Origin of Intrinsically Low Thermal Conductivity in Talnakhite Cu17.6Fe17.6S32 Thermoelectric Material

Correlations between Lattice Dynamics and Thermal Transport

Hongyao Xie, Xianli Su, Xiaomi Zhang, Shiqiang Hao, Trevor P. Bailey, Constantinos C. Stoumpos, Alexios P. Douvalis, Xiaobing Hu, Christopher Wolverton, Vinayak P. Dravid, Ctirad Uher, Xinfeng Tang, Mercouri G Kanatzidis

Research output: Contribution to journalArticle

Abstract

Understanding the nature of phonon transport in solids and the underlying mechanism linking lattice dynamics and thermal conductivity is important in many fields, including the development of efficient thermoelectric materials where a low lattice thermal conductivity is required. Herein, we choose the pair of synthetic chalcopyrite CuFeS2 and talnakhite Cu17.6Fe17.6S32 compounds, which possess the same elements and very similar crystal structures but very different phonon transport, as contrasting examples to study the influence of lattice dynamics and chemical bonding on the thermal transport properties. Chemically, talnakhite derives from chalcopyrite by inserting extra Cu and Fe atoms in the chalcopyrite lattice. The CuFeS2 compound has a lattice thermal conductivity of 2.37 W m-1 K-1 at 625 K, while Cu17.6Fe17.6S32 features Cu/Fe disorder and possesses an extremely low lattice thermal conductivity of merely 0.6 W m-1 K-1 at 625 K, approaching the amorphous limit κmin. Low-temperature heat capacity measurements and phonon calculations point to a large anharmonicity and low Debye temperature in Cu17.6Fe17.6S32, originating from weaker chemical bonds. Moreover, Mössbauer spectroscopy suggests that the state of Fe atoms in Cu17.6Fe17.6S32 is partially disordered, which induces the enhanced alloy scattering. All of the above peculiar features, absent in CuFeS2, contribute to the extremely low lattice thermal conductivity of the Cu17.6Fe17.6S32 compound.

Original languageEnglish
Pages (from-to)10905-10914
Number of pages10
JournalJournal of the American Chemical Society
Volume141
Issue number27
DOIs
Publication statusPublished - Jun 16 2019

Fingerprint

Thermal Conductivity
Lattice vibrations
Phonons
Thermal conductivity
Hot Temperature
Debye temperature
Atoms
Temperature
Chemical bonds
Transport properties
Specific heat
Spectrum Analysis
Crystal structure
Spectroscopy
Scattering
chalcopyrite

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Origin of Intrinsically Low Thermal Conductivity in Talnakhite Cu17.6Fe17.6S32 Thermoelectric Material : Correlations between Lattice Dynamics and Thermal Transport. / Xie, Hongyao; Su, Xianli; Zhang, Xiaomi; Hao, Shiqiang; Bailey, Trevor P.; Stoumpos, Constantinos C.; Douvalis, Alexios P.; Hu, Xiaobing; Wolverton, Christopher; Dravid, Vinayak P.; Uher, Ctirad; Tang, Xinfeng; Kanatzidis, Mercouri G.

In: Journal of the American Chemical Society, Vol. 141, No. 27, 16.06.2019, p. 10905-10914.

Research output: Contribution to journalArticle

Xie, Hongyao ; Su, Xianli ; Zhang, Xiaomi ; Hao, Shiqiang ; Bailey, Trevor P. ; Stoumpos, Constantinos C. ; Douvalis, Alexios P. ; Hu, Xiaobing ; Wolverton, Christopher ; Dravid, Vinayak P. ; Uher, Ctirad ; Tang, Xinfeng ; Kanatzidis, Mercouri G. / Origin of Intrinsically Low Thermal Conductivity in Talnakhite Cu17.6Fe17.6S32 Thermoelectric Material : Correlations between Lattice Dynamics and Thermal Transport. In: Journal of the American Chemical Society. 2019 ; Vol. 141, No. 27. pp. 10905-10914.
@article{677296699cf048d4aa7a02feb0fcc22a,
title = "Origin of Intrinsically Low Thermal Conductivity in Talnakhite Cu17.6Fe17.6S32 Thermoelectric Material: Correlations between Lattice Dynamics and Thermal Transport",
abstract = "Understanding the nature of phonon transport in solids and the underlying mechanism linking lattice dynamics and thermal conductivity is important in many fields, including the development of efficient thermoelectric materials where a low lattice thermal conductivity is required. Herein, we choose the pair of synthetic chalcopyrite CuFeS2 and talnakhite Cu17.6Fe17.6S32 compounds, which possess the same elements and very similar crystal structures but very different phonon transport, as contrasting examples to study the influence of lattice dynamics and chemical bonding on the thermal transport properties. Chemically, talnakhite derives from chalcopyrite by inserting extra Cu and Fe atoms in the chalcopyrite lattice. The CuFeS2 compound has a lattice thermal conductivity of 2.37 W m-1 K-1 at 625 K, while Cu17.6Fe17.6S32 features Cu/Fe disorder and possesses an extremely low lattice thermal conductivity of merely 0.6 W m-1 K-1 at 625 K, approaching the amorphous limit κmin. Low-temperature heat capacity measurements and phonon calculations point to a large anharmonicity and low Debye temperature in Cu17.6Fe17.6S32, originating from weaker chemical bonds. Moreover, M{\"o}ssbauer spectroscopy suggests that the state of Fe atoms in Cu17.6Fe17.6S32 is partially disordered, which induces the enhanced alloy scattering. All of the above peculiar features, absent in CuFeS2, contribute to the extremely low lattice thermal conductivity of the Cu17.6Fe17.6S32 compound.",
author = "Hongyao Xie and Xianli Su and Xiaomi Zhang and Shiqiang Hao and Bailey, {Trevor P.} and Stoumpos, {Constantinos C.} and Douvalis, {Alexios P.} and Xiaobing Hu and Christopher Wolverton and Dravid, {Vinayak P.} and Ctirad Uher and Xinfeng Tang and Kanatzidis, {Mercouri G}",
year = "2019",
month = "6",
day = "16",
doi = "10.1021/jacs.9b05072",
language = "English",
volume = "141",
pages = "10905--10914",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "27",

}

TY - JOUR

T1 - Origin of Intrinsically Low Thermal Conductivity in Talnakhite Cu17.6Fe17.6S32 Thermoelectric Material

T2 - Correlations between Lattice Dynamics and Thermal Transport

AU - Xie, Hongyao

AU - Su, Xianli

AU - Zhang, Xiaomi

AU - Hao, Shiqiang

AU - Bailey, Trevor P.

AU - Stoumpos, Constantinos C.

AU - Douvalis, Alexios P.

AU - Hu, Xiaobing

AU - Wolverton, Christopher

AU - Dravid, Vinayak P.

AU - Uher, Ctirad

AU - Tang, Xinfeng

AU - Kanatzidis, Mercouri G

PY - 2019/6/16

Y1 - 2019/6/16

N2 - Understanding the nature of phonon transport in solids and the underlying mechanism linking lattice dynamics and thermal conductivity is important in many fields, including the development of efficient thermoelectric materials where a low lattice thermal conductivity is required. Herein, we choose the pair of synthetic chalcopyrite CuFeS2 and talnakhite Cu17.6Fe17.6S32 compounds, which possess the same elements and very similar crystal structures but very different phonon transport, as contrasting examples to study the influence of lattice dynamics and chemical bonding on the thermal transport properties. Chemically, talnakhite derives from chalcopyrite by inserting extra Cu and Fe atoms in the chalcopyrite lattice. The CuFeS2 compound has a lattice thermal conductivity of 2.37 W m-1 K-1 at 625 K, while Cu17.6Fe17.6S32 features Cu/Fe disorder and possesses an extremely low lattice thermal conductivity of merely 0.6 W m-1 K-1 at 625 K, approaching the amorphous limit κmin. Low-temperature heat capacity measurements and phonon calculations point to a large anharmonicity and low Debye temperature in Cu17.6Fe17.6S32, originating from weaker chemical bonds. Moreover, Mössbauer spectroscopy suggests that the state of Fe atoms in Cu17.6Fe17.6S32 is partially disordered, which induces the enhanced alloy scattering. All of the above peculiar features, absent in CuFeS2, contribute to the extremely low lattice thermal conductivity of the Cu17.6Fe17.6S32 compound.

AB - Understanding the nature of phonon transport in solids and the underlying mechanism linking lattice dynamics and thermal conductivity is important in many fields, including the development of efficient thermoelectric materials where a low lattice thermal conductivity is required. Herein, we choose the pair of synthetic chalcopyrite CuFeS2 and talnakhite Cu17.6Fe17.6S32 compounds, which possess the same elements and very similar crystal structures but very different phonon transport, as contrasting examples to study the influence of lattice dynamics and chemical bonding on the thermal transport properties. Chemically, talnakhite derives from chalcopyrite by inserting extra Cu and Fe atoms in the chalcopyrite lattice. The CuFeS2 compound has a lattice thermal conductivity of 2.37 W m-1 K-1 at 625 K, while Cu17.6Fe17.6S32 features Cu/Fe disorder and possesses an extremely low lattice thermal conductivity of merely 0.6 W m-1 K-1 at 625 K, approaching the amorphous limit κmin. Low-temperature heat capacity measurements and phonon calculations point to a large anharmonicity and low Debye temperature in Cu17.6Fe17.6S32, originating from weaker chemical bonds. Moreover, Mössbauer spectroscopy suggests that the state of Fe atoms in Cu17.6Fe17.6S32 is partially disordered, which induces the enhanced alloy scattering. All of the above peculiar features, absent in CuFeS2, contribute to the extremely low lattice thermal conductivity of the Cu17.6Fe17.6S32 compound.

UR - http://www.scopus.com/inward/record.url?scp=85069620773&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85069620773&partnerID=8YFLogxK

U2 - 10.1021/jacs.9b05072

DO - 10.1021/jacs.9b05072

M3 - Article

VL - 141

SP - 10905

EP - 10914

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 27

ER -