Synthesis, Crystal Structure, and Stability of Cubic Li7-xLa3Zr2-xBixO12

Reinhard Wagner, Daniel Rettenwander, Günther J. Redhammer, Gerold Tippelt, Gebhard Sabathi, Maurizio E. Musso, Bernhard Stanje, Martin Wilkening, Emmanuelle Suard, Georg Amthauer

Research output: Contribution to journalArticleResearchpeer-review

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 Li7La3Zr2O12 stabilized 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, and 7Li 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 Li2CO3 and 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.

Original languageEnglish
Pages (from-to)12211-12219
Number of pages9
JournalInorganic chemistry
Volume55
Issue number23
DOIs
Publication statusPublished - 5 Dec 2016

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Garnets
Crystal structure
garnets
Nuclear magnetic resonance spectroscopy
crystal structure
Raman spectroscopy
synthesis
Ions
Neutron powder diffraction
Protonation
solid state
X ray powder diffraction
Oxides
nuclear magnetic resonance
Electrolytes
Cations
Substitution reactions
Metals
cells
spectroscopy

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Wagner, R., Rettenwander, D., Redhammer, G. J., Tippelt, G., Sabathi, G., Musso, M. E., ... Amthauer, G. (2016). Synthesis, Crystal Structure, and Stability of Cubic Li7-xLa3Zr2-xBixO12. Inorganic chemistry, 55(23), 12211-12219. https://doi.org/10.1021/acs.inorgchem.6b01825

Synthesis, Crystal Structure, and Stability of Cubic Li7-xLa3Zr2-xBixO12. / Wagner, Reinhard; Rettenwander, Daniel; Redhammer, Günther J.; Tippelt, Gerold; Sabathi, Gebhard; Musso, Maurizio E.; Stanje, Bernhard; Wilkening, Martin; Suard, Emmanuelle; Amthauer, Georg.

In: Inorganic chemistry, Vol. 55, No. 23, 05.12.2016, p. 12211-12219.

Research output: Contribution to journalArticleResearchpeer-review

Wagner, R, Rettenwander, D, Redhammer, GJ, Tippelt, G, Sabathi, G, Musso, ME, Stanje, B, Wilkening, M, Suard, E & Amthauer, G 2016, 'Synthesis, Crystal Structure, and Stability of Cubic Li7-xLa3Zr2-xBixO12' Inorganic chemistry, vol. 55, no. 23, pp. 12211-12219. https://doi.org/10.1021/acs.inorgchem.6b01825
Wagner, Reinhard ; Rettenwander, Daniel ; Redhammer, Günther J. ; Tippelt, Gerold ; Sabathi, Gebhard ; Musso, Maurizio E. ; Stanje, Bernhard ; Wilkening, Martin ; Suard, Emmanuelle ; Amthauer, Georg. / Synthesis, Crystal Structure, and Stability of Cubic Li7-xLa3Zr2-xBixO12. In: Inorganic chemistry. 2016 ; Vol. 55, No. 23. pp. 12211-12219.
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