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Title: Improved thermoelectric performance of n-type Ca and Ca-Ce filled skutterudites

Abstract

Thermoelectric (TE) technology for use in automotive waste heat recovery is being advanced by General Motors with support from the US Department of Energy. Skutterudites are a very promising material for this application of TE technology due to their superior mechanical properties and good TE performance. Double-filled Yb xBa yCo 4Sb 12 with ZT values around 1.1 at 750K are the best performing n-type skutterudites produced on a large scale using an economically viable approach of melt spinning (MS) in conjunction with spark plasma sintering (SPS). Another economical production method on the tons scale, the melt quench annealing (MQA) technique, has been recently claimed by Treibacher Industrie AG, further information is available [G. Rogl et al., Acta Mater. 76, 434-448 (2014)]. A possible hurdle to commercial implementation of these materials is the use of rare earths as the fillers to reduce thermal conductivity and improve the electrical transport properties. It will be shown herein that skutterudites double-filled with Ca and Ce, both of which are lower-cost fillers, display markedly different TE properties depending on whether they are produced by MQA or MS + SPS synthesis techniques. Finally, Ca and Ce double-filled skutterudites prepared by MS + SPS have TE propertiesmore » that are superior to the same compositions prepared by MQA and that are comparable to the best performing Yb and Ba filled materials. Furthermore, the results of this study suggest that the unusually poor transport properties of MQA Ca-filled skutterudites can be ascribed to deleterious secondary phases, which is contrary to reports in the literature attempting to explain these irregularities via band structure features.« less

Authors:
 [1];  [1];  [1];  [2];  [2];  [2];  [3];  [3]
  1. Optimal CAE, Plymouth, MI (United States)
  2. General Motors Research and Development, Warren, MI (United States)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1265387
Alternate Identifier(s):
OSTI ID: 1226633
Grant/Contract Number:  
AC05-00OR22725; FC26-04NT42278; AC05000OR22725
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Applied Physics
Additional Journal Information:
Journal Volume: 116; Journal Issue: 24; Journal ID: ISSN 0021-8979
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATION; 36 MATERIALS SCIENCE; skutterudite; thermoelectric

Citation Formats

Thompson, Daniel R., Liu, Chang, Ellison, Nicole D., Salvador, James R., Meyer, Martin S., Haddad, Daad B., Wang, Hsin, and Cai, W. Improved thermoelectric performance of n-type Ca and Ca-Ce filled skutterudites. United States: N. p., 2014. Web. doi:10.1063/1.4904187.
Thompson, Daniel R., Liu, Chang, Ellison, Nicole D., Salvador, James R., Meyer, Martin S., Haddad, Daad B., Wang, Hsin, & Cai, W. Improved thermoelectric performance of n-type Ca and Ca-Ce filled skutterudites. United States. doi:10.1063/1.4904187.
Thompson, Daniel R., Liu, Chang, Ellison, Nicole D., Salvador, James R., Meyer, Martin S., Haddad, Daad B., Wang, Hsin, and Cai, W. Sun . "Improved thermoelectric performance of n-type Ca and Ca-Ce filled skutterudites". United States. doi:10.1063/1.4904187. https://www.osti.gov/servlets/purl/1265387.
@article{osti_1265387,
title = {Improved thermoelectric performance of n-type Ca and Ca-Ce filled skutterudites},
author = {Thompson, Daniel R. and Liu, Chang and Ellison, Nicole D. and Salvador, James R. and Meyer, Martin S. and Haddad, Daad B. and Wang, Hsin and Cai, W.},
abstractNote = {Thermoelectric (TE) technology for use in automotive waste heat recovery is being advanced by General Motors with support from the US Department of Energy. Skutterudites are a very promising material for this application of TE technology due to their superior mechanical properties and good TE performance. Double-filled YbxBayCo4Sb12 with ZT values around 1.1 at 750K are the best performing n-type skutterudites produced on a large scale using an economically viable approach of melt spinning (MS) in conjunction with spark plasma sintering (SPS). Another economical production method on the tons scale, the melt quench annealing (MQA) technique, has been recently claimed by Treibacher Industrie AG, further information is available [G. Rogl et al., Acta Mater. 76, 434-448 (2014)]. A possible hurdle to commercial implementation of these materials is the use of rare earths as the fillers to reduce thermal conductivity and improve the electrical transport properties. It will be shown herein that skutterudites double-filled with Ca and Ce, both of which are lower-cost fillers, display markedly different TE properties depending on whether they are produced by MQA or MS + SPS synthesis techniques. Finally, Ca and Ce double-filled skutterudites prepared by MS + SPS have TE properties that are superior to the same compositions prepared by MQA and that are comparable to the best performing Yb and Ba filled materials. Furthermore, the results of this study suggest that the unusually poor transport properties of MQA Ca-filled skutterudites can be ascribed to deleterious secondary phases, which is contrary to reports in the literature attempting to explain these irregularities via band structure features.},
doi = {10.1063/1.4904187},
journal = {Journal of Applied Physics},
issn = {0021-8979},
number = 24,
volume = 116,
place = {United States},
year = {2014},
month = {12}
}

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Works referenced in this record:

Beneficial effect of Ni substitution on the thermoelectric properties in partially filled CayCo4−xNixSb12 skutterudites
journal, April 2005

  • Puyet, M.; Dauscher, A.; Lenoir, B.
  • Journal of Applied Physics, Vol. 97, Issue 8
  • DOI: 10.1063/1.1868083

Single-element spark plasma sintering of silicon germanium
journal, November 2012

  • Thompson, Daniel; Hitchcock, Dale; Lahwal, Ali
  • Emerging Materials Research, Vol. 1, Issue 6
  • DOI: 10.1680/emr.12.00019

Some properties of semiconducting IrSb 3
journal, August 1994

  • Slack, Glen A.; Tsoukala, Veneta G.
  • Journal of Applied Physics, Vol. 76, Issue 3
  • DOI: 10.1063/1.357750

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

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

High temperature transport properties of partially filled CaxCo4Sb12 skutterudites
journal, May 2004

  • Puyet, M.; Lenoir, B.; Dauscher, A.
  • Journal of Applied Physics, Vol. 95, Issue 9
  • DOI: 10.1063/1.1688463

Effect of partial void filling on the lattice thermal conductivity of skutterudites
journal, July 1998


Cerium filling and doping of cobalt triantimonide
journal, September 1997

  • Morelli, Donald T.; Meisner, Gregory P.; Chen, Baoxing
  • Physical Review B, Vol. 56, Issue 12
  • DOI: 10.1103/PhysRevB.56.7376

Synthesis and high temperature thermoelectric properties of calcium and cerium double-filled skutterudites Ca 0.1 Ce x Co 4 Sb 12
journal, April 2009


Synthesis and crystal structure of CaxCo4Sb12 skutterudites
journal, June 2004


Electronic Transport in Semimetallic Cerium Sulfide
journal, February 1964


Thermoelectric and mechanical properties of melt spun and spark plasma sintered n-type Yb- and Ba-filled skutterudites
journal, October 2013

  • Salvador, James R.; Waldo, Richard A.; Wong, Curtis A.
  • Materials Science and Engineering: B, Vol. 178, Issue 17
  • DOI: 10.1016/j.mseb.2013.06.023

Thermoelectric properties of the n -type filled skutterudite Ba0.3Co4Sb12 doped with Ni
journal, March 2002

  • Dyck, Jeffrey S.; Chen, Wei; Uher, Ctirad
  • Journal of Applied Physics, Vol. 91, Issue 6
  • DOI: 10.1063/1.1450036

Double-filled skutterudites of the type YbxCayCo4Sb12: Synthesis and properties
journal, February 2010

  • Salvador, J. R.; Yang, J.; Wang, H.
  • Journal of Applied Physics, Vol. 107, Issue 4
  • DOI: 10.1063/1.3296186

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

Electronic, transport, and magnetic properties of Ca x Co 4 Sb 12 partially filled skutterudites
journal, January 2006


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

Portable Thermoelectric Generators
conference, January 1963

  • Neild, A. Bayne
  • Pre-1964 SAE Technical Papers, SAE Technical Paper Series
  • DOI: 10.4271/630019

Thermal to Electrical Energy Conversion of Skutterudite-Based Thermoelectric Modules
journal, October 2012

  • Salvador, James R.; Cho, Jung Y.; Ye, Zuxin
  • Journal of Electronic Materials, Vol. 42, Issue 7
  • DOI: 10.1007/s11664-012-2261-9

Coupled vibrational modes in multiple-filled skutterudites and the effects on lattice thermal conductivity reduction
journal, March 2013

  • Guo, L.; Xu, X.; Salvador, J. R.
  • Applied Physics Letters, Vol. 102, Issue 11
  • DOI: 10.1063/1.4796121

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


Enhanced thermoelectric performance of dual-element-filled skutterudites BaxCeyCo4Sb12
journal, June 2009


Thermoelectric properties of P-type Yb-filled skutterudite YbxFeyCo4-ySb12
journal, October 2011