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

Thompson, Daniel R.; Liu, Chang; Ellison, Nicole D.; Salvador, James R.; Meyer, Martin S.; Haddad, Daad B.; Wang, Hsin; Cai, W.

doi:10.1063/1.4904187

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

Journal Article · Sun Dec 28 00:00:00 EST 2014 · Journal of Applied Physics

DOI:https://doi.org/10.1063/1.4904187· OSTI ID:1265387

Thompson, Daniel R. ^[1]; Liu, Chang ^[1]; Ellison, Nicole D. ^[1]; Salvador, James R. ^[2]; Meyer, Martin S. ^[2]; Haddad, Daad B. ^[2]; Wang, Hsin ^[3]; Cai, W. ^[3]

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)

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_yCo₄Sb₁₂ 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.

View Accepted Manuscript (DOE)

View Accepted Manuscript (Publisher)

Cite

Export

Save

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC05-00OR22725; FC26-04NT42278; AC05000OR22725

OSTI ID:: 1265387

Alternate ID(s):: OSTI ID: 1226633

Journal Information:: Journal of Applied Physics, Vol. 116, Issue 24; ISSN 0021-8979

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 2 works

Citation information provided by
Web of Science

References (26)

Beneficial effect of Ni substitution on the thermoelectric properties in partially filled CayCo4−xNixSb12 skutterudites Puyet, M.; Dauscher, A.; Lenoir, B. Journal of Applied Physics, Vol. 97, Issue 8 https://doi.org/10.1063/1.1868083	journal	April 2005
Single-element spark plasma sintering of silicon germanium Thompson, Daniel; Hitchcock, Dale; Lahwal, Ali Emerging Materials Research, Vol. 1, Issue 6 https://doi.org/10.1680/emr.12.00019	journal	November 2012
Scanning Electron Microscopy and X-ray Microanalysis Goldstein, Joseph I.; Newbury, Dale E.; Echlin, Patrick https://doi.org/10.1007/978-1-4615-0215-9	book	January 2003
Some properties of semiconducting IrSb ₃ Slack, Glen A.; Tsoukala, Veneta G. Journal of Applied Physics, Vol. 76, Issue 3 https://doi.org/10.1063/1.357750	journal	August 1994
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
Realization of high thermoelectric performance in n-type partially filled skutterudites Shi, Xun; Bai, Shengqiang; Xi, Lili Journal of Materials Research, Vol. 26, Issue 15 https://doi.org/10.1557/jmr.2011.84	journal	May 2011
Nanostructuring of p- and n-type skutterudites reaching figures of merit of approximately 1.3 and 1.6, respectively Rogl, G.; Grytsiv, A.; Rogl, P. Acta Materialia, Vol. 76 https://doi.org/10.1016/j.actamat.2014.05.051	journal	September 2014
High temperature transport properties of partially filled CaxCo4Sb12 skutterudites Puyet, M.; Lenoir, B.; Dauscher, A. Journal of Applied Physics, Vol. 95, Issue 9 https://doi.org/10.1063/1.1688463	journal	May 2004
Effect of partial void filling on the lattice thermal conductivity of skutterudites Nolas, G. S.; Cohn, J. L.; Slack, G. A. Physical Review B, Vol. 58, Issue 1 https://doi.org/10.1103/PhysRevB.58.164	journal	July 1998
Cerium filling and doping of cobalt triantimonide Morelli, Donald T.; Meisner, Gregory P.; Chen, Baoxing Physical Review B, Vol. 56, Issue 12 https://doi.org/10.1103/PhysRevB.56.7376	journal	September 1997
Synthesis and high temperature thermoelectric properties of calcium and cerium double-filled skutterudites Ca _0.1 Ce _x Co ₄ Sb ₁₂ Li, D.; Yang, K.; Hng, H. H. Journal of Physics D: Applied Physics, Vol. 42, Issue 10 https://doi.org/10.1088/0022-3727/42/10/105408	journal	April 2009
Synthesis and crystal structure of CaxCo4Sb12 skutterudites Puyet, M.; Lenoir, B.; Dauscher, A. Journal of Solid State Chemistry, Vol. 177, Issue 6 https://doi.org/10.1016/j.jssc.2004.02.010	journal	June 2004
Electronic Transport in Semimetallic Cerium Sulfide Cutler, M.; Leavy, J. F.; Fitzpatrick, R. L. Physical Review, Vol. 133, Issue 4A https://doi.org/10.1103/PhysRev.133.A1143	journal	February 1964
Thermoelectric and mechanical properties of melt spun and spark plasma sintered n-type Yb- and Ba-filled skutterudites Salvador, James R.; Waldo, Richard A.; Wong, Curtis A. Materials Science and Engineering: B, Vol. 178, Issue 17 https://doi.org/10.1016/j.mseb.2013.06.023	journal	October 2013
Thermoelectric properties of the n -type filled skutterudite Ba0.3Co4Sb12 doped with Ni Dyck, Jeffrey S.; Chen, Wei; Uher, Ctirad Journal of Applied Physics, Vol. 91, Issue 6 https://doi.org/10.1063/1.1450036	journal	March 2002
Double-filled skutterudites of the type YbxCayCo4Sb12: Synthesis and properties Salvador, J. R.; Yang, J.; Wang, H. Journal of Applied Physics, Vol. 107, Issue 4 https://doi.org/10.1063/1.3296186	journal	February 2010
Low thermal conductivity and high thermoelectric figure of merit in n-type BaxYbyCo4Sb12 double-filled skutterudites Shi, X.; Kong, H.; Li, C. -P. Applied Physics Letters, Vol. 92, Issue 18 https://doi.org/10.1063/1.2920210	journal	May 2008
Electronic, transport, and magnetic properties of ${Ca}_{x} {Co}_{4} {Sb}_{12}$ partially filled skutterudites Puyet, M.; Lenoir, B.; Dauscher, A. Physical Review B, Vol. 73, Issue 3 https://doi.org/10.1103/PhysRevB.73.035126	journal	January 2006
Synthesis of YbyCo4Sb12∕Yb2O3 composites and their thermoelectric properties Zhao, X. Y.; Shi, X.; Chen, L. D. Applied Physics Letters, Vol. 89, Issue 9 https://doi.org/10.1063/1.2345249	journal	August 2006
Fundamentals of Semiconductors Yu, Peter Y.; Cardona, Manuel Graduate Texts in Physics https://doi.org/10.1007/978-3-642-00710-1	book	January 2010
Portable Thermoelectric Generators Neild, A. Bayne Pre-1964 SAE Technical Papers, SAE Technical Paper Series https://doi.org/10.4271/630019	conference	January 1963
Thermal to Electrical Energy Conversion of Skutterudite-Based Thermoelectric Modules Salvador, James R.; Cho, Jung Y.; Ye, Zuxin Journal of Electronic Materials, Vol. 42, Issue 7 https://doi.org/10.1007/s11664-012-2261-9	journal	October 2012
Coupled vibrational modes in multiple-filled skutterudites and the effects on lattice thermal conductivity reduction Guo, L.; Xu, X.; Salvador, J. R. Applied Physics Letters, Vol. 102, Issue 11 https://doi.org/10.1063/1.4796121	journal	March 2013
SKUTTERUDITES: A Phonon-Glass-Electron Crystal Approach to Advanced Thermoelectric Energy Conversion Applications Nolas, G. S.; Morelli, D. T.; Tritt, Terry M. Annual Review of Materials Science, Vol. 29, Issue 1 https://doi.org/10.1146/annurev.matsci.29.1.89	journal	August 1999
Enhanced thermoelectric performance of dual-element-filled skutterudites BaxCeyCo4Sb12 Bai, S. Q.; Pei, Y. Z.; Chen, L. D. Acta Materialia, Vol. 57, Issue 11 https://doi.org/10.1016/j.actamat.2009.03.018	journal	June 2009
Thermoelectric properties of P-type Yb-filled skutterudite YbxFeyCo4-ySb12 Zhou, Chen; Morelli, Donald; Zhou, Xiaoyuan Intermetallics, Vol. 19, Issue 10 https://doi.org/10.1016/j.intermet.2011.04.015	journal	October 2011

Similar Records

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

Journal Article · Sun Dec 28 00:00:00 EST 2014 · Journal of Applied Physics · OSTI ID:1265387

Thompson, Daniel R.; Liu, Chang; Ellison, Nicole D.; +5 more

Electrical and thermal properties of Fe substituted double-filled Ba{sub x}Yb{sub y}Fe{sub z}Co{sub 4-z}Sb{sub 12} skutterudites

Journal Article · Tue Jan 15 00:00:00 EST 2013 · Journal of Solid State Chemistry · OSTI ID:1265387

Ballikaya, Sedat; Uzar, Neslihan; Yildirim, Saffettin; +1 more

Improved thermoelectric performance of (Fe,Co)Sb{sub 3}-type skutterudites from first-principles

Journal Article · Sun Feb 07 00:00:00 EST 2016 · Journal of Applied Physics · OSTI ID:1265387

Williamson, Izaak; Her, Logan Ju-Yee; Su, Xianli; +3 more

Related Subjects

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATION
36 MATERIALS SCIENCE
skutterudite
thermoelectric

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

Citation Formats

References (26)

Similar Records

Related Subjects