skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Intrinsically low thermal conductivity from a quasi-one-dimensional crystal structure and enhanced electrical conductivity network via Pb doping in SbCrSe 3

Abstract

The development of new routes for the production of thermoelectric materials with low-cost and high-performance characteristics has been one of the long-term strategies for saving and harvesting thermal energy. We report a new approach for improving thermoelectric properties by employing the intrinsically low thermal conductivity of a quasi-one-dimensional (quasi-1D) crystal structure and optimizing the power factor with aliovalent ion doping. As an example, we demonstrated that SbCrSe 3, in which two parallel chains of CrSe 6 octahedra are linked by antimony atoms, possesses a quasi-1D property that resulted in an ultra-low thermal conductivity of 0.56 W m -1 K -1 at 900 K. After maximizing the power factor by Pb doping, the peak ZT value of the optimized Pb-doped sample reached 0.46 at 900 K, which is an enhancement of 24 times that of the parent SbCrSe 3 structure. The mechanisms that lead to low thermal conductivity derive from anharmonic phonons with the presence of the lone-pair electrons of Sb atoms and weak bonds between the CrSe 6 double chains. Our results shed new light on the design of new and high-performance thermoelectric materials.

Authors:
 [1];  [2];  [2]; ORCiD logo [3];  [2];  [2];  [4];  [5];  [6];  [7];  [2]
  1. Chinese Academy of Sciences (CAS), Beijing (China). Congqing Inst. of Green and Intelligent Technology; Chongqing Univ. (China). Colleg of Chemistry and Chemical Engineering; Beijing Univ. of Technology, Beijing (China). Inst. of Microstructure and Properties of Advanced Materials
  2. Chongqing Univ. (China). College of Physics
  3. Chinese Academy of Sciences (CAS), Shanghai (China). Shanghai Inst. of Ceramics
  4. Univ. of Michigan, Ann Arbor, MI (United States). Dept. of Physics
  5. Beijing Univ. of Technology, Beijing (China). Inst. of Microstructure and Properties of Advanced Materials
  6. Chinese Academy of Sciences (CAS), Beijing (China). Congqing Inst. of Green and Intelligent Technology; Univ. of Chinese Academy of Sciences, Beijing (China)
  7. Chongqing Univ. (China). Colleg of Chemistry and Chemical Engineering
Publication Date:
Research Org.:
Univ. of Michigan, Ann Arbor, MI (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1374887
Grant/Contract Number:
PI0000012
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
NPG Asia Materials (Online)
Additional Journal Information:
Journal Name: NPG Asia Materials (Online); Journal Volume: 9; Journal Issue: 6; Journal ID: ISSN 1884-4057
Publisher:
Nature Publishing Group Asia
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Yang, Dingfeng, Yao, Wei, Yan, Yanci, Qiu, Wujie, Guo, Lijie, Lu, Xu, Uher, Ctirad, Han, Xiaodong, Wang, Guoyu, Yang, Tao, and Zhou, Xiaoyuan. Intrinsically low thermal conductivity from a quasi-one-dimensional crystal structure and enhanced electrical conductivity network via Pb doping in SbCrSe3. United States: N. p., 2017. Web. doi:10.1038/am.2017.77.
Yang, Dingfeng, Yao, Wei, Yan, Yanci, Qiu, Wujie, Guo, Lijie, Lu, Xu, Uher, Ctirad, Han, Xiaodong, Wang, Guoyu, Yang, Tao, & Zhou, Xiaoyuan. Intrinsically low thermal conductivity from a quasi-one-dimensional crystal structure and enhanced electrical conductivity network via Pb doping in SbCrSe3. United States. doi:10.1038/am.2017.77.
Yang, Dingfeng, Yao, Wei, Yan, Yanci, Qiu, Wujie, Guo, Lijie, Lu, Xu, Uher, Ctirad, Han, Xiaodong, Wang, Guoyu, Yang, Tao, and Zhou, Xiaoyuan. Fri . "Intrinsically low thermal conductivity from a quasi-one-dimensional crystal structure and enhanced electrical conductivity network via Pb doping in SbCrSe3". United States. doi:10.1038/am.2017.77. https://www.osti.gov/servlets/purl/1374887.
@article{osti_1374887,
title = {Intrinsically low thermal conductivity from a quasi-one-dimensional crystal structure and enhanced electrical conductivity network via Pb doping in SbCrSe3},
author = {Yang, Dingfeng and Yao, Wei and Yan, Yanci and Qiu, Wujie and Guo, Lijie and Lu, Xu and Uher, Ctirad and Han, Xiaodong and Wang, Guoyu and Yang, Tao and Zhou, Xiaoyuan},
abstractNote = {The development of new routes for the production of thermoelectric materials with low-cost and high-performance characteristics has been one of the long-term strategies for saving and harvesting thermal energy. We report a new approach for improving thermoelectric properties by employing the intrinsically low thermal conductivity of a quasi-one-dimensional (quasi-1D) crystal structure and optimizing the power factor with aliovalent ion doping. As an example, we demonstrated that SbCrSe3, in which two parallel chains of CrSe6 octahedra are linked by antimony atoms, possesses a quasi-1D property that resulted in an ultra-low thermal conductivity of 0.56 W m-1 K-1 at 900 K. After maximizing the power factor by Pb doping, the peak ZT value of the optimized Pb-doped sample reached 0.46 at 900 K, which is an enhancement of 24 times that of the parent SbCrSe3 structure. The mechanisms that lead to low thermal conductivity derive from anharmonic phonons with the presence of the lone-pair electrons of Sb atoms and weak bonds between the CrSe6 double chains. Our results shed new light on the design of new and high-performance thermoelectric materials.},
doi = {10.1038/am.2017.77},
journal = {NPG Asia Materials (Online)},
number = 6,
volume = 9,
place = {United States},
year = {Fri Jun 09 00:00:00 EDT 2017},
month = {Fri Jun 09 00:00:00 EDT 2017}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 2works
Citation information provided by
Web of Science

Save / Share:
  • The thermoelectric properties of Pb5Bi6Se14, a member of the cannizzarite homologous series; Pb3Bi2S6, a member of the lillianite homologous series; and PbBi2S4, a member of the galenobismuthite homologous series were investigated over the temperature range of 300 K to 723 K. The samples were synthesized by a solid state reaction of the binary precursors PbQ and Bi(2)Q(3) (Q = S and Se) in evacuated and sealed quartz tubes, followed by pulsed electric current sintering. The crystal structure of Pb5Bi6Se14 consists of alternating two-dimensional infinite layers of PbSe and Bi2Se3. In the Pb5Bi6Se14 sintered compacts, the ab-plane was preferentially oriented perpendicularmore » to the pressing direction, resulting in highly anisotropic electrical and thermal transport properties. The crystal structure of Pb3Bi2S6 is formed by stacking NaCl-type (Pb/Bi) S layers with a mirror as twinning operation, while that of PbBi2S4 consists of the NaCl-type and Bi2S3-type strips (broken layers) of finite widths. The crystal grains of Pb3Bi2S6 and PbBi2S4 were grown randomly, leading to nearly isotropic electrical and thermal transport properties in the sintered compacts. For all the samples, an n-type degenerate semiconductor-like behavior was found, providing a notable thermoelectric power factor of similar to 3.0 mu W K-2 cm(-1) at 705 K for Pb5Bi6Se14, similar to 2.4 mu W K-2 cm(-1) at 715 K for Pb3Bi2S6, and similar to 2.6 mu W K-2 cm(-1) at 515 K for PbBi2S4 in a direction perpendicular to the pressing direction. Moreover, these materials exhibited effective phonon scattering, presumably at the interfaces between the layers, leading to extremely low lattice thermal conductivity in the range of 0.29 W K-1 m(-1) to 0.80 W K-1 m(-1) over the temperature range of 300 K to 723 K. The highest ZT of similar to 0.46 at 705 K was observed in Pb5Bi6Se14 for the ab-plane direction.« less
  • The structure of La{sub 3}MoO{sub 7} was solved in P2{sub 1}2{sub 1}2{sub 1} with Z = 4 and a = 7.597(1) {angstrom}, b = 7.7192(4) {angstrom}, and c = 11.0953(8) {angstrom} and refined to the reliability factors of R(F) = 0.0366 and wR (F2) = 0.0782 for 102 variables and 5352 reflections. A structural feature of interest is the presence of zigzag chains of trans-corner-sharing octahedra of composition MoO{sub 5}{sup 5{minus}} parallel to the b-axis. Resistivity data taken along the b-axis direction show semiconducting behavior in the range 140 to 298 K with an activation energy of 0.16 eV. Themore » magnetic susceptibility is quite complex. The main feature is a broad maximum at 655 K which is interpreted as due to intrachain spin correlations of the Mo(5+) ions. Assuming the S = 1/2 Heisenberg model this implies a J/k= -511 K. Several other anomalies are observed at 483, 140, and 100 K. Differential scanning calorimetry data also show the 483 K feature and disclose another at 373 K not seen in the susceptibility. There is no evidence from powder neutron diffraction data of any structural changes from 298 to 10 K but no data are available above room temperature. There is an indication from neutron diffraction data for the onset of long-range antiferromagnetic order below 100 K.« less
  • Electrochemical oxidation of (triazatetrabenzoporphyrinato)nickel(II) or (triazatetrabenzoporphyrinato)copper(II), Ni(tatbp) or Cu(tatbp), dissolved in 1-chloronaphthalene in the presence of the perrhenate ion affords the new molecular conductors (Ni(tatbp)){sub 3}(ReO{sub 4}){sub 2}{center dot}C{sub 10}H{sub 7}Cl and (Cu(tatbp)){sub 3}(ReO{sub 4}){sub 2}{center dot}C{sup 10}H{sub 7}Cl. The isostructural compounds are composed of partially ligand-oxidized (+2/3) M(tatbp) molecules that form trimerized stacks. Trimerization of the conducting stacks renders the compounds semiconductors with conductivity along the needle axis (crystallographic a) in the range of 2.5 {times} 10{sup {minus}4}-3.0 {times} 10{sup {minus}4} {Omega}{sup {minus}1} cm{sup {minus}1} and an activation energy for conduction in the range of 0.24-0.26 eV. Magnetic susceptibilitymore » measurements on the Ni(II) derivative show that the valence band has the diamagnetic ground state expected for a semiconductor. Nonetheless, the valence-band electrons are shown to mediate a strong intratrimer Cu-Cu coupling characterized by a Weiss constant {Theta} = {minus}5.2 K in the Cu(II) analogue. The magnetic properties are rationalized in terms of a band structure derived by considering the trimers as weakly interacting supermolecules, with {Theta} dominated by intratrimer interactions. A structure determination was performed on the Cu(II) analogue.« less
  • A novel one-dimensional copper (II) chlorophosphate, Na{sub 3}[CuO(HPO{sub 4})Cl] has been prepared by using the low-temperature flux method. It crystallizes in the orthorhombic system, space group Pnma, a=11.096(2), b=6.5703(13) and c=8.3623(17)A, V=609.7(2)A{sup 3}, Z=4. Its crystal structure presents a one-dimensional character in such a way that the edge-sharing CuO{sub 4}Cl{sub 2} building blocks yield a novel linear octahedral chains via Cu-O-Cu and Cu-Cl-Cu bridges. The HPO{sub 4} groups, as the modifier, are grafted onto these chains and sodium ions are located between the chains to satisfy the charge balance. The magnetic susceptibility obeys a Curie-Weiss law above 120K with C=0.38more » (emuK)/mol and {theta}=-150K, showing the Cu{sup 2+} character and antiferromagnetic interactions.« less
  • Na{sub 2}OsO{sub 4} crystals were grown by a NaCl flux method under high pressure. It crystallizes in the Ca{sub 2}IrO{sub 4}-type structure without having additional elements or metal vacancies, which are usually accommodated. It appears that Na{sub 2}OsO{sub 4} is a metal-stoichiometric Ca{sub 2}IrO{sub 4}-type compound never been synthesized to date. Na{sub 2}OsO{sub 4} has the octahedral environment of Os{sup 6+}O{sub 6} so that the electronic configuration is 5d{sup 2}, suggesting the magnetic S=1 ground state. However, magnetization, electrical resistivity, and specific heat measurements indicated that the non-magnetic S=0 state is much likely for Na{sub 2}OsO{sub 4} than the S=1more » state. Band structure calculations and the structure analysis found that the disagreement is probably due to the statically uniaxial compression of the OsO{sub 6} octahedra, resulting in splitting of the t{sub 2{sub g}} band.« less