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A type-II clathrate with a Li-Ge framework

Bodo Böhme, Kaya Wei, Matej Bobnar, Yurii Prots, Ulrich Burkhardt, Michael Baitinger, George S. Nolas and Yuri Grin

Abstract

Na16Cs8LixGe136−x (x≈2.8, space group Fdm) is the first intermetallic type-II clathrate with a lithium-substituted framework. The phase was obtained from the elements in sealed Ta ampoules by annealing at 650°C for 5 days. Samples were investigated by synchrotron X-ray powder diffraction, solid-state NMR, microstructure and chemical analysis. The substitution of Ge by Li atoms causes a marked shrinking of the lattice parameter. Studies by 7Li NMR confirmed the presence of Li in the clathrate phase and the 23Na and 133Cs NMR spectra consistently showed distinct changes as compared to the ternary Na16Cs8Ge136. The SEDOR technique revealed a distance between Li and Cs atoms in agreement with the result of crystal structure refinement, indicating Li substitution at site 96g. The distinct Knight shift of all NMR signals implies metallic behaviour of the clathrate phase, measurements of the magnetic susceptibility indicate diamagnetic behaviour.

Acknowledgements

We thank S. Kostmann for the preparation of specimens for microstructure analyses, P. Scheppan and M. Eckert for SEM/EDXS/WDXS experiments, Dr. H. Borrmann and S. Hückmann for laboratory XRPD experiments, Dr. G. Auffermann, U. Schmidt, A. Völzke and S. Schwinger for chemical analyses, and the team of Prof. Dr. A. Fitch at beamline ID22 at ESRF Grenoble, France, for technical support during the synchrotron XRPD experiments.

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Supplemental Material:

The online version of this article (DOI: https://doi.org/10.1515/zkri-2017-2046) offers supplementary material, available to authorized users.

Received: 2017-2-3
Accepted: 2017-4-5
Published Online: 2017-5-4
Published in Print: 2017-7-26

©2017 Walter de Gruyter GmbH, Berlin/Boston