Switching on fast lithium ion conductivity in garnets: the structure and transport properties of Li3+xNd3Te2-xSbxO12

M.P. O'Callaghan, A.S. Powell, J.J. Titman, G.Z. Chen, E.J. Cussen

Research output: Contribution to journalArticle

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Abstract

Polycrystalline samples of the garnets Li3+xNd3Te2-xSbxO12 have been prepared by high temperature solid state synthesis. X-ray and neutron powder diffraction data show that all compounds crystallize in the space group Ia3j d with lattice parameters in the range 12.55576(12) Å for x ) 0.05 to 12.6253(2) Å for x ) 1.5. The lithium is distributed over a mixture of oxide tetrahedra and heavily distorted octahedra. Increasing the lithium content in these compounds leads to the introduction of vacancies onto the tetrahedral position and an increasing concentration of lithium found in the octahedra. The latter exhibit considerable positional disorder with two lithium cations positions within each octahedron. Impedance measurements show fast ion conduction with an activation energy of ca. 0.59(6) eV that is largely invariant with composition. Solid-state Li NMR measurements indicate that there is no exchange of lithium between the different coordination environments. These results indicate that lithium conduction in the garnet structure occurs exclusively via a network of edge-linked distorted oxide octahedra and that the tetrahedrally coordination lithium plays no part in the transport properties.
LanguageEnglish
Pages2360-2369
Number of pages10
JournalChemistry of Materials
Volume20
Issue number6
DOIs
Publication statusPublished - 25 Mar 2008

Fingerprint

Garnets
Lithium
Transport properties
Ions
Oxides
Lead compounds
Neutron powder diffraction
X ray powder diffraction
Lattice constants
Vacancies
Cations
Activation energy
Positive ions
Nuclear magnetic resonance

Keywords

  • garnets
  • ion conductivity
  • lithium

Cite this

O'Callaghan, M.P. ; Powell, A.S. ; Titman, J.J. ; Chen, G.Z. ; Cussen, E.J. / Switching on fast lithium ion conductivity in garnets : the structure and transport properties of Li3+xNd3Te2-xSbxO12. In: Chemistry of Materials. 2008 ; Vol. 20, No. 6. pp. 2360-2369.
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Switching on fast lithium ion conductivity in garnets : the structure and transport properties of Li3+xNd3Te2-xSbxO12. / O'Callaghan, M.P.; Powell, A.S.; Titman, J.J.; Chen, G.Z.; Cussen, E.J.

In: Chemistry of Materials, Vol. 20, No. 6, 25.03.2008, p. 2360-2369.

Research output: Contribution to journalArticle

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T2 - Chemistry of Materials

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N2 - Polycrystalline samples of the garnets Li3+xNd3Te2-xSbxO12 have been prepared by high temperature solid state synthesis. X-ray and neutron powder diffraction data show that all compounds crystallize in the space group Ia3j d with lattice parameters in the range 12.55576(12) Å for x ) 0.05 to 12.6253(2) Å for x ) 1.5. The lithium is distributed over a mixture of oxide tetrahedra and heavily distorted octahedra. Increasing the lithium content in these compounds leads to the introduction of vacancies onto the tetrahedral position and an increasing concentration of lithium found in the octahedra. The latter exhibit considerable positional disorder with two lithium cations positions within each octahedron. Impedance measurements show fast ion conduction with an activation energy of ca. 0.59(6) eV that is largely invariant with composition. Solid-state Li NMR measurements indicate that there is no exchange of lithium between the different coordination environments. These results indicate that lithium conduction in the garnet structure occurs exclusively via a network of edge-linked distorted oxide octahedra and that the tetrahedrally coordination lithium plays no part in the transport properties.

AB - Polycrystalline samples of the garnets Li3+xNd3Te2-xSbxO12 have been prepared by high temperature solid state synthesis. X-ray and neutron powder diffraction data show that all compounds crystallize in the space group Ia3j d with lattice parameters in the range 12.55576(12) Å for x ) 0.05 to 12.6253(2) Å for x ) 1.5. The lithium is distributed over a mixture of oxide tetrahedra and heavily distorted octahedra. Increasing the lithium content in these compounds leads to the introduction of vacancies onto the tetrahedral position and an increasing concentration of lithium found in the octahedra. The latter exhibit considerable positional disorder with two lithium cations positions within each octahedron. Impedance measurements show fast ion conduction with an activation energy of ca. 0.59(6) eV that is largely invariant with composition. Solid-state Li NMR measurements indicate that there is no exchange of lithium between the different coordination environments. These results indicate that lithium conduction in the garnet structure occurs exclusively via a network of edge-linked distorted oxide octahedra and that the tetrahedrally coordination lithium plays no part in the transport properties.

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