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

Wang, Shanyu; Salvador, James R.; Yang, Jiong; Wei, Ping; Duan, Bo; Yang, Jihui

doi:10.1038/am.2016.77

Title: High-performance n-type Yb_xCo₄Sb₁₂: from partially filled skutterudites towards composite thermoelectrics

Journal Article · Fri Jul 01 00:00:00 EDT 2016 · NPG Asia Materials (Online)

DOI:https://doi.org/10.1038/am.2016.77· OSTI ID:1363865

Wang, Shanyu ^[1]; Salvador, James R. ^[2]; Yang, Jiong ^[1]; Wei, Ping ^[1]; Duan, Bo ^[1]; Yang, Jihui ^[1]

Univ. of Washington, Seattle, WA (United States). Materials Science adn Engineering Dept.
General Motors Research and Development, Warren, MI (United States)

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_xCo₄Sb₁₂ 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 Yb_0.35Co₄Sb₁₂ and YbSb₂ composites. A maximum ZT of 1.5 at 850 K is achieved for Yb_0.3Co₄Sb₁₂, 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.

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Research Organization:: Univ. of Washington, Seattle, WA (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: EE0005432

OSTI ID:: 1363865

Journal Information:: NPG Asia Materials (Online), Vol. 8, Issue 7; ISSN 1884-4057

Publisher:: Nature Publishing Group AsiaCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 86 works

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References (60)

High figure of merit in partially filled ytterbium skutterudite materials Nolas, G. S.; Kaeser, M.; Littleton, R. T. Applied Physics Letters, Vol. 77, Issue 12 https://doi.org/10.1063/1.1311597	journal	January 2000
Thermoelectric property enhancement in Yb-doped n-type skutterudites YbxCo4Sb12 Dahal, Tulashi; Jie, Qing; Joshi, Giri Acta Materialia, Vol. 75 https://doi.org/10.1016/j.actamat.2014.05.019	journal	August 2014
Anomalous Lattice Dynamics near the Ferroelectric Instability in PbTe Zhang, Yi; Ke, Xuezhi; Kent, Paul R. C. Physical Review Letters, Vol. 107, Issue 17 https://doi.org/10.1103/physrevlett.107.175503	journal	October 2011
High thermoelectric performance of In, Yb, Ce multiple filled CoSb3 based skutterudite compounds Ballikaya, Sedat; Uzar, Neslihan; Yildirim, Saffettin Journal of Solid State Chemistry, Vol. 193 https://doi.org/10.1016/j.jssc.2012.03.029	journal	September 2012
The realization of a high thermoelectric figure of merit in Ge-substituted β-Zn4Sb3 through band structure modification Wang, Shanyu; Tan, Xiaojian; Tan, Gangjian Journal of Materials Chemistry, Vol. 22, Issue 28 https://doi.org/10.1039/c2jm30906h	journal	January 2012
Optimum Carrier Concentration in n-Type PbTe Thermoelectrics Pei, Yanzhong; Gibbs, Zachary M.; Gloskovskii, Andrei Advanced Energy Materials, Vol. 4, Issue 13 https://doi.org/10.1002/aenm.201400486	journal	May 2014
Low effective mass leading to high thermoelectric performance Pei, Yanzhong; LaLonde, Aaron D.; Wang, Heng Energy & Environmental Science, Vol. 5, Issue 7 https://doi.org/10.1039/c2ee21536e	journal	January 2012
On Intensifying Carrier Impurity Scattering to Enhance Thermoelectric Performance in Cr-Doped Ce _y Co ₄ Sb ₁₂ Wang, Shanyu; Yang, Jiong; Wu, Lihua Advanced Functional Materials, Vol. 25, Issue 42 https://doi.org/10.1002/adfm.201502782	journal	October 2015
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
Resonant bonding leads to low lattice thermal conductivity Lee, Sangyeop; Esfarjani, Keivan; Luo, Tengfei Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms4525	journal	April 2014
Enhanced thermoelectric properties of Bi2(Te1−xSex)3-based compounds as n-type legs for low-temperature power generation Wang, Shanyu; Tan, Gangjian; Xie, Wenjie Journal of Materials Chemistry, Vol. 22, Issue 39 https://doi.org/10.1039/c2jm34608g	journal	January 2012
Conductivity-limiting bipolar thermal conductivity in semiconductors Wang, Shanyu; Yang, Jiong; Toll, Trevor Scientific Reports, Vol. 5, Issue 1 https://doi.org/10.1038/srep10136	journal	May 2015
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
Improving thermoelectric performance of caged compounds through light-element filling Pei, Y. Z.; Yang, Jiong; Chen, L. D. Applied Physics Letters, Vol. 95, Issue 4 https://doi.org/10.1063/1.3182800	journal	July 2009
Thermoelectric properties of Te-doped CoSb3 by spark plasma sintering Li, X. Y.; Chen, L. D.; Fan, J. F. Journal of Applied Physics, Vol. 98, Issue 8 https://doi.org/10.1063/1.2067704	journal	October 2005
Thermoelectric Materials for Space and Automotive Power Generation Yang, Jihui; Caillat, Thierry MRS Bulletin, Vol. 31, Issue 3 https://doi.org/10.1557/mrs2006.49	journal	March 2006
Transport and mechanical properties of Yb-filled skutterudites Salvador, J. R.; Yang, J.; Shi, X. Philosophical Magazine, Vol. 89, Issue 19 https://doi.org/10.1080/14786430903019099	journal	July 2009
Rapid preparation of CeFe4Sb12 skutterudite by melt spinning: rich nanostructures and high thermoelectric performance Tan, Gangjian; Liu, Wei; Wang, Shanyu Journal of Materials Chemistry A, Vol. 1, Issue 40 https://doi.org/10.1039/c3ta13024j	journal	January 2013
Thermoelectrics Nolas, George S.; Sharp, Jeffrey; Goldsmid, H. Julian Springer Series in Materials Science https://doi.org/10.1007/978-3-662-04569-5	book	January 2001
Identifying the Specific Nanostructures Responsible for the High Thermoelectric Performance of (Bi,Sb) ₂ Te ₃ Nanocomposites Xie, Wenjie; He, Jian; Kang, Hye Jung Nano Letters, Vol. 10, Issue 9 https://doi.org/10.1021/nl100804a	journal	September 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
Opportunities and challenges for a sustainable energy future Chu, Steven; Majumdar, Arun Nature, Vol. 488, Issue 7411, p. 294-303 https://doi.org/10.1038/nature11475	journal	August 2012
Searching for a Better Thermal Battery Gur, I.; Sawyer, K.; Prasher, R. Science, Vol. 335, Issue 6075, p. 1454-1455 https://doi.org/10.1126/science.1218761	journal	March 2012
Thermoelectric properties of chemically substituted skutterudites YbyCo4SnxSb12−x Dilley, N. R.; Bauer, E. D.; Maple, M. B. Journal of Applied Physics, Vol. 88, Issue 4 https://doi.org/10.1063/1.1305837	journal	August 2000
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
High performance InxCeyCo4Sb12 thermoelectric materials with in situ forming nanostructured InSb phase Li, Han; Tang, Xinfeng; Zhang, Qingjie Applied Physics Letters, Vol. 94, Issue 10 https://doi.org/10.1063/1.3099804	journal	March 2009
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
The maximum possible conversion efficiency of silicon‐germanium thermoelectric generators Slack, Glen A.; Hussain, Moayyed A. Journal of Applied Physics, Vol. 70, Issue 5 https://doi.org/10.1063/1.349385	journal	September 1991
Thermoelectric properties of a composite medium Bergman, David J.; Levy, Ohad Journal of Applied Physics, Vol. 70, Issue 11 https://doi.org/10.1063/1.349830	journal	December 1991
Valence of Cr in skutterudites: Electrical transport and magnetic properties of Cr-doped ${CoSb}_{3}$ Yang, J.; Endres, M. G.; Meisner, G. P. Physical Review B, Vol. 66, Issue 1 https://doi.org/10.1103/physrevb.66.014436	journal	July 2002
Anisotropic Multicenter Bonding and High Thermoelectric Performance in Electron-Poor CdSb Wang, Shanyu; Yang, Jiong; Wu, Lihua Chemistry of Materials, Vol. 27, Issue 3 https://doi.org/10.1021/cm504398d	journal	January 2015
Thermoelectric properties of p-type skutterudites YbxFe3.5Ni0.5Sb12 (0.8⩽x⩽1) Cho, J. Y.; Ye, Z.; Tessema, M. M. Acta Materialia, Vol. 60, Issue 5 https://doi.org/10.1016/j.actamat.2011.12.022	journal	March 2012
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
Anomalous barium filling fraction and n -type thermoelectric performance of BayCo4Sb12 Chen, L. D.; Kawahara, T.; Tang, X. F. Journal of Applied Physics, Vol. 90, Issue 4 https://doi.org/10.1063/1.1388162	journal	August 2001
Avoided crossing of rattler modes in thermoelectric materials Christensen, Mogens; Abrahamsen, Asger B.; Christensen, Niels B. Nature Materials, Vol. 7, Issue 10 https://doi.org/10.1038/nmat2273	journal	August 2008
Cooling, Heating, Generating Power, and Recovering Waste Heat with Thermoelectric Systems Bell, L. E. Science, Vol. 321, Issue 5895, p. 1457-1461 https://doi.org/10.1126/science.1158899	journal	September 2008
High thermoelectric performance of Yb0.26Co4Sb12/yGaSb nanocomposites originating from scattering electrons of low energy Xiong, Zhen; Chen, Xihong; Huang, Xiangyang Acta Materialia, Vol. 58, Issue 11 https://doi.org/10.1016/j.actamat.2010.03.025	journal	June 2010
p-Type skutterudites RxMyFe3CoSb12 (R, M = Ba, Ce, Nd, and Yb): Effectiveness of double-filling for the lattice thermal conductivity reduction Liu, Ruiheng; Yang, Jiong; Chen, Xihong Intermetallics, Vol. 19, Issue 11 https://doi.org/10.1016/j.intermet.2011.06.010	journal	November 2011
Temperature dependent solubility of Yb in Yb–CoSb3 skutterudite and its effect on preparation, optimization and lifetime of thermoelectrics Tang, Yinglu; Chen, Sinn-wen; Snyder, G. Jeffrey Journal of Materiomics, Vol. 1, Issue 1 https://doi.org/10.1016/j.jmat.2015.03.008	journal	March 2015
Rapid preparation method of bulk nanostructured Yb0.3Co4Sb12+y compounds and their improved thermoelectric performance Li, Han; Tang, Xinfeng; Zhang, Qingjie Applied Physics Letters, Vol. 93, Issue 25 https://doi.org/10.1063/1.3054158	journal	December 2008
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 Su, Xianli; Li, Han; Wang, Guoyu Chemistry of Materials, Vol. 23, Issue 11 https://doi.org/10.1021/cm200560s	journal	June 2011
Creation of Yb2O3 Nanoprecipitates Through an Oxidation Process in Bulk Yb-Filled Skutterudites Ding, Juan; Gu, Hui; Qiu, Pengfei Journal of Electronic Materials, Vol. 42, Issue 3 https://doi.org/10.1007/s11664-012-2370-5	journal	January 2013
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. 134, Issue 5 https://doi.org/10.1021/ja211185w	journal	January 2012
High-performance nanostructured thermoelectric materials Li, Jing-Feng; Liu, Wei-Shu; Zhao, Li-Dong NPG Asia Materials, Vol. 2, Issue 4 https://doi.org/10.1038/asiamat.2010.138	journal	October 2010
Simultaneously optimizing the independent thermoelectric properties in (Ti,Zr,Hf)(Co,Ni)Sb alloy by in situ forming InSb nanoinclusions Xie, W. J.; He, J.; Zhu, S. Acta Materialia, Vol. 58, Issue 14 https://doi.org/10.1016/j.actamat.2010.05.005	journal	August 2010
Conversion efficiency of skutterudite-based thermoelectric modules Salvador, James R.; Cho, Jung Y.; Ye, Zuxin Phys. Chem. Chem. Phys., Vol. 16, Issue 24 https://doi.org/10.1039/C4CP01582G	journal	January 2014
Einstein modes in the phonon density of states of the single-filled skutterudite ${Yb}_{0.2} {Co}_{4} {Sb}_{12}$ Dimitrov, I. K.; Manley, M. E.; Shapiro, S. M. Physical Review B, Vol. 82, Issue 17 https://doi.org/10.1103/PhysRevB.82.174301	journal	November 2010
Solubility study of Yb in $n$ -type skutterudites ${Yb}_{x} {Co}_{4} {Sb}_{12}$ and their enhanced thermoelectric properties Yang, J.; Hao, Q.; Wang, H. Physical Review B, Vol. 80, Issue 11 https://doi.org/10.1103/PhysRevB.80.115329	journal	September 2009
Filling Fraction Limit for Intrinsic Voids in Crystals: Doping in Skutterudites Shi, X.; Zhang, W.; Chen, L. D. Physical Review Letters, Vol. 95, Issue 18 https://doi.org/10.1103/PhysRevLett.95.185503	journal	October 2005
Filling fraction limits for rare-earth atoms in $Co {Sb}_{3}$ : An ab initio approach Mei, Z. G.; Zhang, W.; Chen, L. D. Physical Review B, Vol. 74, Issue 15 https://doi.org/10.1103/PhysRevB.74.153202	journal	October 2006
Dynamics of coherent acoustic phonons in thin films of ${CoSb}_{3}$ and partially filled ${Yb}_{x}$ ${Co}_{4}$ ${Sb}_{12}$ skutterudites He, Chuan; Daniel, Marcus; Grossmann, Martin Physical Review B, Vol. 89, Issue 17 https://doi.org/10.1103/PhysRevB.89.174303	journal	May 2014
Recent advances in magnetic structure determination by neutron powder diffraction Rodríguez-Carvajal, Juan Physica B: Condensed Matter, Vol. 192, Issue 1-2 https://doi.org/10.1016/0921-4526(93)90108-I	journal	October 1993
Intermediate valence in the filled skutterudite compound ${YbFe}_{4} {Sb}_{12}$ Dilley, N. R.; Freeman, E. J.; Bauer, E. D. Physical Review B, Vol. 58, Issue 10 https://doi.org/10.1103/PhysRevB.58.6287	journal	September 1998
Chemical properties and thermopower of the new series of skutterudite Ce1−pYbpFe4Sb12 Bérardan, D.; Godart, C.; Alleno, E. Journal of Alloys and Compounds, Vol. 351, Issue 1-2 https://doi.org/10.1016/S0925-8388(02)01047-2	journal	March 2003
Iron valence in skutterudites: Transport and magnetic properties of ${Co}_{1 - x} {Fe}_{x} {Sb}_{3}$ Yang, J.; Meisner, G. P.; Morelli, D. T. Physical Review B, Vol. 63, Issue 1 https://doi.org/10.1103/PhysRevB.63.014410	journal	December 2000
Electrical Properties of Silicon Containing Arsenic and Boron Morin, F. J.; Maita, J. P. Physical Review, Vol. 96, Issue 1 https://doi.org/10.1103/PhysRev.96.28	journal	October 1954
Temperature Dependence of the Effective Masses in PbTe Lyden, Henry A. Physical Review, Vol. 135, Issue 2A https://doi.org/10.1103/PhysRev.135.A514	journal	July 1964
Influence of electron-phonon interaction on the lattice thermal conductivity of ${Co}_{1 - x} {Ni}_{x} {Sb}_{3}$ Yang, J.; Morelli, D. T.; Meisner, G. P. Physical Review B, Vol. 65, Issue 9 https://doi.org/10.1103/PhysRevB.65.094115	journal	February 2002
Electron and phonon scattering in the high-temperature thermoelectric ${La}_{3} {Te}_{4 - z} M_{z}$ $(M = Sb, Bi)$ May, Andrew F.; Flage-Larsen, Espen; Snyder, G. Jeffrey Physical Review B, Vol. 81, Issue 12 https://doi.org/10.1103/PhysRevB.81.125205	journal	March 2010
Einstein Modes in the Phonon Density of States of the Single-Filled Skutterudite Yb$_{0.2}$Co$_{4}$Sb$_{12}$ Dimitrov, I. K.; Manley, M. E.; Shapiro, S. M. arXiv https://doi.org/10.48550/arxiv.1005.3867	text	January 2010

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