Crystal chemistry of "li7La3Zr2O12" garnet doped with Al, Ga, and Fe: A short review on local structures as revealed by NMR and Mößbauer spectroscopy studies

Daniel Rettenwander, Reinhard Wagner, Julia Langer, Maria Elisabeth Maier, Martin Wilkening, Georg Amthauer

Research output: Contribution to journalArticleResearchpeer-review

Abstract

Cubic Li7La3Zr2O12 (LLZO) garnets stabilized by substitution of Li by supervalent cations (Al3+, Ga3+ and Fe3+) are exceptionally well suited to be used as protecting layer to enable Li-metal based battery concepts. On the one hand this dopants are needed to provide the outstanding properties of LLZO at room temperature (RT), but on the other hand dopants occupying Li sites are suspected to hinder the long-range Li-ion transport properties within the structure. This depends on the type of dopant species and their amount in the LLZO garnet. In particular, the way these dopants can be distributed in the garnet structure is thought to play a critical role in the Li-diffusion behaviour. This short review addresses the difficulty to obtain structural information onminor amounts of cations in a large complicated structure such as LLZO by diffraction methods and the advantages of the application of complementary spectroscopic methods, such as Mößbauer and NMR spectroscopy, which provide information on the valence state and the distribution of the dopants Al, Ga, and Fe over the possible cation positions of the garnet structure. Finally, (i) NMR spectroscopy at very high magnetic fields (21.1 T) shows that Al and Ga are similarly distributed over the 24d and 96h sites in the garnet structure and (ii) Mößbauer spectroscopy proves that Fe occurs in the trivalent state, also at the 24d and 96h sites of the cubic garnet framework. The solubility limit of Fe, Al, and Ga is up to 0.25 pfu, 0.39 pfu, and 0.72 pfu, respectively.

Original languageEnglish
Pages (from-to)619-629
Number of pages11
JournalEuropean journal of mineralogy
Volume28
Issue number3
DOIs
Publication statusPublished - 2016

Fingerprint

Crystal chemistry
crystal chemistry
Garnets
nuclear magnetic resonance
garnet
spectroscopy
Nuclear magnetic resonance
Spectroscopy
Doping (additives)
Cations
cation
Nuclear magnetic resonance spectroscopy
Transport properties
diffraction
solubility
substitution
Substitution reactions
Solubility
Diffraction
Metals

Keywords

  • Ionic Conductor
  • LLZO Garnet
  • Mößbauer Spectroscopy
  • NMR Spectroscopy
  • XRD

ASJC Scopus subject areas

  • Geochemistry and Petrology

Cite this

Crystal chemistry of "li7La3Zr2O12" garnet doped with Al, Ga, and Fe : A short review on local structures as revealed by NMR and Mößbauer spectroscopy studies. / Rettenwander, Daniel; Wagner, Reinhard; Langer, Julia; Maier, Maria Elisabeth; Wilkening, Martin; Amthauer, Georg.

In: European journal of mineralogy, Vol. 28, No. 3, 2016, p. 619-629.

Research output: Contribution to journalArticleResearchpeer-review

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abstract = "Cubic Li7La3Zr2O12 (LLZO) garnets stabilized by substitution of Li by supervalent cations (Al3+, Ga3+ and Fe3+) are exceptionally well suited to be used as protecting layer to enable Li-metal based battery concepts. On the one hand this dopants are needed to provide the outstanding properties of LLZO at room temperature (RT), but on the other hand dopants occupying Li sites are suspected to hinder the long-range Li-ion transport properties within the structure. This depends on the type of dopant species and their amount in the LLZO garnet. In particular, the way these dopants can be distributed in the garnet structure is thought to play a critical role in the Li-diffusion behaviour. This short review addresses the difficulty to obtain structural information onminor amounts of cations in a large complicated structure such as LLZO by diffraction methods and the advantages of the application of complementary spectroscopic methods, such as M{\"o}{\ss}bauer and NMR spectroscopy, which provide information on the valence state and the distribution of the dopants Al, Ga, and Fe over the possible cation positions of the garnet structure. Finally, (i) NMR spectroscopy at very high magnetic fields (21.1 T) shows that Al and Ga are similarly distributed over the 24d and 96h sites in the garnet structure and (ii) M{\"o}{\ss}bauer spectroscopy proves that Fe occurs in the trivalent state, also at the 24d and 96h sites of the cubic garnet framework. The solubility limit of Fe, Al, and Ga is up to 0.25 pfu, 0.39 pfu, and 0.72 pfu, respectively.",
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