) Co–O bond length. In the tenth Co3+ site, Co3+ is bonded to six O2- atoms to form CoO6 octahedra that share a cornercorner with one MgO4 tetrahedra, corners with five CoO4 tetrahedra, edges with three MgO6 octahedra, and edges with three CoO6 octahedra. There are a spread of Co–O bond distances ranging from 1.91–1.99 Å. In the eleventh Co3+ site, Co3+ is bonded to four O2- atoms to form CoO4 tetrahedra that share corners with six MgO6 octahedra and corners with six CoO6 octahedra. The corner-sharing octahedra tilt angles range from 55–60°. There is two shorter (1.86 Å) and two longer (1.94 Å) Co–O bond length. In the twelfth Co3+ site, Co3+ is bonded to four O2- atoms to form CoO4 tetrahedra that share corners with three MgO6 octahedra and corners with nine CoO6 octahedra. The corner-sharing octahedra tilt angles range from 56–62°. There are a spread of Co–O bond distances ranging from 1.89–1.97 Å. There are twenty-four inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two Mg2+ and two Co3+ atoms. In the second O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Mg2+ and three Co3+ atoms. In the third O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Mg2+ and two Co3+ atoms. In the fourth O2- site, O2- is bonded to one Mg2+ and three Co3+ atoms to form distorted corner-sharing OMgCo3 trigonal pyramids. In the fifth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Mg2+ and two Co3+ atoms. In the sixth O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Mg2+ and three Co3+ atoms. In the seventh O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Mg2+ and three Co3+ atoms. In the eighth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Mg2+ and two Co3+ atoms. In the ninth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Mg2+ and two Co3+ atoms. In the tenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Mg2+ and three Co3+ atoms. In the eleventh O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Mg2+ and three Co3+ atoms. In the twelfth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Mg2+ and two Co3+ atoms. In the thirteenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Mg2+ and two Co3+ atoms. In the fourteenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Mg2+ and three Co3+ atoms. In the fifteenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Mg2+ and two Co3+ atoms. In the sixteenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Mg2+ and two Co3+ atoms. In the seventeenth O2- site, O2- is bonded to two Mg2+ and two Co3+ atoms to form distorted corner-sharing OMg2Co2 trigonal pyramids. In the eighteenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Mg2+ and three Co3+ atoms. In the nineteenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Mg2+ and three Co3+ atoms. In the twentieth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Mg2+ and two Co3+ atoms. In the twenty-first O2- site, O2- is bonded to four Co3+ atoms to form distorted corner-sharing OCo4 trigonal pyramids. In the twenty-second O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Mg2+ and three Co3+ atoms. In the twenty-third O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Mg2+ and three Co3+ atoms. In the twenty-fourth O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Mg2+ and three Co3+ atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Zn(CoO2)2 by Materials Project

ZnCo2O4 is Spinel-like structured and crystallizes in the monoclinic Cm space group. The structure is three-dimensional. there are twelve inequivalent Co3+ sites. In the first Co3+ site, Co3+ is bonded to six O2- atoms to form CoO6 octahedra that share corners with three CoO4 tetrahedra, corners with three ZnO4 tetrahedra, edges with two equivalent ZnO6 octahedra, and edges with four CoO6 octahedra. There are a spread of Co–O bond distances ranging from 1.92–1.97 Å. In the second Co3+ site, Co3+ is bonded to six O2- atoms to form CoO6 octahedra that share corners with three equivalent CoO4 tetrahedra, corners with three equivalent ZnO4 tetrahedra, edges with two ZnO6 octahedra, and edges with four CoO6 octahedra. There are a spread of Co–O bond distances ranging from 1.91–1.97 Å. In the third Co3+ site, Co3+ is bonded to four O2- atoms to form CoO4 tetrahedra that share corners with six CoO6 octahedra and corners with six ZnO6 octahedra. The corner-sharing octahedra tilt angles range from 53–61°. There are a spread of Co–O bond distances ranging from 1.87–1.93 Å. In the fourth Co3+ site, Co3+ is bonded to six O2- atoms to form CoO6 octahedra that share corners with two equivalent ZnO4 tetrahedra, corners with four CoO4 tetrahedra, edges with three CoO6 octahedra, and edges with three ZnO6 octahedra. There are a spread of Co–O bond distances ranging from 1.90–1.98 Å. In the fifth Co3+ site, Co3+ is bonded to four O2- atoms to form CoO4 tetrahedra that share corners with three ZnO6 octahedra and corners with nine CoO6 octahedra. The corner-sharing octahedra tilt angles range from 57–63°. There are a spread of Co–O bond distances ranging from 1.94–2.01 Å. In the sixth Co3+ site, Co3+ is bonded to four O2- atoms to form CoO4 tetrahedra that share corners with six CoO6 octahedra and corners with six ZnO6 octahedra. The corner-sharing octahedra tilt angles range from 53–62°. There is two shorter (1.87 Å) and two longer (1.92 Å) Co–O bond length. In the seventh Co3+ site, Co3+ is bonded to six O2- atoms to form CoO6 octahedra that share corners with six CoO4 tetrahedra, edges with two equivalent CoO6 octahedra, and edges with four ZnO6 octahedra. There are a spread of Co–O bond distances ranging from 1.91–1.96 Å. In the eighth Co3+ site, Co3+ is bonded to four O2- atoms to form CoO4 tetrahedra that share corners with six CoO6 octahedra and corners with six ZnO6 octahedra. The corner-sharing octahedra tilt angles range from 53–61°. There are a spread of Co–O bond distances ranging from 1.87–1.93 Å. In the ninth Co3+ site, Co3+ is bonded to six O2- atoms to form CoO6 octahedra that share a cornercorner with one ZnO4 tetrahedra, corners with five CoO4 tetrahedra, edges with three CoO6 octahedra, and edges with three ZnO6 octahedra. There are a spread of Co–O bond distances ranging from 1.91–1.98 Å. In the tenth Co3+ site, Co3+ is bonded to four O2- atoms to form CoO4 tetrahedra that share corners with six CoO6 octahedra and corners with six ZnO6 octahedra. The corner-sharing octahedra tilt angles range from 53–61°. There are a spread of Co–O bond distances ranging from 1.87–1.94 Å. In the eleventh Co3+ site, Co3+ is bonded to six O2- atoms to form CoO6 octahedra that share corners with three equivalent CoO4 tetrahedra, corners with three equivalent ZnO4 tetrahedra, edges with two ZnO6 octahedra, and edges with four CoO6 octahedra. There are a spread of Co–O bond distances ranging from 1.91–1.97 Å. In the twelfth Co3+ site, Co3+ is bonded to four O2- atoms to form CoO4 tetrahedra that share corners with three ZnO6 octahedra and corners with nine CoO6 octahedra. The corner-sharing octahedra tilt angles range from 57–63°. There is three shorter (1.95 Å) and one longer (2.03 Å) Co–O bond length. There are eight inequivalent Zn2+ sites. In the first Zn2+ site, Zn2+ is bonded to four O2- atoms to form ZnO4 tetrahedra that share corners with three ZnO6 octahedra and corners with nine CoO6 octahedra. The corner-sharing octahedra tilt angles range from 57–63°. There are three shorter (1.96 Å) and one longer (2.04 Å) Zn–O bond lengths. In the second Zn2+ site, Zn2+ is bonded to six O2- atoms to form ZnO6 octahedra that share corners with three CoO4 tetrahedra, corners with three ZnO4 tetrahedra, and edges with six CoO6 octahedra. There are a spread of Zn–O bond distances ranging from 2.05–2.07 Å. In the third Zn2+ site, Zn2+ is bonded to four O2- atoms to form ZnO4 tetrahedra that share corners with three ZnO6 octahedra and corners with nine CoO6 octahedra. The corner-sharing octahedra tilt angles range from 58–63°. There are a spread of Zn–O bond distances ranging from 1.96–2.05 Å. In the fourth Zn2+ site, Zn2+ is bonded to six O2- atoms to form ZnO6 octahedra that share corners with two equivalent ZnO4 tetrahedra, corners with four CoO4 tetrahedra, an edgeedge with one ZnO6 octahedra, and edges with five CoO6 octahedra. There are a spread of Zn–O bond distances ranging from 2.03–2.12 Å. In the fifth Zn2+ site, Zn2+ is bonded to six O2- atoms to form ZnO6 octahedra that share corners with six CoO4 tetrahedra, edges with two ZnO6 octahedra, and edges with four equivalent CoO6 octahedra. There are four shorter (2.05 Å) and two longer (2.10 Å) Zn–O bond lengths. In the sixth Zn2+ site, Zn2+ is bonded to six O2- atoms to form ZnO6 octahedra that share corners with six CoO4 tetrahedra, edges with two ZnO6 octahedra, and edges with four CoO6 octahedra. There are a spread of Zn–O bond distances ranging from 2.05–2.11 Å. In the seventh Zn2+ site, Zn2+ is bonded to six O2- atoms to form ZnO6 octahedra that share a cornercorner with one ZnO4 tetrahedra, corners with five CoO4 tetrahedra, an edgeedge with one ZnO6 octahedra, and edges with five CoO6 octahedra. There are a spread of Zn–O bond distances ranging from 2.05–2.09 Å. In the eighth Zn2+ site, Zn2+ is bonded to six O2- atoms to form ZnO6 octahedra that share corners with six CoO4 tetrahedra, edges with two ZnO6 octahedra, and edges with four CoO6 octahedra. There are four shorter (2.06 Å) and two longer (2.11 Å) Zn–O bond lengths. There are twenty-four inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two Co3+ and two Zn2+ atoms. In the second O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two equivalent Co3+ and two Zn2+ atoms. In the third O2- site, O2- is bonded to three Co3+ and one Zn2+ atom to form distorted OZnCo3 trigonal pyramids that share a cornercorner with one OZn2Co2 tetrahedra and corners with three OCo4 trigonal pyramids. In the fourth O2- site, O2- is bonded to four Co3+ atoms to form distorted corner-sharing OCo4 trigonal pyramids. In the fifth O2- site, O2- is bonded to two Co3+ and two Zn2+ atoms to form a mixture of distorted edge and corner-sharing OZn2Co2 trigonal pyramids. In the sixth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to three Co3+ and one Zn2+ atom. In the seventh O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Co3+ and one Zn2+ atom. In the eighth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to three Co3+ and one Zn2+ atom. In the ninth O2- site, O2- is bonded to three Co3+ and one Zn2+ atom to form distorted OZnCo3 trigonal pyramids that share corners with five OZnCo3 trigonal pyramids and edges with two equivalent OZn2Co2 trigonal pyramids. In the tenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Co3+ and two Zn2+ atoms. In the eleventh O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Co3+ and one Zn2+ atom. In the twelfth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Co3+ and two Zn2+ atoms. In the thirteenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Co3+ and one Zn2+ atom. In the fourteenth O2- site, O2- is bonded to three Co3+ and one Zn2+ atom to form distorted corner-sharing OZnCo3 trigonal pyramids. In the fifteenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Co3+ and one Zn2+ atom. In the sixteenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Co3+ and one Zn2+ atom. In the seventeenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Co3+ and two Zn2+ atoms. In the eighteenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Co3+ and two Zn2+ atoms. In the nineteenth O2- site, O2- is bonded to two equivalent Co3+ and two Zn2+ atoms to form distorted corner-sharing OZn2Co2 tetrahedra. In the twentieth O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Co3+ and one Zn2+ atom. In the twenty-first O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Co3+ and one Zn2+ atom. In the twenty-second O2- site, O2- is bonded to four Co3+ atoms to form distorted OCo4 trigonal pyramids that share corners with two equivalent OZn2Co2 tetrahedra and a cornercorner with one OZnCo3 trigonal pyramid. In the twenty-third O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to three Co3+ and one Zn2+ atom. In the twenty-fourth O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Co3+ and one Zn2+ atom.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Ca(CoO2)2 by Materials Project

CaCo2O4 is Spinel-like structured and crystallizes in the monoclinic Cm space group. The structure is three-dimensional. there are eight inequivalent Ca2+ sites. In the first Ca2+ site, Ca2+ is bonded to four O2- atoms to form CaO4 tetrahedra that share corners with three CaO6 octahedra and corners with nine CoO6 octahedra. The corner-sharing octahedra tilt angles range from 57–74°. There are a spread of Ca–O bond distances ranging from 2.14–2.28 Å. In the second Ca2+ site, Ca2+ is bonded to six O2- atoms to form distorted CaO6 octahedra that share corners with three CaO4 tetrahedra, corners with three CoO4 tetrahedra, and edges with six CoO6 octahedra. There are four shorter (2.24 Å) and two longer (2.25 Å) Ca–O bond lengths. In the third Ca2+ site, Ca2+ is bonded to four O2- atoms to form CaO4 tetrahedra that share corners with three CaO6 octahedra and corners with nine CoO6 octahedra. The corner-sharing octahedra tilt angles range from 52–74°. There are a spread of Ca–O bond distances ranging from 2.14–2.25 Å. In the fourth Ca2+ site, Ca2+ is bonded to six O2- atoms to form CaO6 octahedra that share corners with two equivalent CaO4 tetrahedra, corners with four CoO4 tetrahedra, an edgeedge with one CaO6 octahedra, and edges with five CoO6 octahedra. There are a spread of Ca–O bond distances ranging from 2.22–2.29 Å. In the fifth Ca2+ site, Ca2+ is bonded to six O2- atoms to form CaO6 octahedra that share corners with six CoO4 tetrahedra, edges with two CaO6 octahedra, and edges with four equivalent CoO6 octahedra. There are a spread of Ca–O bond distances ranging from 2.23–2.30 Å. In the sixth Ca2+ site, Ca2+ is bonded to six O2- atoms to form CaO6 octahedra that share corners with six CoO4 tetrahedra, edges with two CaO6 octahedra, and edges with four CoO6 octahedra. There are a spread of Ca–O bond distances ranging from 2.23–2.31 Å. In the seventh Ca2+ site, Ca2+ is bonded to six O2- atoms to form CaO6 octahedra that share a cornercorner with one CaO4 tetrahedra, corners with five CoO4 tetrahedra, an edgeedge with one CaO6 octahedra, and edges with five CoO6 octahedra. All Ca–O bond lengths are 2.25 Å. In the eighth Ca2+ site, Ca2+ is bonded to six O2- atoms to form CaO6 octahedra that share corners with six CoO4 tetrahedra, edges with two CaO6 octahedra, and edges with four CoO6 octahedra. There are four shorter (2.23 Å) and two longer (2.30 Å) Ca–O bond lengths. There are twelve inequivalent Co3+ sites. In the first Co3+ site, Co3+ is bonded to six O2- atoms to form CoO6 octahedra that share corners with three CaO4 tetrahedra, corners with three CoO4 tetrahedra, edges with two equivalent CaO6 octahedra, and edges with four CoO6 octahedra. There are a spread of Co–O bond distances ranging from 1.89–2.05 Å. In the second Co3+ site, Co3+ is bonded to six O2- atoms to form CoO6 octahedra that share corners with three equivalent CaO4 tetrahedra, corners with three equivalent CoO4 tetrahedra, edges with two CaO6 octahedra, and edges with four CoO6 octahedra. There are a spread of Co–O bond distances ranging from 1.84–2.02 Å. In the third Co3+ site, Co3+ is bonded to four O2- atoms to form CoO4 tetrahedra that share corners with six CaO6 octahedra and corners with six CoO6 octahedra. The corner-sharing octahedra tilt angles range from 49–64°. There are a spread of Co–O bond distances ranging from 1.85–2.04 Å. In the fourth Co3+ site, Co3+ is bonded to six O2- atoms to form CoO6 octahedra that share corners with two equivalent CaO4 tetrahedra, corners with four CoO4 tetrahedra, edges with three CaO6 octahedra, and edges with three CoO6 octahedra. There are a spread of Co–O bond distances ranging from 1.89–2.09 Å. In the fifth Co3+ site, Co3+ is bonded to four O2- atoms to form CoO4 tetrahedra that share corners with three CaO6 octahedra and corners with nine CoO6 octahedra. The corner-sharing octahedra tilt angles range from 56–65°. There are a spread of Co–O bond distances ranging from 1.94–2.39 Å. In the sixth Co3+ site, Co3+ is bonded to four O2- atoms to form CoO4 tetrahedra that share corners with six CaO6 octahedra and corners with six CoO6 octahedra. The corner-sharing octahedra tilt angles range from 48–66°. There are a spread of Co–O bond distances ranging from 1.85–1.98 Å. In the seventh Co3+ site, Co3+ is bonded to six O2- atoms to form CoO6 octahedra that share corners with six CoO4 tetrahedra, edges with two equivalent CoO6 octahedra, and edges with four CaO6 octahedra. There are a spread of Co–O bond distances ranging from 1.93–2.06 Å. In the eighth Co3+ site, Co3+ is bonded to four O2- atoms to form CoO4 tetrahedra that share corners with six CaO6 octahedra and corners with six CoO6 octahedra. The corner-sharing octahedra tilt angles range from 48–65°. There are a spread of Co–O bond distances ranging from 1.86–2.03 Å. In the ninth Co3+ site, Co3+ is bonded to six O2- atoms to form CoO6 octahedra that share a cornercorner with one CaO4 tetrahedra, corners with five CoO4 tetrahedra, edges with three CaO6 octahedra, and edges with three CoO6 octahedra. There are a spread of Co–O bond distances ranging from 1.91–2.13 Å. In the tenth Co3+ site, Co3+ is bonded to four O2- atoms to form CoO4 tetrahedra that share corners with six CaO6 octahedra and corners with six CoO6 octahedra. The corner-sharing octahedra tilt angles range from 49–63°. There are a spread of Co–O bond distances ranging from 1.86–2.05 Å. In the eleventh Co3+ site, Co3+ is bonded to six O2- atoms to form CoO6 octahedra that share corners with three equivalent CaO4 tetrahedra, corners with three equivalent CoO4 tetrahedra, edges with two CaO6 octahedra, and edges with four CoO6 octahedra. There are a spread of Co–O bond distances ranging from 1.85–2.00 Å. In the twelfth Co3+ site, Co3+ is bonded to four O2- atoms to form CoO4 tetrahedra that share corners with three CaO6 octahedra and corners with nine CoO6 octahedra. The corner-sharing octahedra tilt angles range from 55–64°. There are a spread of Co–O bond distances ranging from 1.94–2.41 Å. There are twenty-four inequivalent O2- sites. In the first O2- site, O2- is bonded to two Ca2+ and two Co3+ atoms to form distorted OCa2Co2 trigonal pyramids that share a cornercorner with one OCa2Co2 tetrahedra, corners with eleven OCo4 trigonal pyramids, and edges with three OCa2Co2 trigonal pyramids. In the second O2- site, O2- is bonded to two Ca2+ and two equivalent Co3+ atoms to form distorted OCa2Co2 trigonal pyramids that share a cornercorner with one OCaCo3 tetrahedra, corners with eleven OCo4 trigonal pyramids, and edges with three OCa2Co2 trigonal pyramids. In the third O2- site, O2- is bonded to one Ca2+ and three Co3+ atoms to form distorted OCaCo3 trigonal pyramids that share a cornercorner with one OCa2Co2 tetrahedra, corners with eleven OCo4 trigonal pyramids, and edges with three OCa2Co2 trigonal pyramids. In the fourth O2- site, O2- is bonded to four Co3+ atoms to form a mixture of distorted corner and edge-sharing OCo4 trigonal pyramids. In the fifth O2- site, O2- is bonded to two Ca2+ and two Co3+ atoms to form distorted OCa2Co2 trigonal pyramids that share a cornercorner with one OCaCo3 tetrahedra, corners with seven OCaCo3 trigonal pyramids, an edgeedge with one OCaCo3 tetrahedra, and an edgeedge with one OCa2Co2 trigonal pyramid. In the sixth O2- site, O2- is bonded to one Ca2+ and three Co3+ atoms to form a mixture of distorted corner and edge-sharing OCaCo3 trigonal pyramids. In the seventh O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Ca2+ and three Co3+ atoms. In the eighth O2- site, O2- is bonded to one Ca2+ and three Co3+ atoms to form a mixture of distorted corner and edge-sharing OCaCo3 trigonal pyramids. In the ninth O2- site, O2- is bonded to one Ca2+ and three Co3+ atoms to form distorted OCaCo3 tetrahedra that share corners with eight OCaCo3 trigonal pyramids and edges with two equivalent OCa2Co2 trigonal pyramids. In the tenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Ca2+ and two Co3+ atoms. In the eleventh O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Ca2+ and three Co3+ atoms. In the twelfth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Ca2+ and two Co3+ atoms. In the thirteenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Ca2+ and three Co3+ atoms. In the fourteenth O2- site, O2- is bonded to one Ca2+ and three Co3+ atoms to form distorted OCaCo3 trigonal pyramids that share corners with two equivalent OCaCo3 tetrahedra and corners with seven OCo4 trigonal pyramids. In the fifteenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Ca2+ and three Co3+ atoms. In the sixteenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Ca2+ and three Co3+ atoms. In the seventeenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Ca2+ and two Co3+ atoms. In the eighteenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Ca2+ and two Co3+ atoms. In the nineteenth O2- site, O2- is bonded to two Ca2+ and two equivalent Co3+ atoms to form distorted corner-sharing OCa2Co2 tetrahedra. In the twentieth O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Ca2+ and three Co3+ atoms. In the twenty-first O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Ca2+ and three Co3+ atoms. In the twenty-second O2- site, O2- is bonded to four Co3+ atoms to form distorted OCo4 trigonal pyramids that share corners with two equivalent OCa2Co2 tetrahedra, corners with six OCaCo3 trigonal pyramids, and edges with two equivalent OCaCo3 trigonal pyramids. In the twenty-third O2- site, O2- is bonded to one Ca2+ and three Co3+ atoms to form distorted OCaCo3 trigonal pyramids that share corners with two equivalent OCa2Co2 tetrahedra, corners with six OCo4 trigonal pyramids, and edges with two OCo4 trigonal pyramids. In the twenty-fourth O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Ca2+ and three Co3+ atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Controlling Cation-Cation Interactions in Uranyl Coordination Dimers by Varying the Length of the Dicarboxylate Linker

The chemistry of linear uranyl(V/VI) dioxo cations, [O yl –U–O yl ] +/2+ , is dominated by coordination of uranium in the equatorial plane. Effects of this constraint were evaluated by experiment and theory for gas-phase mixed-valence U V/VI coordination dimers in which uranyl moieties are linked by alkyl dicarboxylates, [(UO 2 + )(UO 2 2+ )(OOC-(CH 2 ) n-2 -COO 2– ) 2 ] – (n = 3–12). Faster O 2 -addition to dimers with short linkers n = 3 and 4, vs. n ≥ 5, suggests a structural difference. Computed structures with the shortest linkers have bridging dicarboxylates and nearly parallel, non-interacting uranyls. Longer linkers, n = 5–7, accommodate uranyl orientations with distinct U V –U VI end-on cation-cation interactions (CCIs), whereby Lewis base O yl from U V coordinates to the acid U VI , denoted as U V O yl ···U VI . The dimer structure for n = 8 has a U V –U VI side-on diamond-shape CCI, with U V O yl ···U VI and U VI O yl ···U V interactions. Addition of O 2 to the n = 4 and 5 dimers yields [(UO22+)2(OOC-(CH2)n-2-COO2–)2(O2–)]–, with U V oxidized to U VI and O 2 reduced to O 2 – . Whereas O 2 can associate to and oxidize the exposed U V center for dimers with n = 3 and 4, the more crowded U V site in the CCI structures inhibits O 2 addition. Finally, the results demonstrate rational structural control of uranyl-uranyl bonding and reactivity in small coordination complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1992

Effects of 12-crown-4 ether on the electrochemical performance of CoO2 and TiS2 cathodes in Li polymer electrolyte cells

The effect of adding 12-crown-4 ether (12Cr4) to the polyethylene oxide (PEO) electrolyte on the electrochemical properties of cells with Li(x)CoO2 or TiS2 as the cathode was investigated. The polymer electrolyte films were: (1) PEO, LiBF4; (2) PEO, LiBF4 with 12Cr4; (3) Li(x)CoO2, PEO, and LiBF4; and (4) Li(x)CoO2, PEO, LiBF4, and 12Cr4. It was found that, although 12Cr4 improved the cell performance over cells without 12Cr4 in the shallow c/d cycles (cyclic voltammetric behavior), it did not seem to prolong the active life of the cell. The cells with CoO2 as the cathode failed after a few c/d cycles, while similar cells with TiS2 did not fail even after 12 c/d cycles. The probable cause of failure in the case of CoO2 is ascribed to the instability of the CoO2 cathode.

Nagasubramanian, G.↗
NASA NTRS1989

A survey of advanced battery systems for space applications

The results of a survey on advanced secondary battery systems for space applications are presented. The objectives were: to identify advanced battery systems capable of meeting the requirements of various types of space missions, with significant advantages over currently available batteries, to obtain an accurate estimate of the anticipated improvements of these advanced systems, and to obtain a consensus for the selection of systems most likely to yield the desired improvements. Few advanced systems are likely to exceed a specific energy of 150 Wh/kg and meet the additional requirements of safety and reliability within the next 15 years. The few that have this potential are: (1) regenerative fuel cells, both alkaline and solid polymer electrolyte (SPE) types for large power systems; (2) lithium-intercalatable cathodes, particularly the metal ozides intercalatable cathodes (MnO2 or CoO2), with applications limited to small spacecrafts requiring limited cycle life and low power levels; (3) lithium molten salt systems (e.g., LiAl-FeS2); and (4) Na/beta Alumina/Sulfur or metal chlorides cells. Likely technological advances that would enhance the performance of all the above systems are also identified, in particular: improved bifunctional oxygen electrodes; improved manufacturing technology for thin film lithium electrodes in combination with polymeric electrolytes; improved seals for the lithium molten salt cells; and improved ceramics for sodium/solid electrolyte cells.

Attia, Alan I.↗
DOE OSTI2020

Materials Data on Na(CoO2)3 by Materials Project

Na(CoO2)3 crystallizes in the triclinic P1 space group. The structure is three-dimensional. Na1+ is bonded in a 7-coordinate geometry to seven O2- atoms. There are a spread of Na–O bond distances ranging from 2.28–2.92 Å. There are three inequivalent Co+3.67+ sites. In the first Co+3.67+ site, Co+3.67+ is bonded to five O2- atoms to form distorted CoO5 trigonal bipyramids that share a cornercorner with one CoO6 octahedra, corners with three equivalent CoO4 tetrahedra, and edges with two equivalent CoO6 octahedra. The corner-sharing octahedral tilt angles are 36°. There are a spread of Co–O bond distances ranging from 1.75–2.21 Å. In the second Co+3.67+ site, Co+3.67+ is bonded to four O2- atoms to form CoO4 tetrahedra that share corners with four equivalent CoO6 octahedra and corners with three equivalent CoO5 trigonal bipyramids. The corner-sharing octahedra tilt angles range from 33–71°. There are a spread of Co–O bond distances ranging from 1.79–1.96 Å. In the third Co+3.67+ site, Co+3.67+ is bonded to six O2- atoms to form CoO6 octahedra that share corners with four equivalent CoO4 tetrahedra, a cornercorner with one CoO5 trigonal bipyramid, and edges with two equivalent CoO5 trigonal bipyramids. There are a spread of Co–O bond distances ranging from 1.86–2.02 Å. There are six inequivalent O2- sites. In the first O2- site, O2- is bonded in a 2-coordinate geometry to two equivalent Na1+ and three Co+3.67+ atoms. In the second O2- site, O2- is bonded in a 3-coordinate geometry to one Na1+ and two Co+3.67+ atoms. In the third O2- site, O2- is bonded in a 2-coordinate geometry to one Na1+, two Co+3.67+, and one O2- atom. The O–O bond length is 1.47 Å. In the fourth O2- site, O2- is bonded to one Na1+ and three Co+3.67+ atoms to form distorted corner-sharing ONaCo3 tetrahedra. In the fifth O2- site, O2- is bonded to one Na1+ and three Co+3.67+ atoms to form distorted corner-sharing ONaCo3 tetrahedra. In the sixth O2- site, O2- is bonded in a 4-coordinate geometry to one Na1+, two Co+3.67+, and one O2- atom.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Na3(CoO2)4 by Materials Project

Na3(CoO2)4 crystallizes in the triclinic P-1 space group. The structure is three-dimensional. there are two inequivalent Na1+ sites. In the first Na1+ site, Na1+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Na–O bond distances ranging from 2.29–2.52 Å. In the second Na1+ site, Na1+ is bonded in a 6-coordinate geometry to six O2- atoms. There are four shorter (2.37 Å) and two longer (2.40 Å) Na–O bond lengths. There are three inequivalent Co+3.25+ sites. In the first Co+3.25+ site, Co+3.25+ is bonded to six O2- atoms to form edge-sharing CoO6 octahedra. There are a spread of Co–O bond distances ranging from 1.90–2.03 Å. In the second Co+3.25+ site, Co+3.25+ is bonded to six O2- atoms to form edge-sharing CoO6 octahedra. There are a spread of Co–O bond distances ranging from 1.96–2.01 Å. In the third Co+3.25+ site, Co+3.25+ is bonded to six O2- atoms to form edge-sharing CoO6 octahedra. There are a spread of Co–O bond distances ranging from 1.95–2.04 Å. There are four inequivalent O2- sites. In the first O2- site, O2- is bonded to two equivalent Na1+ and three Co+3.25+ atoms to form ONa2Co3 square pyramids that share corners with three equivalent ONa3Co3 octahedra, corners with six ONa2Co3 square pyramids, edges with three equivalent ONa3Co3 octahedra, and edges with five ONa2Co3 square pyramids. The corner-sharing octahedra tilt angles range from 1–2°. In the second O2- site, O2- is bonded to two Na1+ and three Co+3.25+ atoms to form ONa2Co3 square pyramids that share corners with nine ONa2Co3 square pyramids, edges with four equivalent ONa3Co3 octahedra, and edges with four ONa2Co3 square pyramids. In the third O2- site, O2- is bonded to three Na1+ and three Co+3.25+ atoms to form distorted ONa3Co3 octahedra that share corners with three equivalent ONa3Co3 octahedra, corners with three equivalent ONa2Co3 square pyramids, an edgeedge with one ONa3Co3 octahedra, and edges with eleven ONa2Co3 square pyramids. The corner-sharing octahedral tilt angles are 0°. In the fourth O2- site, O2- is bonded to two Na1+ and three Co+3.25+ atoms to form ONa2Co3 square pyramids that share corners with nine ONa2Co3 square pyramids, edges with four equivalent ONa3Co3 octahedra, and edges with four ONa2Co3 square pyramids.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Li3(CoO2)4 by Materials Project

Li3(CoO2)4 crystallizes in the triclinic P1 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 six equivalent LiO6 octahedra, edges with two equivalent LiO6 octahedra, and edges with eight CoO6 octahedra. The corner-sharing octahedra tilt angles range from 11–13°. There are a spread of Li–O bond distances ranging from 2.00–2.12 Å. In the second Li1+ site, Li1+ is bonded to six O2- atoms to form LiO6 octahedra that share corners with six equivalent LiO6 octahedra, edges with two equivalent LiO6 octahedra, and edges with eight CoO6 octahedra. The corner-sharing octahedra tilt angles range from 11–13°. There are a spread of Li–O bond distances ranging from 1.99–2.10 Å. In the third Li1+ site, Li1+ is bonded to six O2- atoms to form LiO6 octahedra that share corners with six equivalent CoO6 octahedra, edges with four LiO6 octahedra, and edges with six CoO6 octahedra. The corner-sharing octahedra tilt angles range from 2–13°. There are a spread of Li–O bond distances ranging from 2.11–2.33 Å. There are four inequivalent Co+3.25+ sites. In the first Co+3.25+ site, Co+3.25+ is bonded to six O2- atoms to form CoO6 octahedra that share corners with six equivalent LiO6 octahedra, edges with four LiO6 octahedra, and edges with six CoO6 octahedra. The corner-sharing octahedra tilt angles range from 2–13°. There is four shorter (1.89 Å) and two longer (1.95 Å) Co–O bond length. In the second Co+3.25+ site, Co+3.25+ is bonded to six O2- atoms to form CoO6 octahedra that share corners with six equivalent CoO6 octahedra, edges with four CoO6 octahedra, and edges with six LiO6 octahedra. The corner-sharing octahedra tilt angles range from 8–12°. There are a spread of Co–O bond distances ranging from 2.04–2.13 Å. In the third Co+3.25+ site, Co+3.25+ is bonded to six O2- atoms to form CoO6 octahedra that share edges with six LiO6 octahedra and edges with six CoO6 octahedra. There are a spread of Co–O bond distances ranging from 1.87–1.92 Å. In the fourth Co+3.25+ site, Co+3.25+ is bonded to six O2- atoms to form CoO6 octahedra that share corners with six equivalent CoO6 octahedra, edges with four CoO6 octahedra, and edges with six LiO6 octahedra. The corner-sharing octahedra tilt angles range from 8–12°. There are a spread of Co–O bond distances ranging from 1.96–2.09 Å. There are eight inequivalent O2- sites. In the first O2- site, O2- is bonded to three Li1+ and two Co+3.25+ atoms to form OLi3Co2 square pyramids that share corners with nine OLi2Co3 square pyramids, edges with four OLi3Co3 octahedra, and edges with four OLi2Co3 square pyramids. In the second O2- site, O2- is bonded to two Li1+ and three Co+3.25+ atoms to form OLi2Co3 square pyramids that share corners with nine OLi3Co2 square pyramids, edges with four OLi3Co3 octahedra, and edges with four OLi3Co2 square pyramids. In the third O2- site, O2- is bonded to one Li1+ and four Co+3.25+ atoms to form OLiCo4 square pyramids that share corners with nine OLi3Co2 square pyramids, edges with four OLi3Co3 octahedra, and edges with four OLi3Co2 square pyramids. In the fourth O2- site, O2- is bonded to three Li1+ and three Co+3.25+ atoms to form OLi3Co3 octahedra that share corners with six equivalent OLi3Co3 octahedra and edges with twelve OLi3Co2 square pyramids. The corner-sharing octahedra tilt angles range from 0–1°. In the fifth O2- site, O2- is bonded to three Li1+ and three Co+3.25+ atoms to form OLi3Co3 octahedra that share corners with six equivalent OLi3Co3 octahedra and edges with twelve OLi3Co2 square pyramids. The corner-sharing octahedra tilt angles range from 0–1°. In the sixth O2- site, O2- is bonded to one Li1+ and four Co+3.25+ atoms to form OLiCo4 square pyramids that share corners with nine OLi3Co2 square pyramids, edges with four OLi3Co3 octahedra, and edges with four OLi3Co2 square pyramids. In the seventh O2- site, O2- is bonded to two Li1+ and three Co+3.25+ atoms to form OLi2Co3 square pyramids that share corners with nine OLi3Co2 square pyramids, edges with four OLi3Co3 octahedra, and edges with four OLi3Co2 square pyramids. In the eighth O2- site, O2- is bonded to three Li1+ and two Co+3.25+ atoms to form OLi3Co2 square pyramids that share corners with nine OLi3Co2 square pyramids, edges with four OLi3Co3 octahedra, and edges with four OLi2Co3 square pyramids.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Na11(CoO2)13 by Materials Project

Na11(CoO2)13 crystallizes in the trigonal P-3 space group. The structure is three-dimensional. there are five inequivalent Na1+ sites. In the first Na1+ site, Na1+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Na–O bond distances ranging from 2.36–2.47 Å. In the second Na1+ site, Na1+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Na–O bond distances ranging from 2.37–2.47 Å. In the third Na1+ site, Na1+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Na–O bond distances ranging from 2.36–2.51 Å. In the fourth Na1+ site, Na1+ is bonded in a 6-coordinate geometry to six O2- atoms. There are three shorter (2.37 Å) and three longer (2.43 Å) Na–O bond lengths. In the fifth Na1+ site, Na1+ is bonded to six O2- atoms to form distorted NaO6 pentagonal pyramids that share corners with six CoO6 octahedra and edges with six CoO6 octahedra. The corner-sharing octahedral tilt angles are 12°. There are three shorter (2.38 Å) and three longer (2.39 Å) Na–O bond lengths. There are six inequivalent Co+3.15+ sites. In the first Co+3.15+ site, Co+3.15+ is bonded to six O2- atoms to form CoO6 octahedra that share edges with six CoO6 octahedra and an edgeedge with one NaO6 pentagonal pyramid. There are a spread of Co–O bond distances ranging from 1.97–2.08 Å. In the second Co+3.15+ site, Co+3.15+ is bonded to six O2- atoms to form CoO6 octahedra that share a cornercorner with one NaO6 pentagonal pyramid and edges with six CoO6 octahedra. There are a spread of Co–O bond distances ranging from 2.00–2.06 Å. In the third Co+3.15+ site, Co+3.15+ is bonded to six equivalent O2- atoms to form edge-sharing CoO6 octahedra. All Co–O bond lengths are 1.91 Å. In the fourth Co+3.15+ site, Co+3.15+ is bonded to six O2- atoms to form CoO6 octahedra that share a cornercorner with one NaO6 pentagonal pyramid and edges with six CoO6 octahedra. There are a spread of Co–O bond distances ranging from 1.99–2.05 Å. In the fifth Co+3.15+ site, Co+3.15+ is bonded to six O2- atoms to form CoO6 octahedra that share edges with six CoO6 octahedra and an edgeedge with one NaO6 pentagonal pyramid. There are a spread of Co–O bond distances ranging from 1.96–2.08 Å. In the sixth Co+3.15+ site, Co+3.15+ is bonded to six equivalent O2- atoms to form edge-sharing CoO6 octahedra. All Co–O bond lengths are 1.93 Å. There are ten inequivalent O2- sites. In the first O2- site, O2- is bonded to three Na1+ and three Co+3.15+ atoms to form ONa3Co3 octahedra that share corners with five ONa3Co3 octahedra, corners with two ONa2Co3 square pyramids, corners with two ONa2Co3 trigonal bipyramids, edges with six ONa3Co3 octahedra, edges with two equivalent ONa2Co3 square pyramids, an edgeedge with one ONa2Co3 trigonal bipyramid, and a faceface with one ONa3Co3 octahedra. The corner-sharing octahedra tilt angles range from 2–51°. In the second O2- site, O2- is bonded to three Na1+ and three Co+3.15+ atoms to form ONa3Co3 octahedra that share corners with five ONa3Co3 octahedra, corners with two equivalent ONa2Co3 square pyramids, corners with two ONa2Co3 trigonal bipyramids, edges with five ONa3Co3 octahedra, edges with three equivalent ONa2Co3 square pyramids, an edgeedge with one ONa2Co3 trigonal bipyramid, and a faceface with one ONa3Co3 octahedra. The corner-sharing octahedra tilt angles range from 2–51°. In the third O2- site, O2- is bonded to three Na1+ and three Co+3.15+ atoms to form ONa3Co3 octahedra that share corners with five ONa3Co3 octahedra, corners with two ONa2Co3 square pyramids, corners with two ONa2Co3 trigonal bipyramids, edges with six ONa3Co3 octahedra, edges with two equivalent ONa2Co3 square pyramids, an edgeedge with one ONa2Co3 trigonal bipyramid, and a faceface with one ONa3Co3 octahedra. The corner-sharing octahedra tilt angles range from 1–51°. In the fourth O2- site, O2- is bonded to two Na1+ and three Co+3.15+ atoms to form distorted ONa2Co3 trigonal bipyramids that share corners with four ONa3Co3 octahedra, corners with two equivalent ONa2Co3 square pyramids, corners with three ONa2Co3 trigonal bipyramids, edges with two ONa3Co3 octahedra, an edgeedge with one ONa2Co3 square pyramid, and edges with five ONa2Co3 trigonal bipyramids. The corner-sharing octahedra tilt angles range from 3–40°. In the fifth O2- site, O2- is bonded to two Na1+ and three Co+3.15+ atoms to form ONa2Co3 square pyramids that share corners with five ONa3Co3 octahedra, corners with two equivalent ONa2Co3 square pyramids, corners with two equivalent ONa2Co3 trigonal bipyramids, edges with six ONa3Co3 octahedra, an edgeedge with one ONa2Co3 square pyramid, and an edgeedge with one ONa2Co3 trigonal bipyramid. The corner-sharing octahedra tilt angles range from 2–42°. In the sixth O2- site, O2- is bonded to two Na1+ and three Co+3.15+ atoms to form ONa2Co3 square pyramids that share corners with five ONa3Co3 octahedra, corners with two equivalent ONa2Co3 square pyramids, corners with two equivalent ONa2Co3 trigonal bipyramids, edges with six ONa3Co3 octahedra, an edgeedge with one ONa2Co3 square pyramid, and an edgeedge with one ONa2Co3 trigonal bipyramid. The corner-sharing octahedra tilt angles range from 1–43°. In the seventh O2- site, O2- is bonded to three Na1+ and three Co+3.15+ atoms to form ONa3Co3 octahedra that share corners with five ONa3Co3 octahedra, corners with two equivalent ONa2Co3 square pyramids, corners with two ONa2Co3 trigonal bipyramids, edges with five ONa3Co3 octahedra, edges with three equivalent ONa2Co3 square pyramids, an edgeedge with one ONa2Co3 trigonal bipyramid, and a faceface with one ONa3Co3 octahedra. The corner-sharing octahedra tilt angles range from 1–51°. In the eighth O2- site, O2- is bonded to three equivalent Na1+ and three equivalent Co+3.15+ atoms to form ONa3Co3 octahedra that share corners with six ONa3Co3 octahedra, corners with three equivalent ONa2Co3 square pyramids, edges with six ONa3Co3 octahedra, edges with three equivalent ONa2Co3 square pyramids, and a faceface with one ONa3Co3 octahedra. The corner-sharing octahedra tilt angles range from 2–45°. In the ninth O2- site, O2- is bonded to two Na1+ and three Co+3.15+ atoms to form distorted ONa2Co3 trigonal bipyramids that share corners with four ONa3Co3 octahedra, corners with two equivalent ONa2Co3 square pyramids, corners with three ONa2Co3 trigonal bipyramids, edges with two ONa3Co3 octahedra, an edgeedge with one ONa2Co3 square pyramid, and edges with five ONa2Co3 trigonal bipyramids. The corner-sharing octahedra tilt angles range from 3–39°. In the tenth O2- site, O2- is bonded to three equivalent Na1+ and three equivalent Co+3.15+ atoms to form ONa3Co3 octahedra that share corners with six ONa3Co3 octahedra, corners with three equivalent ONa2Co3 square pyramids, edges with six ONa3Co3 octahedra, edges with three equivalent ONa2Co3 square pyramids, and a faceface with one ONa3Co3 octahedra. The corner-sharing octahedra tilt angles range from 3–45°.

36 MATERIALS SCIENCE↗