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Single-crystal neutron diffraction on γ-LiAlO2: structure determination and estimation of lithium diffusion pathway

  • Dennis Wiedemann EMAIL logo , Sylvio Indris , Martin Meven , Björn Pedersen , Hans Boysen , Reinhard Uecker , Paul Heitjans and Martin Lerch
Published/Copyright: November 20, 2015
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Zeitschrift für Kristallographie - Crystalline Materials
From the journal Zeitschrift für Kristallographie - Crystalline Materials Volume 231 Issue 3

Abstract

γ-Lithium aluminum oxide is a paradigmatic example of an ultraslow lithium ion conductor. This characteristic plays a crucial role in its proposed and actual applications. Herein, we report on the outcome of single-crystal neutron diffraction studies at ambient and high temperature. Careful evaluation confirms the commonly assumed room-temperature structure as derived by powder neutron diffraction in 1965. At 1043 K, a split of the lithium position hints at the onset of intrinsic diffusion. Analysis of the negative scattering-length density using the maximum-entropy method (MEM) indicates a preference for a strongly curved diffusion pathway traversing octahedral voids between adjacent lithium sites. These results help to understand ultraslow lithium diffusion in well-ordered ionic solids on the microscopic scale and, ultimately, to establish structure–property relationships.

Keywords: anisotropic displacement parameters; diffusion pathways; high-temperature neutron diffraction; lithium aluminum oxide; maximum-entropy method
Corresponding author: Dennis Wiedemann, Institut für Chemie, Technische Universität Berlin, Straße des 17. Juni 135, 10623 Berlin, Germany, E-mail:
aPresent address: Karlsruher Institut für Technologie, Institut für Angewandte Materialien (IAM-ESS), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany

Acknowledgments

Financial support by the Deutsche Forschungsgemeinschaft (FOR 1277: “Mobilität von Lithiumionen in Festkörpern [molife]”) is gratefully acknowledged. This work is based on experiments performed at the RESI instrument operated by FRM II and the HEiDi instrument operated by RWTH Aachen and Forschungszentrum Jülich within the JARA-FIT initiative at the Forschungs-Neutronenquelle Heinz Maier-Leibnitz (FRM II), Garching, Germany.

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Received: 2015-9-7
Accepted: 2015-10-26
Published Online: 2015-11-20
Published in Print: 2016-3-1

©2016 by De Gruyter

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https://doi.org/10.1515/zkri-2015-1896
Keywords for this article
anisotropic displacement parameters; diffusion pathways; high-temperature neutron diffraction; lithium aluminum oxide; maximum-entropy method

Articles in the same Issue

  1. Frontmatter
  2. Graphical Synopsis
  3. Inorganic Crystal Structures
  4. SrPt2Al2 – A (3+2)D-incommensurately modulated variant of the CaBe2Ge2 type structure
  5. The modulated structure of intermediate-valent CeCoGa
  6. Organic and Metalorganic Crystal Structures
  7. Serendipitous compositional and structural diversity in urotropine adducts of binary cadmium xanthates
  8. Crystal structures of 2-[5-nitrothien-2-yl)- CH=N–NR–CO(CH2)n]thiophene compounds (R = H or Me; n = 0 or 1)
  9. Molecular structure studies of novel bronchodilatory-active 4-azafluorenes
  10. Letter
  11. Single-crystal neutron diffraction on γ-LiAlO2: structure determination and estimation of lithium diffusion pathway
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