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Synthesis, Crystal Structure, and Stability of Cubic Li_7-xLa₃Zr_2-xBi_xO₁₂.

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, 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.

SUBMITTER: Wagner R

PROVIDER: S-EPMC5141546 | biostudies-literature | 2016 Dec

REPOSITORIES: biostudies-literature

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Publications

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

Wagner Reinhard R Rettenwander Daniel D Redhammer Günther J GJ Tippelt Gerold G Sabathi Gebhard G Musso Maurizio E ME Stanje Bernhard B Wilkening Martin M Suard Emmanuelle E Amthauer Georg G

Inorganic chemistry 20161115 23

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-xLa ...[more]

PMID: 27934443

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Project description:Several "Beyond Li-Ion Battery" concepts such as all solid-state batteries and hybrid liquid/solid systems envision the use of a solid electrolyte to protect Li-metal anodes. These configurations are very attractive due to the possibility of exceptionally high energy densities and high (dis)charge rates, but they are far from being realized practically due to a number of issues including high interfacial resistance and difficulties associated with fabrication. One of the most promising solid electrolyte systems for these applications is Al or Ga stabilized Li7La3Zr2O12 (LLZO) based on high ionic conductivities and apparent stability against reduction by Li metal. Nevertheless, the fabrication of dense LLZO membranes with high ionic conductivity and low interfacial resistances remains challenging; it definitely requires a better understanding of the structural and electrochemical properties. In this study, the phase transition from garnet (Ia3̅d, No. 230) to "non-garnet" (I4̅3d, No. 220) space group as a function of composition and the different sintering behavior of Ga and Al stabilized LLZO are identified as important factors in determining the electrochemical properties. The phase transition was located at an Al:Ga substitution ratio of 0.05:0.15 and is accompanied by a significant lowering of the activation energy for Li-ion transport to 0.26 eV. The phase transition combined with microstructural changes concomitant with an increase of the Ga/Al ratio continuously improves the Li-ion conductivity from 2.6 × 10-4 S cm-1 to 1.2 × 10-3 S cm-1, which is close to the calculated maximum for garnet-type materials. The increase in Ga content is also associated with better densification and smaller grains and is accompanied by a change in the area specific resistance (ASR) from 78 to 24 Ω cm2, the lowest reported value for LLZO so far. These results illustrate that understanding the structure-properties relationships in this class of materials allows practical obstacles to its utilization to be readily overcome.

Dataset Information

Synthesis, Crystal Structure, and Stability of Cubic Li_7-xLa₃Zr_2-xBi_xO₁₂.

Publications

Synthesis, Crystal Structure, and Stability of Cubic Li<sub>7-x</sub>La<sub>3</sub>Zr<sub>2-x</sub>Bi<sub>x</sub>O<sub>12</sub>.

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