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.

doi:10.1021/jacs.9b05072

Title: Origin of Intrinsically Low Thermal Conductivity in Talnakhite Cu_17.6Fe_17.6S₃₂ Thermoelectric Material: Correlations between Lattice Dynamics and Thermal Transport

Journal Article · 15 June 2019 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.9b05072 · OSTI ID:1777380

^[1];

^[2]; Zhang, Xiaomi ^[3];

^[3]; Bailey, Trevor P. ^[4];

^[3]; Douvalis, Alexios P. ^[5];

^[3];

^[3]; Uher, Ctirad ^[4];

^[6];

^[3]

Wuhan Univ. of Technology (China); Northwestern Univ., Evanston, IL (United States); Northwestern University
Wuhan Univ. of Technology (China); Northwestern Univ., Evanston, IL (United States)
Northwestern Univ., Evanston, IL (United States)
Univ. of Michigan, Ann Arbor, MI (United States)
Univ. of Ioannina (Greece)
Wuhan Univ. of Technology (China)

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 Cu_17.6Fe_17.6S₃₂ 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 Cu_17.6Fe_17.6S₃₂ 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 Cu_17.6Fe_17.6S₃₂, originating from weaker chemical bonds. Moreover, Mössbauer spectroscopy suggests that the state of Fe atoms in Cu_17.6Fe_17.6S₃₂ 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 Cu_17.6Fe_17.6S₃₂ compound.

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Research Organization:: Northwestern Univ., Evanston, IL (United States)

Sponsoring Organization:: 111 Project of China; Natural Science Foundation of China; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0014520

OSTI ID:: 1777380

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 27 Vol. 141; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (58)

Charge-Compensated Compound Defects in Ga-containing Thermoelectric Skutterudites Qiu, Yuting; Xi, Lili; Shi, Xun Advanced Functional Materials, Vol. 23, Issue 25 https://doi.org/10.1002/adfm.201202571	journal	February 2013
Beneficial Contribution of Alloy Disorder to Electron and Phonon Transport in Half-Heusler Thermoelectric Materials Xie, Hanhui; Wang, Heng; Pei, Yanzhong Advanced Functional Materials, Vol. 23, Issue 41 https://doi.org/10.1002/adfm.201300663	journal	April 2013
Atomic Disorders Induced by Silver and Magnesium Ion Migrations Favor High Thermoelectric Performance in α-MgAgSb-Based Materials Li, Dandan; Zhao, Huaizhou; Li, Shanming Advanced Functional Materials, Vol. 25, Issue 41 https://doi.org/10.1002/adfm.201503022	journal	September 2015
Hierarchical Chemical Bonds Contributing to the Intrinsically Low Thermal Conductivity in α-MgAgSb Thermoelectric Materials Ying, Pingjun; Li, Xin; Wang, Yancheng Advanced Functional Materials, Vol. 27, Issue 1 https://doi.org/10.1002/adfm.201604145	journal	October 2016
High Thermoelectric Performance in the Wide Band‐Gap AgGa _1‐ _x Te ₂ Compounds: Directional Negative Thermal Expansion and Intrinsically Low Thermal Conductivity Su, Xianli; Zhao, Na; Hao, Shiqiang Advanced Functional Materials, Vol. 29, Issue 6 https://doi.org/10.1002/adfm.201806534	journal	December 2018
Low Sound Velocity Contributing to the High Thermoelectric Performance of Ag ₈ SnSe ₆ Li, Wen; Lin, Siqi; Ge, Binghui Advanced Science, Vol. 3, Issue 11 https://doi.org/10.1002/advs.201600196	journal	July 2016
Mechanically Robust BiSbTe Alloys with Superior Thermoelectric Performance: A Case Study of Stable Hierarchical Nanostructured Thermoelectric Materials Zheng, Yun; Zhang, Qiang; Su, Xianli Advanced Energy Materials, Vol. 5, Issue 5 https://doi.org/10.1002/aenm.201401391	journal	November 2014
Progressive Regulation of Electrical and Thermal Transport Properties to High-Performance CuInTe ₂ Thermoelectric Materials Luo, Yubo; Yang, Junyou; Jiang, Qinghui Advanced Energy Materials, Vol. 6, Issue 12 https://doi.org/10.1002/aenm.201600007	journal	April 2016
The Role of Zn in Chalcopyrite CuFeS ₂ : Enhanced Thermoelectric Properties of Cu _1- _x Zn _x FeS ₂ with In Situ Nanoprecipitates Xie, Hongyao; Su, Xianli; Zheng, Gang Advanced Energy Materials, Vol. 7, Issue 3 https://doi.org/10.1002/aenm.201601299	journal	October 2016
Specific Heats at Low Temperatures Gopal, E. S. R. https://doi.org/10.1007/978-1-4684-9081-7	book	January 1966
Introduction to Thermoelectricity Goldsmid, H. Julian Springer Series in Materials Science https://doi.org/10.1007/978-3-662-49256-7	book	January 2016
Mössbauer study of antiferromagnetic CuFeS2 Ok, Hang Nam; Kim, Chul Sung Il Nuovo Cimento B, Vol. 28, Issue 1 https://doi.org/10.1007/BF02722811	journal	July 1975
Synthesis, structural and magnetic properties of self-organized single-crystalline nanobricks of chalcopyrite CuFeS2 Lyubutin, Igor S.; Lin, Chun-Rong; Starchikov, Sergey S. Acta Materialia, Vol. 61, Issue 11 https://doi.org/10.1016/j.actamat.2013.03.009	journal	June 2013
Ultralow thermal conductivity of β -Cu2Se by atomic fluidity and structure distortion Kim, Hyoungchul; Ballikaya, Sedat; Chi, Hang Acta Materialia, Vol. 86 https://doi.org/10.1016/j.actamat.2014.12.008	journal	March 2015
Synthesis and property evaluation of CuFeS2−x as earth-abundant and environmentally-friendly thermoelectric materials Li, Jianhui; Tan, Qing; Li, Jing-Feng Journal of Alloys and Compounds, Vol. 551 https://doi.org/10.1016/j.jallcom.2012.09.067	journal	February 2013
Thermoelectric properties of n-type cobalt doped chalcopyrite Cu1−xCoxFeS2 and p-type eskebornite CuFeSe2 Berthebaud, D.; Lebedev, O. I.; Maignan, A. Journal of Materiomics, Vol. 1, Issue 1 https://doi.org/10.1016/j.jmat.2015.03.007	journal	March 2015
Reduction of thermal conductivity by low energy multi-Einstein optic modes Liu, Huili; Yang, Jiong; Shi, Xun Journal of Materiomics, Vol. 2, Issue 2 https://doi.org/10.1016/j.jmat.2016.05.006	journal	June 2016
Cu and Fe valence states in CuFeS2 Boekema, C.; Krupski, A. M.; Varasteh, M. Journal of Magnetism and Magnetic Materials, Vol. 272-276 https://doi.org/10.1016/j.jmmm.2003.11.206	journal	May 2004
High Thermoelectric Performance and Enhanced Mechanical Stability of p -type Ge _{1– x} Sb _x Te Perumal, Suresh; Roychowdhury, Subhajit; Negi, Devendra S. Chemistry of Materials, Vol. 27, Issue 20 https://doi.org/10.1021/acs.chemmater.5b03434	journal	October 2015
Rationally Designing High-Performance Bulk Thermoelectric Materials Tan, Gangjian; Zhao, Li-Dong; Kanatzidis, Mercouri G. Chemical Reviews, Vol. 116, Issue 19 https://doi.org/10.1021/acs.chemrev.6b00255	journal	August 2016
Nonmagnetic In Substituted CuFe _{1– x} In _x S ₂ Solid Solution Thermoelectric Xie, Hongyao; Su, Xianli; Zheng, Gang The Journal of Physical Chemistry C, Vol. 120, Issue 49 https://doi.org/10.1021/acs.jpcc.6b10308	journal	December 2016
Thermoelectric Properties of Ga/Ag Codoped Type-III Ba ₂₄ Ge ₁₀₀ Clathrates with in Situ Nanostructures Fu, Jiefei; Su, Xianli; Zheng, Yun ACS Applied Materials & Interfaces, Vol. 7, Issue 34 https://doi.org/10.1021/acsami.5b04910	journal	August 2015
Structure and Transport Properties of Double-Doped CoSb _2.75 Ge _{0.25– x} Te _x ( x = 0.125–0.20) with in Situ Nanostructure Su, Xianli; Li, Han; Wang, Guoyu Chemistry of Materials, Vol. 23, Issue 11 https://doi.org/10.1021/cm200560s	journal	June 2011
High Performance α-MgAgSb Thermoelectric Materials for Low Temperature Power Generation Ying, Pingjun; Liu, Xiaohua; Fu, Chenguang Chemistry of Materials, Vol. 27, Issue 3 https://doi.org/10.1021/cm5041826	journal	January 2015
Anisotropic Multicenter Bonding and High Thermoelectric Performance in Electron-Poor CdSb Wang, Shanyu; Yang, Jiong; Wu, Lihua Chemistry of Materials, Vol. 27, Issue 3 https://doi.org/10.1021/cm504398d	journal	January 2015
Preparation and characterization of the system copper gallium iron sulfide (CuGa1-xFexS2) DiGiuseppe, M.; Steger, J.; Wold, A. Inorganic Chemistry, Vol. 13, Issue 8 https://doi.org/10.1021/ic50138a009	journal	August 1974
Multiple-Filled Skutterudites: High Thermoelectric Figure of Merit through Separately Optimizing Electrical and Thermal Transports Shi, Xun; Yang, Jiong; Salvador, James R. Journal of the American Chemical Society, Vol. 133, Issue 20 https://doi.org/10.1021/ja111199y	journal	May 2011
High Performance Thermoelectrics from Earth-Abundant Materials: Enhanced Figure of Merit in PbS by Second Phase Nanostructures Zhao, Li-Dong; Lo, Shih-Han; He, Jiaqing Journal of the American Chemical Society, Vol. 133, Issue 50 https://doi.org/10.1021/ja208658w	journal	December 2011
High Thermoelectric Performance of p-Type SnTe via a Synergistic Band Engineering and Nanostructuring Approach Tan, Gangjian; Zhao, Li-Dong; Shi, Fengyuan Journal of the American Chemical Society, Vol. 136, Issue 19 https://doi.org/10.1021/ja500860m	journal	May 2014
Realizing High Figure of Merit in Phase-Separated Polycrystalline Sn _{1– x} Pb _x Se Tang, Guodong; Wei, Wei; Zhang, Jian Journal of the American Chemical Society, Vol. 138, Issue 41 https://doi.org/10.1021/jacs.6b07010	journal	October 2016
Intrinsic Rattler-Induced Low Thermal Conductivity in Zintl Type TlInTe ₂ Jana, Manoj K.; Pal, Koushik; Warankar, Avinash Journal of the American Chemical Society, Vol. 139, Issue 12 https://doi.org/10.1021/jacs.7b01434	journal	March 2017
Identifying the Specific Nanostructures Responsible for the High Thermoelectric Performance of (Bi,Sb) ₂ Te ₃ Nanocomposites Xie, Wenjie; He, Jian; Kang, Hye Jung Nano Letters, Vol. 10, Issue 9 https://doi.org/10.1021/nl100804a	journal	September 2010
Thermoelectric performance of CuFeS2+2x composites prepared by rapid thermal explosion Xie, Hongyao; Su, Xianli; Yan, Yonggao NPG Asia Materials, Vol. 9, Issue 6 https://doi.org/10.1038/am.2017.80	journal	June 2017
Convergence of electronic bands for high performance bulk thermoelectrics Pei, Yanzhong; Shi, Xiaoya; LaLonde, Aaron Nature, Vol. 473, Issue 7345, p. 66-69 https://doi.org/10.1038/nature09996	journal	May 2011
High-performance bulk thermoelectrics with all-scale hierarchical architectures Biswas, Kanishka; He, Jiaqing; Blum, Ivan D. Nature, Vol. 489, Issue 7416, p. 414-418 https://doi.org/10.1038/nature11439	journal	September 2012
Ultralow thermal conductivity and high thermoelectric figure of merit in SnSe crystals Zhao, Li-Dong; Lo, Shih-Han; Zhang, Yongsheng Nature, Vol. 508, Issue 7496, p. 373-377 https://doi.org/10.1038/nature13184	journal	April 2014
Realizing high figure of merit in heavy-band p-type half-Heusler thermoelectric materials Fu, Chenguang; Bai, Shengqiang; Liu, Yintu Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms9144	journal	September 2015
Complex thermoelectric materials Snyder, G. Jeffrey; Toberer, Eric S. Nature Materials, Vol. 7, Issue 2, p. 105-114 https://doi.org/10.1038/nmat2090	journal	February 2008
Copper ion liquid-like thermoelectrics Liu, Huili; Shi, Xun; Xu, Fangfang Nature Materials, Vol. 11, Issue 5, p. 422-425 https://doi.org/10.1038/nmat3273	journal	March 2012
Low effective mass and carrier concentration optimization for high performance p-type Mg _2(1−x) Li _2x Si _0.3 Sn _0.7 solid solutions Zhang, Qiang; Cheng, Long; Liu, Wei Phys. Chem. Chem. Phys., Vol. 16, Issue 43 https://doi.org/10.1039/C4CP03468F	journal	January 2014
Electronegative guests in CoSb ₃ Duan, Bo; Yang, Jiong; Salvador, James R. Energy & Environmental Science, Vol. 9, Issue 6 https://doi.org/10.1039/C6EE00322B	journal	January 2016
High thermoelectric performance in Te-free (Bi,Sb) ₂ Se ₃ via structural transition induced band convergence and chemical bond softening Wang, Shanyu; Sun, Yongxing; Yang, Jiong Energy & Environmental Science, Vol. 9, Issue 11 https://doi.org/10.1039/C6EE02674E	journal	January 2016
Enhanced thermoelectric properties of n-type Mg2.16(Si0.4Sn0.6)1−ySby due to nano-sized Sn-rich precipitates and an optimized electron concentration Liu, Wei; Tang, Xinfeng; Li, Han Journal of Materials Chemistry, Vol. 22, Issue 27 https://doi.org/10.1039/c2jm31919e	journal	January 2012
Thermoelectric transport properties of diamond-like Cu _1−x Fe _1+x S ₂ tetrahedral compounds Li, Yulong; Zhang, Tiansong; Qin, Yuting Journal of Applied Physics, Vol. 116, Issue 20 https://doi.org/10.1063/1.4902849	journal	November 2014
Part-crystalline part-liquid state and rattling-like thermal damping in materials with chemical-bond hierarchy Qiu, Wujie; Xi, Lili; Wei, Ping Proceedings of the National Academy of Sciences, Vol. 111, Issue 42 https://doi.org/10.1073/pnas.1410349111	journal	October 2014
IMSG09: A ⁵⁷ Fe- ¹¹⁹ Sn Mössbauer spectra computer fitting program with novel interactive user interface Douvalis, A. P.; Polymeros, A.; Bakas, T. Journal of Physics: Conference Series, Vol. 217 https://doi.org/10.1088/1742-6596/217/1/012014	journal	March 2010
Model for Lattice Thermal Conductivity at Low Temperatures Callaway, Joseph Physical Review, Vol. 113, Issue 4 https://doi.org/10.1103/PhysRev.113.1046	journal	February 1959
Effect of Point Imperfections on Lattice Thermal Conductivity Callaway, Joseph; von Baeyer, Hans C. Physical Review, Vol. 120, Issue 4 https://doi.org/10.1103/PhysRev.120.1149	journal	November 1960
Lower limit to the thermal conductivity of disordered crystals Cahill, David G.; Watson, S. K.; Pohl, R. O. Physical Review B, Vol. 46, Issue 10, p. 6131-6140 https://doi.org/10.1103/PhysRevB.46.6131	journal	September 1992
Iron valence in skutterudites: Transport and magnetic properties of Co 1 − x Fe x Sb 3 Yang, J.; Meisner, G. P.; Morelli, D. T. Physical Review B, Vol. 63, Issue 1 https://doi.org/10.1103/PhysRevB.63.014410	journal	December 2000
Intrinsically Minimal Thermal Conductivity in Cubic I−V−VI2 Semiconductors Morelli, D. T.; Jovovic, V.; Heremans, J. P. Physical Review Letters, Vol. 101, Issue 3, Article No. 035901 https://doi.org/10.1103/PhysRevLett.101.035901	journal	July 2008
Role of Lone-Pair Electrons in Producing Minimum Thermal Conductivity in Nitrogen-Group Chalcogenide Compounds Skoug, Eric J.; Morelli, Donald T. Physical Review Letters, Vol. 107, Issue 23 https://doi.org/10.1103/PhysRevLett.107.235901	journal	November 2011
Convergence of Conduction Bands as a Means of Enhancing Thermoelectric Performance of n -Type Mg 2 Si 1 − x Sn x Solid Solutions Liu, Wei; Tan, Xiaojian; Yin, Kang Physical Review Letters, Vol. 108, Issue 16 https://doi.org/10.1103/PhysRevLett.108.166601	journal	April 2012
Glasslike Heat Conduction in High-Mobility Crystalline Semiconductors Cohn, J. L.; Nolas, G. S.; Fessatidis, V. Physical Review Letters, Vol. 82, Issue 4 https://doi.org/10.1103/PhysRevLett.82.779	journal	January 1999
Ultrahigh power factor and thermoelectric performance in hole-doped single-crystal SnSe Zhao, L.-D.; Tan, G.; Hao, S. Science, Vol. 351, Issue 6269, p. 141-144 https://doi.org/10.1126/science.aad3749	journal	November 2015
Advances in thermoelectric materials research: Looking back and moving forward He, Jian; Tritt, Terry M. Science, Vol. 357, Issue 6358 https://doi.org/10.1126/science.aak9997	journal	September 2017
Thermoelectric Materials, Phenomena, and Applications: A Bird's Eye View Tritt, Terry M.; Subramanian, M. A. MRS Bulletin, Vol. 31, Issue 3 https://doi.org/10.1557/mrs2006.44	journal	March 2006
High Thermoelectric Power Factor in a Carrier-Doped Magnetic Semiconductor CuFeS ₂ Tsujii, Naohito; Mori, Takao Applied Physics Express, Vol. 6, Issue 4 https://doi.org/10.7567/APEX.6.043001	journal	April 2013

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Title: Origin of Intrinsically Low Thermal Conductivity in Talnakhite Cu17.6Fe17.6S32 Thermoelectric Material: Correlations between Lattice Dynamics and Thermal Transport

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Title: Origin of Intrinsically Low Thermal Conductivity in Talnakhite Cu_17.6Fe_17.6S₃₂ Thermoelectric Material: Correlations between Lattice Dynamics and Thermal Transport