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 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 tomore »
- Authors:
-
- Optimal CAE, Plymouth, MI (United States)
- General Motors Research and Development, Warren, MI (United States)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (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:
- 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. https://doi.org/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. https://doi.org/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},
number = 24,
volume = 116,
place = {United States},
year = {Sun Dec 28 00:00:00 EST 2014},
month = {Sun Dec 28 00:00:00 EST 2014}
}
Web of Science
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
Single-element spark plasma sintering of silicon germanium
journal, November 2012
- Thompson, Daniel; Hitchcock, Dale; Lahwal, Ali
- Emerging Materials Research, Vol. 1, Issue 6
Scanning Electron Microscopy and X-ray Microanalysis
book, January 2003
- Goldstein, Joseph I.; Newbury, Dale E.; Echlin, Patrick
Some properties of semiconducting IrSb 3
journal, August 1994
- Slack, Glen A.; Tsoukala, Veneta G.
- Journal of Applied Physics, Vol. 76, Issue 3
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
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
Nanostructuring of p- and n-type skutterudites reaching figures of merit of approximately 1.3 and 1.6, respectively
journal, September 2014
- Rogl, G.; Grytsiv, A.; Rogl, P.
- Acta Materialia, Vol. 76
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
Effect of partial void filling on the lattice thermal conductivity of skutterudites
journal, July 1998
- Nolas, G. S.; Cohn, J. L.; Slack, G. A.
- Physical Review B, Vol. 58, Issue 1
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
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
- Li, D.; Yang, K.; Hng, H. H.
- Journal of Physics D: Applied Physics, Vol. 42, Issue 10
Synthesis and crystal structure of CaxCo4Sb12 skutterudites
journal, June 2004
- Puyet, M.; Lenoir, B.; Dauscher, A.
- Journal of Solid State Chemistry, Vol. 177, Issue 6
Electronic Transport in Semimetallic Cerium Sulfide
journal, February 1964
- Cutler, M.; Leavy, J. F.; Fitzpatrick, R. L.
- Physical Review, Vol. 133, Issue 4A
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
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
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
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
Electronic, transport, and magnetic properties of partially filled skutterudites
journal, January 2006
- Puyet, M.; Lenoir, B.; Dauscher, A.
- Physical Review B, Vol. 73, Issue 3
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
Fundamentals of Semiconductors
book, January 2010
- Yu, Peter Y.; Cardona, Manuel
- Graduate Texts in Physics
Portable Thermoelectric Generators
conference, January 1963
- Neild, A. Bayne
- Pre-1964 SAE Technical Papers, SAE Technical Paper Series
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
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
SKUTTERUDITES: A Phonon-Glass-Electron Crystal Approach to Advanced Thermoelectric Energy Conversion Applications
journal, August 1999
- Nolas, G. S.; Morelli, D. T.; Tritt, Terry M.
- Annual Review of Materials Science, Vol. 29, Issue 1
Enhanced thermoelectric performance of dual-element-filled skutterudites BaxCeyCo4Sb12
journal, June 2009
- Bai, S. Q.; Pei, Y. Z.; Chen, L. D.
- Acta Materialia, Vol. 57, Issue 11
Thermoelectric properties of P-type Yb-filled skutterudite YbxFeyCo4-ySb12
journal, October 2011
- Zhou, Chen; Morelli, Donald; Zhou, Xiaoyuan
- Intermetallics, Vol. 19, Issue 10