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Title: High-performance n-type Yb xCo 4Sb 12: 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 Yb xCo 4Sb 12 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 CoSb 3, which is consistent with previous theoretical calculations. For the excess Yb in samples with x>0.35 mainly form metallic YbSb 2 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 Yb 0.35Co 4Sb 12 and YbSb 2 composites. A maximum ZT of 1.5 at 850 K is achieved for Yb 0.3Co 4Sb 12, which is the highest value for a single-element-filled CoSb 3. The high ZT originates from the high-power factor (in excess of 50 μW cm -Kmore » -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 CoSb 3, 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:
Journal Article: 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. doi: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. doi:10.1038/am.2016.77.
Wang, Shanyu, Salvador, James R., Yang, Jiong, Wei, Ping, Duan, Bo, and Yang, Jihui. 2016. "High-performance n-type YbxCo4Sb12: from partially filled skutterudites towards composite thermoelectrics". United States. doi: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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  • Cited by 1
  • 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,more » 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.« less
  • In this study, Zn-substituted polycrystalline skutterudites CeFe{sub 4-x}Zn{sub x}Sb{sub 12} (x=0, 0.05, 0.1, 0.2, 0.3) were successfully prepared by a traditional melting-annealing method. The solubility of Zn in Fe site is {approx}1.2%, exceeding which trace amount of ZnSb phase can be detected in the XRD. This ZnSb impurity phase, with size of several hundred nanometers for the sample with x=0.2 but showing surprisingly small size of {approx}10 nm for the sample with x=0.3, selectively distributes on the grain boundaries. In particular, the introduction of Zn in Fe site effectively improves the Seebeck coefficient in a manner of enhancement in holemore » effective mass, but it has negligible influence on both electrical and thermal conductivities though the hole concentration is increased. Consequently the corresponding improvement in power factor leads to an improved thermoelectric figure of merit (ZT) of 0.9 at 800 K for the sample with x=0.1, which is {approx}15% higher than that of Zn-free sample. This study demonstrates a favorable effect of Zn iso-substitution and opens a new strategy to improve the thermoelectric properties of p-type Fe-based skutterudites beyond the sole phonon engineering. - Graphical abstract: (a)-(c) ZnSb nanoinclusions emerge when Zn exceeds its solubility limit. (d), (e) The introduction of Zn boosts the Seebeck coefficient and thus enhances the ZT value. Highlights: Black-Right-Pointing-Pointer Zn is successfully employed to substitute Fe atom for the first time. Black-Right-Pointing-Pointer ZnSb nanoinclusions emerge when Zn exceeds its solubility limit {approx}0.12. Black-Right-Pointing-Pointer The introduction of Zn boosts the Seebeck coefficient and enhances the ZT value.« less
  • 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{sub x}Ba{sub y}Co{sub 4}Sb{sub 12} with ZT values around 1.1 at 750 K 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,more » 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. 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.« less