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

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review


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
Issue number23
Publication statusPublished - 5 Dec 2016

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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