title: Synthesis, Crystal Structure, and Stability of Cubic Li7-xLa3Zr2-xBixO12.
abstract: Li oxide garnets are among the most promising candidates for solid-state electrolytes in novel Li ion and Li metal based battery concepts. Cubic Li7La3Zr2O12stabilized by a partial substitution of Zr4+by Bi5+has not been the focus of research yet, despite the fact that Bi5+would be a cost-effective alternative to other stabilizing cations such as Nb5+and Ta5+. In this study, Li7-xLa3Zr2-xBixO12(x = 0.10, 0.20, ..., 1.00) was prepared by a low-temperature solid-state synthesis route. The samples have been characterized by a rich portfolio of techniques, including scanning electron microscopy, X-ray powder diffraction, neutron powder diffraction, Raman spectroscopy, and7Li NMR spectroscopy. Pure-phase cubic garnet samples were obtained for x ≥ 0.20. The introduction of Bi5+leads to an increase in the unit-cell parameters. Samples are sensitive to air, which causes the formation of LiOH and Li2CO3and the protonation of the garnet phase, leading to a further increase in the unit-cell parameters. The incorporation of Bi5+on the octahedral 16a site was confirmed by Raman spectroscopy.7Li NMR spectroscopy shows that fast Li ion dynamics are only observed for samples with high Bi5+contents.
authors.affiliation: Department of Chemistry and Physics of Materials, University of Salzburg , 5020 Salzburg, Austria.
authors.forename: Reinhard
authors.initials: R
authors.lastname: Wagner
authors.affiliation: Department of Chemistry and Physics of Materials, University of Salzburg , 5020 Salzburg, Austria.
authors.forename: Daniel
authors.initials: D
authors.lastname: Rettenwander
authors.affiliation: Department of Chemistry and Physics of Materials, University of Salzburg , 5020 Salzburg, Austria.
authors.forename: Günther J
authors.initials: GJ
authors.lastname: Redhammer
authors.affiliation: Department of Chemistry and Physics of Materials, University of Salzburg , 5020 Salzburg, Austria.
authors.forename: Gerold
authors.initials: G
authors.lastname: Tippelt
authors.affiliation: Department of Chemistry and Physics of Materials, University of Salzburg , 5020 Salzburg, Austria.
authors.forename: Gebhard
authors.initials: G
authors.lastname: Sabathi
authors.affiliation: Department of Chemistry and Physics of Materials, University of Salzburg , 5020 Salzburg, Austria.
authors.forename: Maurizio E
authors.initials: ME
authors.lastname: Musso
authors.affiliation: Christian Doppler Laboratory for Lithium Batteries, Institute for Chemistry and Technology of Materials, Graz University of Technology , 8010 Graz, Austria.
authors.forename: Bernhard
authors.initials: B
authors.lastname: Stanje
authors.affiliation: Christian Doppler Laboratory for Lithium Batteries, Institute for Chemistry and Technology of Materials, Graz University of Technology , 8010 Graz, Austria.
authors.forename: Martin
authors.initials: M
authors.lastname: Wilkening
authors.affiliation: Diffraction Group, Institut Laue-Langevin (ILL) , 71 avenue des Martyrs, 38000 Grenoble, France.
authors.forename: Emmanuelle
authors.initials: E
authors.lastname: Suard
authors.affiliation: Department of Chemistry and Physics of Materials, University of Salzburg , 5020 Salzburg, Austria.
authors.forename: Georg
authors.initials: G
authors.lastname: Amthauer