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Impact of Noble-Gas Filler Atoms on the Lattice Thermal Conductivity of CoSb3 Skutterudites: First-Principles Modelling

preprint
submitted on 12.11.2020, 11:12 and posted on 16.11.2020, 05:17 by Jianqin Tang, Jonathan Skelton
We present a systematic first-principles modelling study of the structural dynamics and thermal transport in the CoSb3 skutterudites with a series of noble-gas filler atoms. A range of analysis techniques are proposed to estimate the filler rattling frequencies, to quantify the separate impacts of filling on the phonon group velocities and lifetimes, and to show how changes to the phonon spectra and interaction strengths lead to suppressed lifetimes. The fillers are found to reduce the thermal conductivity of the CoSb3 framework by up to 15 % primarily by suppressing the group velocities of low-lying optic modes. Calculations show that the filler rattling frequencies are determined by a detailed balance of increasing atomic mass and stronger interactions with the framework, and are a good predictor of their impact on the heat transport. Lowering the rattling frequency below ~1.5 THz by selecting heavy fillers that interact weakly with the framework is predicted to produce a much larger suppression of the thermal transport, by inducing avoided crossings in the acoustic-mode dispersion and facilitating resonant scattering with a consequent large reduction in the lifetimes. Approximate rattling frequencies determined from the harmonic force constants may therefore provide a useful metric for selecting filler atoms to optimise the thermal transport in skutterudites and other cage compounds such as clathrates.

Funding

MR/T043121/1

MATERIALS CHEMISTRY HIGH END COMPUTING CONSORTIUM

Engineering and Physical Sciences Research Council

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HIGH END COMPUTING MATERIALS CHEMISTRY CONSORTIUM

Engineering and Physical Sciences Research Council

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History

Email Address of Submitting Author

jonathan.skelton@manchester.ac.uk

Institution

University of Manchester

Country

United Kingdom

ORCID For Submitting Author

0000-0002-0395-1202

Declaration of Conflict of Interest

No conflict of interest.

Version Notes

Initial submission.

Licence

Exports