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• 作者：Reinhard Wagner ; Daniel Rettenwander ; Günther J. Redhammer ; Gerold Tippelt ; Gebhard Sabathi ; Maurizio E. Musso ; Bernhard Stanje ; Martin Wilkening ; Emmanuelle Suard ; Georg Amthauer
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：December 5, 2016
• 年：2016
• 卷：55
• 期：23
• 页码：12211-12219
• 全文大小：628K
• ISSN：1520-510X

文摘

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, Li_7–xLa₃Zr_2–xBi_xO₁₂ (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.