A novel crystallographic location of rattling atoms in filled Eu
x
Co4Sb12 skutterudites prepared under high-pressure conditions

João Elias F. S. Rodrigues; Javier Gainza; Federico Serrano-Sánchez; Norbert M. Nemes; Oscar J. Dura; Jose Luis Martínez; Jose Antonio Alonso

doi:10.1515/zkri-2022-0051

Published by De Gruyter (O) December 12, 2022

A novel crystallographic location of rattling atoms in filled Eu_xCo₄Sb₁₂ skutterudites prepared under high-pressure conditions

João Elias F. S. Rodrigues , Javier Gainza , Federico Serrano-Sánchez , Norbert M. Nemes , Oscar J. Dura , Jose Luis Martínez and Jose Antonio Alonso

From the journal Zeitschrift für Kristallographie - Crystalline Materials

https://doi.org/10.1515/zkri-2022-0051

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Abstract

Thermoelectric M_xCo₄Sb₁₂ skutterudites are well-known to exhibit a reduced thermal conductivity thanks to the rattling effect of the M-filler at the large cages occurring in the framework, centered at the 2a sites of the I m 3 ‾ space group. A novel Eu-filled skutterudite has been synthesized under high-pressure conditions at 3.5 GPa in a piston-cylinder hydrostatic press. The structural refinement from high-angular resolution synchrotron X-ray diffraction (SXRD) patterns unveils an unusual position for Eu filler atoms. By difference Fourier synthesis they are found at 12d sites, conforming statistically occupied octahedra within the mentioned cages around 2a positions. The Debye temperature was estimated by averaging the isotropic displacements by the atomic masses, leading to θ D of 273(2) K. Oftedal plots concerning the y and z Sb fractional positions, the unit-cell parameter a and M filling fraction include the novel Eu specimen in the trend observed for other filled materials prepared under high-pressure, including rare-earths, alkali or alkali-earth elements, all accepted as rattlers in filled skutterudites. A total thermal conductivity (κ) of 0.82 W m⁻¹ K⁻¹ is measured at 773 K for Eu_0.02(1)Co₄Sb₁₂, below that of other filled skutterudites, which is promoted by the enhanced phonon scattering of Eu located at 12d sites. FE-SEM images showed large, homogeneous grains, well compacted after the high-pressure synthesis.

Keywords: filled skutterudites; synchrotron X-ray powder diffraction; thermal conductivity reduction; thermoelectrics

Corresponding author: Jose Antonio Alonso, Instituto de Ciencia de Materiales de Madrid (ICMM), Consejo Superior de Investigaciones Científicas (CSIC), Sor Juana Inés de la Cruz 3, E-28049, Madrid, Spain, E-mail: ja.alonso@icmm.csic.es

Acknowledgements

All the authors thank the Spanish Ministry for Science and Innovation (MCIN/AEI/10.13039/501100011033) for funding the project numbers: PID2021-122477OB-I00 and TED2021-129254B-C22. J.G. thanks MICINN for granting the contract PRE2018-083398. The authors wish to express their gratitude to ALBA technical staff for making the facilities available for the synchrotron X-ray diffraction experiment number 2017072260.

Author contributions: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.
Research funding: None declared.
Conflict of interest statement: There are no conflicts to declare.

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Supplementary Material

The online version of this article offers supplementary material (https://doi.org/10.1515/zkri-2022-0051).

Received: 2022-08-30

Accepted: 2022-11-14

Published Online: 2022-12-12

Published in Print: 2023-01-27

A novel crystallographic location of rattling atoms in filled Eu_xCo₄Sb₁₂ skutterudites prepared under high-pressure conditions

Abstract

Acknowledgements

References

Supplementary Material

Journal and Issue

Articles in the same Issue

A novel crystallographic location of rattling atoms in filled Eu x Co4Sb12 skutterudites prepared under high-pressure conditions

Abstract

Acknowledgements

References

Supplementary Material

Journal and Issue

Articles in the same Issue

A novel crystallographic location of rattling atoms in filled Eu_xCo₄Sb₁₂ skutterudites prepared under high-pressure conditions