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Title: High-performance n-type YbxCo4Sb12: from partially filled skutterudites towards composite thermoelectrics

Abstract

The filling fraction limit (FFL) of skutterudites, that is, the complex balance of formation enthalpies among different species, is an intricate but crucial parameter for achieving high thermoelectric performance. In this work, we synthesized a series of YbxCo4Sb12 samples with x=0.2–0.6 and systemically studied the FFL of Yb, which is still debated even though this system has been extensively investigated for decades. Our combined experimental efforts of X-ray diffraction, microstructural and quantitative compositional analyses clearly reveal a Yb FFL of ~0.29 in CoSb3, which is consistent with previous theoretical calculations. For the excess Yb in samples with x>0.35 mainly form metallic YbSb2 precipitates, the Fermi level increases significantly and thus increases the electrical conductivity and decreasing the Seebeck coefficient. Our result is further corroborated by the numerical calculations based on the Bergman’s composite theory, which accurately reproduces the transport properties of the x>0.35 samples based on nominal Yb0.35Co4Sb12 and YbSb2 composites. A maximum ZT of 1.5 at 850 K is achieved for Yb0.3Co4Sb12, which is the highest value for a single-element-filled CoSb3. The high ZT originates from the high-power factor (in excess of 50 μW cm-K-2) and low lattice thermal conductivity (well below 1.0 W m-K-1). More importantly, the largemore » average ZTs, for example, ~1.05 for 300–850 K and ~1.27 for 500–850 K, are comparable to the best values for n-type skutterudites. The high thermoelectric and thermomechanical performances and the relatively low air and moisture sensitivities of Yb make Yb-filled CoSb3, a promising candidate for large-scale power generation applications.« less

Authors:
 [1];  [2];  [1];  [1];  [1];  [1]
  1. Univ. of Washington, Seattle, WA (United States). Materials Science adn Engineering Dept.
  2. General Motors Research and Development, Warren, MI (United States)
Publication Date:
Research Org.:
Univ. of Washington, Seattle, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1363865
Grant/Contract Number:  
EE0005432
Resource Type:
Accepted Manuscript
Journal Name:
NPG Asia Materials (Online)
Additional Journal Information:
Journal Name: NPG Asia Materials (Online); Journal Volume: 8; Journal Issue: 7; Journal ID: ISSN 1884-4057
Publisher:
Nature Publishing Group Asia
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Wang, Shanyu, Salvador, James R., Yang, Jiong, Wei, Ping, Duan, Bo, and Yang, Jihui. High-performance n-type YbxCo4Sb12: from partially filled skutterudites towards composite thermoelectrics. United States: N. p., 2016. Web. https://doi.org/10.1038/am.2016.77.
Wang, Shanyu, Salvador, James R., Yang, Jiong, Wei, Ping, Duan, Bo, & Yang, Jihui. High-performance n-type YbxCo4Sb12: from partially filled skutterudites towards composite thermoelectrics. United States. https://doi.org/10.1038/am.2016.77
Wang, Shanyu, Salvador, James R., Yang, Jiong, Wei, Ping, Duan, Bo, and Yang, Jihui. Fri . "High-performance n-type YbxCo4Sb12: from partially filled skutterudites towards composite thermoelectrics". United States. https://doi.org/10.1038/am.2016.77. https://www.osti.gov/servlets/purl/1363865.
@article{osti_1363865,
title = {High-performance n-type YbxCo4Sb12: from partially filled skutterudites towards composite thermoelectrics},
author = {Wang, Shanyu and Salvador, James R. and Yang, Jiong and Wei, Ping and Duan, Bo and Yang, Jihui},
abstractNote = {The filling fraction limit (FFL) of skutterudites, that is, the complex balance of formation enthalpies among different species, is an intricate but crucial parameter for achieving high thermoelectric performance. In this work, we synthesized a series of YbxCo4Sb12 samples with x=0.2–0.6 and systemically studied the FFL of Yb, which is still debated even though this system has been extensively investigated for decades. Our combined experimental efforts of X-ray diffraction, microstructural and quantitative compositional analyses clearly reveal a Yb FFL of ~0.29 in CoSb3, which is consistent with previous theoretical calculations. For the excess Yb in samples with x>0.35 mainly form metallic YbSb2 precipitates, the Fermi level increases significantly and thus increases the electrical conductivity and decreasing the Seebeck coefficient. Our result is further corroborated by the numerical calculations based on the Bergman’s composite theory, which accurately reproduces the transport properties of the x>0.35 samples based on nominal Yb0.35Co4Sb12 and YbSb2 composites. A maximum ZT of 1.5 at 850 K is achieved for Yb0.3Co4Sb12, which is the highest value for a single-element-filled CoSb3. The high ZT originates from the high-power factor (in excess of 50 μW cm-K-2) and low lattice thermal conductivity (well below 1.0 W m-K-1). More importantly, the large average ZTs, for example, ~1.05 for 300–850 K and ~1.27 for 500–850 K, are comparable to the best values for n-type skutterudites. The high thermoelectric and thermomechanical performances and the relatively low air and moisture sensitivities of Yb make Yb-filled CoSb3, a promising candidate for large-scale power generation applications.},
doi = {10.1038/am.2016.77},
journal = {NPG Asia Materials (Online)},
number = 7,
volume = 8,
place = {United States},
year = {2016},
month = {7}
}

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Works referenced in this record:

High figure of merit in partially filled ytterbium skutterudite materials
journal, January 2000

  • Nolas, G. S.; Kaeser, M.; Littleton, R. T.
  • Applied Physics Letters, Vol. 77, Issue 12
  • DOI: 10.1063/1.1311597

Thermoelectric property enhancement in Yb-doped n-type skutterudites YbxCo4Sb12
journal, August 2014


Anomalous Lattice Dynamics near the Ferroelectric Instability in PbTe
journal, October 2011


High thermoelectric performance of In, Yb, Ce multiple filled CoSb3 based skutterudite compounds
journal, September 2012

  • Ballikaya, Sedat; Uzar, Neslihan; Yildirim, Saffettin
  • Journal of Solid State Chemistry, Vol. 193
  • DOI: 10.1016/j.jssc.2012.03.029

The realization of a high thermoelectric figure of merit in Ge-substituted β-Zn4Sb3 through band structure modification
journal, January 2012

  • Wang, Shanyu; Tan, Xiaojian; Tan, Gangjian
  • Journal of Materials Chemistry, Vol. 22, Issue 28
  • DOI: 10.1039/c2jm30906h

Iron valence in skutterudites: Transport and magnetic properties of Co 1 x Fe x Sb 3
journal, December 2000


Optimum Carrier Concentration in n-Type PbTe Thermoelectrics
journal, May 2014

  • Pei, Yanzhong; Gibbs, Zachary M.; Gloskovskii, Andrei
  • Advanced Energy Materials, Vol. 4, Issue 13
  • DOI: 10.1002/aenm.201400486

Low effective mass leading to high thermoelectric performance
journal, January 2012

  • Pei, Yanzhong; LaLonde, Aaron D.; Wang, Heng
  • Energy & Environmental Science, Vol. 5, Issue 7
  • DOI: 10.1039/c2ee21536e

On Intensifying Carrier Impurity Scattering to Enhance Thermoelectric Performance in Cr-Doped Ce y Co 4 Sb 12
journal, October 2015

  • Wang, Shanyu; Yang, Jiong; Wu, Lihua
  • Advanced Functional Materials, Vol. 25, Issue 42
  • DOI: 10.1002/adfm.201502782

Multiple-Filled Skutterudites: High Thermoelectric Figure of Merit through Separately Optimizing Electrical and Thermal Transports
journal, May 2011

  • Shi, Xun; Yang, Jiong; Salvador, James R.
  • Journal of the American Chemical Society, Vol. 133, Issue 20
  • DOI: 10.1021/ja111199y

Resonant bonding leads to low lattice thermal conductivity
journal, April 2014

  • Lee, Sangyeop; Esfarjani, Keivan; Luo, Tengfei
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms4525

Enhanced thermoelectric properties of Bi2(Te1−xSex)3-based compounds as n-type legs for low-temperature power generation
journal, January 2012

  • Wang, Shanyu; Tan, Gangjian; Xie, Wenjie
  • Journal of Materials Chemistry, Vol. 22, Issue 39
  • DOI: 10.1039/c2jm34608g

Conductivity-limiting bipolar thermal conductivity in semiconductors
journal, May 2015

  • Wang, Shanyu; Yang, Jiong; Toll, Trevor
  • Scientific Reports, Vol. 5, Issue 1
  • DOI: 10.1038/srep10136

Improving thermoelectric performance of caged compounds through light-element filling
journal, July 2009

  • Pei, Y. Z.; Yang, Jiong; Chen, L. D.
  • Applied Physics Letters, Vol. 95, Issue 4
  • DOI: 10.1063/1.3182800

Filling fraction limits for rare-earth atoms in Co Sb 3 : An ab initio approach
journal, October 2006


Thermoelectric properties of Te-doped CoSb3 by spark plasma sintering
journal, October 2005

  • Li, X. Y.; Chen, L. D.; Fan, J. F.
  • Journal of Applied Physics, Vol. 98, Issue 8
  • DOI: 10.1063/1.2067704

Thermoelectric Materials for Space and Automotive Power Generation
journal, March 2006


Transport and mechanical properties of Yb-filled skutterudites
journal, July 2009


Rapid preparation of CeFe4Sb12 skutterudite by melt spinning: rich nanostructures and high thermoelectric performance
journal, January 2013

  • Tan, Gangjian; Liu, Wei; Wang, Shanyu
  • Journal of Materials Chemistry A, Vol. 1, Issue 40
  • DOI: 10.1039/c3ta13024j

Conversion efficiency of skutterudite-based thermoelectric modules
journal, January 2014

  • Salvador, James R.; Cho, Jung Y.; Ye, Zuxin
  • Phys. Chem. Chem. Phys., Vol. 16, Issue 24
  • DOI: 10.1039/c4cp01582g

Identifying the Specific Nanostructures Responsible for the High Thermoelectric Performance of (Bi,Sb) 2 Te 3 Nanocomposites
journal, September 2010

  • Xie, Wenjie; He, Jian; Kang, Hye Jung
  • Nano Letters, Vol. 10, Issue 9
  • DOI: 10.1021/nl100804a

Filling Fraction Limit for Intrinsic Voids in Crystals: Doping in Skutterudites
journal, October 2005


Low thermal conductivity and high thermoelectric figure of merit in n-type BaxYbyCo4Sb12 double-filled skutterudites
journal, May 2008

  • Shi, X.; Kong, H.; Li, C. -P.
  • Applied Physics Letters, Vol. 92, Issue 18
  • DOI: 10.1063/1.2920210

Opportunities and challenges for a sustainable energy future
journal, August 2012

  • Chu, Steven; Majumdar, Arun
  • Nature, Vol. 488, Issue 7411, p. 294-303
  • DOI: 10.1038/nature11475

Searching for a Better Thermal Battery
journal, March 2012


Thermoelectric properties of chemically substituted skutterudites YbyCo4SnxSb12−x
journal, August 2000

  • Dilley, N. R.; Bauer, E. D.; Maple, M. B.
  • Journal of Applied Physics, Vol. 88, Issue 4
  • DOI: 10.1063/1.1305837

Chemical properties and thermopower of the new series of skutterudite Ce1−pYbpFe4Sb12
journal, March 2003


Synthesis of YbyCo4Sb12∕Yb2O3 composites and their thermoelectric properties
journal, August 2006

  • Zhao, X. Y.; Shi, X.; Chen, L. D.
  • Applied Physics Letters, Vol. 89, Issue 9
  • DOI: 10.1063/1.2345249

High performance InxCeyCo4Sb12 thermoelectric materials with in situ forming nanostructured InSb phase
journal, March 2009

  • Li, Han; Tang, Xinfeng; Zhang, Qingjie
  • Applied Physics Letters, Vol. 94, Issue 10
  • DOI: 10.1063/1.3099804

SKUTTERUDITES: A Phonon-Glass-Electron Crystal Approach to Advanced Thermoelectric Energy Conversion Applications
journal, August 1999


The maximum possible conversion efficiency of silicon‐germanium thermoelectric generators
journal, September 1991

  • Slack, Glen A.; Hussain, Moayyed A.
  • Journal of Applied Physics, Vol. 70, Issue 5
  • DOI: 10.1063/1.349385

Thermoelectric properties of a composite medium
journal, December 1991

  • Bergman, David J.; Levy, Ohad
  • Journal of Applied Physics, Vol. 70, Issue 11
  • DOI: 10.1063/1.349830

Valence of Cr in skutterudites: Electrical transport and magnetic properties of Cr-doped CoSb 3
journal, July 2002


Anisotropic Multicenter Bonding and High Thermoelectric Performance in Electron-Poor CdSb
journal, January 2015

  • Wang, Shanyu; Yang, Jiong; Wu, Lihua
  • Chemistry of Materials, Vol. 27, Issue 3
  • DOI: 10.1021/cm504398d

Thermoelectric properties of p-type skutterudites YbxFe3.5Ni0.5Sb12 (0.8⩽x⩽1)
journal, March 2012


Temperature Dependence of the Effective Masses in PbTe
journal, July 1964


Intermediate valence in the filled skutterudite compound YbFe 4 Sb 12
journal, September 1998


Solubility study of Yb in n -type skutterudites Yb x Co 4 Sb 12 and their enhanced thermoelectric properties
journal, September 2009


Dynamics of coherent acoustic phonons in thin films of CoSb 3 and partially filled Yb x Co 4 Sb 12 skutterudites
journal, May 2014


Realization of high thermoelectric performance in n-type partially filled skutterudites
journal, May 2011

  • Shi, Xun; Bai, Shengqiang; Xi, Lili
  • Journal of Materials Research, Vol. 26, Issue 15
  • DOI: 10.1557/jmr.2011.84

Anomalous barium filling fraction and n -type thermoelectric performance of BayCo4Sb12
journal, August 2001

  • Chen, L. D.; Kawahara, T.; Tang, X. F.
  • Journal of Applied Physics, Vol. 90, Issue 4
  • DOI: 10.1063/1.1388162

Avoided crossing of rattler modes in thermoelectric materials
journal, August 2008

  • Christensen, Mogens; Abrahamsen, Asger B.; Christensen, Niels B.
  • Nature Materials, Vol. 7, Issue 10
  • DOI: 10.1038/nmat2273

Einstein modes in the phonon density of states of the single-filled skutterudite Yb 0.2 Co 4 Sb 12
journal, November 2010


Cooling, Heating, Generating Power, and Recovering Waste Heat with Thermoelectric Systems
journal, September 2008


High thermoelectric performance of Yb0.26Co4Sb12/yGaSb nanocomposites originating from scattering electrons of low energy
journal, June 2010


Electrical Properties of Silicon Containing Arsenic and Boron
journal, October 1954


Temperature dependent solubility of Yb in Yb–CoSb3 skutterudite and its effect on preparation, optimization and lifetime of thermoelectrics
journal, March 2015


Rapid preparation method of bulk nanostructured Yb0.3Co4Sb12+y compounds and their improved thermoelectric performance
journal, December 2008

  • Li, Han; Tang, Xinfeng; Zhang, Qingjie
  • Applied Physics Letters, Vol. 93, Issue 25
  • DOI: 10.1063/1.3054158

Electron and phonon scattering in the high-temperature thermoelectric La 3 Te 4 z M z ( M = Sb , Bi )
journal, March 2010


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
journal, June 2011

  • Su, Xianli; Li, Han; Wang, Guoyu
  • Chemistry of Materials, Vol. 23, Issue 11
  • DOI: 10.1021/cm200560s

Creation of Yb2O3 Nanoprecipitates Through an Oxidation Process in Bulk Yb-Filled Skutterudites
journal, January 2013


Multiple-Filled Skutterudites: High Thermoelectric Figure of Merit through Separately Optimizing Electrical and Thermal Transports
journal, January 2012

  • Shi, Xun; Yang, Jiong; Salvador, James R.
  • Journal of the American Chemical Society, Vol. 134, Issue 5
  • DOI: 10.1021/ja211185w

Recent advances in magnetic structure determination by neutron powder diffraction
journal, October 1993


High-performance nanostructured thermoelectric materials
journal, October 2010


Influence of electron-phonon interaction on the lattice thermal conductivity of Co 1 x Ni x Sb 3
journal, February 2002


Conversion efficiency of skutterudite-based thermoelectric modules
journal, January 2014

  • Salvador, James R.; Cho, Jung Y.; Ye, Zuxin
  • Phys. Chem. Chem. Phys., Vol. 16, Issue 24
  • DOI: 10.1039/C4CP01582G

Einstein modes in the phonon density of states of the single-filled skutterudite Yb 0.2 Co 4 Sb 12
journal, November 2010


Solubility study of Yb in n -type skutterudites Yb x Co 4 Sb 12 and their enhanced thermoelectric properties
journal, September 2009


Filling Fraction Limit for Intrinsic Voids in Crystals: Doping in Skutterudites
journal, October 2005


Filling fraction limits for rare-earth atoms in Co Sb 3 : An ab initio approach
journal, October 2006


Dynamics of coherent acoustic phonons in thin films of CoSb 3 and partially filled Yb x Co 4 Sb 12 skutterudites
journal, May 2014


Recent advances in magnetic structure determination by neutron powder diffraction
journal, October 1993


Intermediate valence in the filled skutterudite compound YbFe 4 Sb 12
journal, September 1998


Chemical properties and thermopower of the new series of skutterudite Ce1−pYbpFe4Sb12
journal, March 2003


Iron valence in skutterudites: Transport and magnetic properties of Co 1 x Fe x Sb 3
journal, December 2000


Valence of Cr in skutterudites: Electrical transport and magnetic properties of Cr-doped CoSb 3
journal, July 2002


Electrical Properties of Silicon Containing Arsenic and Boron
journal, October 1954


Temperature Dependence of the Effective Masses in PbTe
journal, July 1964


Anomalous Lattice Dynamics near the Ferroelectric Instability in PbTe
journal, October 2011


Influence of electron-phonon interaction on the lattice thermal conductivity of Co 1 x Ni x Sb 3
journal, February 2002


Electron and phonon scattering in the high-temperature thermoelectric La 3 Te 4 z M z ( M = Sb , Bi )
journal, March 2010


    Works referencing / citing this record:

    Boosting the thermoelectric performance of PbSe through dynamic doping and hierarchical phonon scattering
    journal, January 2018

    • You, Li; Liu, Yefeng; Li, Xin
    • Energy & Environmental Science, Vol. 11, Issue 7
    • DOI: 10.1039/c8ee00418h

    Enhanced thermoelectric and mechanical properties of p-type skutterudites with in situ formed Fe 3 Si nanoprecipitate
    journal, January 2017

    • Peng, Shengyuan; Sun, Jianhui; Cui, Bo
    • Inorganic Chemistry Frontiers, Vol. 4, Issue 10
    • DOI: 10.1039/c7qi00304h

    High-Efficiency Skutterudite Modules at a Low Temperature Gradient
    journal, November 2019

    • Li, Wenjie; Stokes, David; Poudel, Bed
    • Energies, Vol. 12, Issue 22
    • DOI: 10.3390/en12224292

    Powering the Hydrogen Economy from Waste Heat: A Review of Heat‐to‐Hydrogen Concepts
    journal, August 2019


    Quantitative nanoscale mapping of three-phase thermal conductivities in filled skutterudites via scanning thermal microscopy
    journal, June 2017

    • Nasr Esfahani, Ehsan; Ma, Feiyue; Wang, Shanyu
    • National Science Review, Vol. 5, Issue 1
    • DOI: 10.1093/nsr/nwx074

    Enhanced Thermoelectric and Mechanical Properties in Yb 0.3 Co 4 Sb 12 with In Situ Formed CoSi Nanoprecipitates
    journal, October 2019

    • Qin, Dandan; Wu, Haijun; Cai, Songting
    • Advanced Energy Materials, Vol. 9, Issue 42
    • DOI: 10.1002/aenm.201902435

    Effects of partial La filling and Sb vacancy defects on CoS b 3 skutterudites
    journal, April 2017


    A facile energy-saving route of fabricating thermoelectric Sb 2 Te 3 -Te nanocomposites and nanosized Te
    journal, October 2018

    • Liu, En-Yu; Lin, Fei-Hung; Yang, Zong-Ren
    • Royal Society Open Science, Vol. 5, Issue 10
    • DOI: 10.1098/rsos.180698

    Effect of Fe ion implantation on the thermoelectric properties and electronic structures of CoSb 3 thin films
    journal, January 2019

    • Masarrat, Anha; Bhogra, Anuradha; Meena, Ramcharan
    • RSC Advances, Vol. 9, Issue 62
    • DOI: 10.1039/c9ra06873b

    Resonant level-induced high thermoelectric response in indium-doped GeTe
    journal, January 2017

    • Wu, Lihua; Li, Xin; Wang, Shanyu
    • NPG Asia Materials, Vol. 9, Issue 1
    • DOI: 10.1038/am.2016.203

    Grain Boundary Engineering for Achieving High Thermoelectric Performance in n-Type Skutterudites
    journal, February 2017


    Odyssey of thermoelectric materials: foundation of the complex structure
    journal, June 2018

    • Masood, Khalid Bin; Kumar, Pushpendra; Singh, R. A.
    • Journal of Physics Communications, Vol. 2, Issue 6
    • DOI: 10.1088/2399-6528/aab64f