On the True Indium Content of In-Filled Skutterudites

[en] The incongruently melting single-filled skutterudite In<inf>x</inf>Co<inf>4</inf>Sb<inf>12</inf> is known as a promising bulk thermoelectric material. However, the products of current bulk syntheses contain always impurities of InSb, Sb, CoSb, or CoSb<inf>2</inf>, which prevent an unbiased determination of its thermoelectric properties. We report a new two-step synthesis of high-purity In<inf>x</inf>Co<inf>4</inf>Sb<inf>12</inf> with nominal compositions x = 0.12, 0.15, 0.18, and 0.20 that separates the kieftite (CoSb<inf>3</inf>) formation from the topotactic filler insertion. This approach allows conducting the reactions at lower temperatures with shorter reaction times and circumventing the formation of impurity phases. The synthesis can be extended to other filled skutterudites. High-density (>98%) pellets for thermoelectric characterization were prepared by current-assisted short-time sintering. Sample homogeneity was demonstrated by potential and Seebeck microprobe measurements of the complete pellet surfaces. Synchrotron X-ray diffraction showed a purity of 99.9% product with traces (≤0.1%) of InSb in samples of nominal composition In<inf>0.18</inf>Co<inf>4</inf>Sb<inf>12</inf> and In<inf>0.20</inf>Co<inf>4</inf>Sb<inf>12</inf>. Rietveld refinements revealed a linear correlation between the true In occupancy and the lattice parameter a. This allows the determination of the true In filling in skutterudites and predicting the In content of unknown A<inf>x</inf>Co<inf>4</inf>Sb<inf>12</inf>. The high purity of In<inf>x</inf>Co<inf>4</inf>Sb<inf>12</inf> allowed studying the transport properties without bias from side phases. A figure of merit close to unity at 420 °C was obtained for a sample of a true composition of In<inf>0.160(2)</inf>Co<inf>4</inf>Sb<inf>12</inf> (nominal composition In<inf>0.18</inf>Co<inf>4</inf>Sb<inf>12</inf>). The lower degree of In filling has a dramatic effect on the thermoelectric properties as demonstrated by the sample of nominal composition In<inf>0.20</inf>Co<inf>4</inf>Sb<inf>12</inf>. The presence of InSb in amounts of ∼0.1 vol% led to a substantially lower degree of interstitial site filling of 0.144, and the figure of merit zT decreased by 18%, which demonstrates the significance of the true filler atom content in skutterudite materials. (Graph Presented). © 2015 American Chemical Society.

Disciplines :

Chemistry

Author, co-author :

Visnow, E.; Institut für Anorganische Chemie und Analytische Chemie, Johannes Gutenberg-Universität, Duesbergweg 10-14, Mainz, Germany

Heinrich, C. P.; Institut für Anorganische Chemie und Analytische Chemie, Johannes Gutenberg-Universität, Duesbergweg 10-14, Mainz, Germany, Graduate School Materials Science in Mainz, Johannes Gutenberg-Universität, Staudinger Weg 9, Mainz, Germany

Schmitz, A.; Deutsches Zentrum für Luft- und Raumfahrt E.V. (DLR), Institut für Werkstoff-Forschung, Linder Höhe, Köln, Germany

De Boor, J.; Deutsches Zentrum für Luft- und Raumfahrt E.V. (DLR), Institut für Werkstoff-Forschung, Linder Höhe, Köln, Germany

Leidich, P.; Institut für Anorganische Chemie und Analytische Chemie, Johannes Gutenberg-Universität, Duesbergweg 10-14, Mainz, Germany

Klobes, B.; Jülich Centre for Neutron Science JCNS, Peter Grünberg Institute PGI, Forschungszentrum Jülich GmbH, Jülich, Germany

Hermann, Raphaël ; Université de Liège - ULiège > Département de chimie (sciences) > Département de chimie (sciences)

Müller, W. E.; Deutsches Zentrum für Luft- und Raumfahrt E.V. (DLR), Institut für Werkstoff-Forschung, Linder Höhe, Köln, Germany, Institute of Inorganic and Analytical Chemistry, Justus Liebig University Giessen, Heinrich-Buff-Ring 58, Giessen, Germany

Tremel, W.; Institut für Anorganische Chemie und Analytische Chemie, Johannes Gutenberg-Universität, Duesbergweg 10-14, Mainz, Germany

Language :

English

Title :

On the True Indium Content of In-Filled Skutterudites

Publication date :

2015

Journal title :

Inorganic Chemistry

ISSN :

0020-1669

eISSN :

1520-510X

Publisher :

American Chemical Society

Volume :

Issue :

Pages :

7818-7827

Peer reviewed :

Peer Reviewed verified by ORBi

Name of the research project :

DFG priority program SPP1386 “Nanostructured Thermoelectrics”

Funders :

DFG - Deutsche Forschungsgemeinschaft
DOE - United States. Department of Energy

Available on ORBi :

since 14 November 2020

Statistics

Number of views

52 (1 by ULiège)

Number of downloads

1 (1 by ULiège)

More statistics

Scopus citations^®

Scopus citations^®
without self-citations

OpenCitations

OpenAlex citations

Bibliography

DiSalvo, F. J. Science 1999, 285, 703-706 10.1126/science.285.5428.703
Slack, G. A. In Handbook of thermoelectrics; Rowe, D. M., Ed.; CRC Press: Boca Raton, FL, 1995; pp 407-440.
Snyder, G. J.; Toberer, E. S. Nat. Mater. 2008, 7, 105-114 10.1038/nmat2090
Venkatasubramanian, R.; Siivola, E.; Colpitts, T.; O'Quinn, B. Nature 2001, 413, 597-602 10.1038/35098012
Harman, T. C.; Taylor, P. J.; Walsh, M. P.; LaForge, B. E. Science 2002, 297, 2229-2232 10.1126/science.1072886
Hsu, K. F.; Loo, S.; Guo, F.; Chen, W.; Dyck, J. S.; Uher, C.; Hogan, T.; Polychroniadis, E. K.; Kanatzidis, M. G. Science 2004, 303, 818-821 10.1126/science.1092963
Poudel, B.; Hao, Q.; Ma, Y.; Lan, Y. C.; Minnich, A.; Yu, B.; Yan, X.; Wang, D. Z.; Muto, A.; Vashaee, D.; Chen, X. Y.; Liu, J. M.; Dresselhaus, M. S.; Chen, G.; Ren, Z. Science 2008, 320, 634-638 10.1126/science.1156446
Zeier, W. G.; LaLonde, A.; Heinrich, C.; Panthöfer, M.; Snyder, G. J.; Tremel, W. J. Am. Chem. Soc. 2012, 134, 7147-7154 10.1021/ja301452j
Sales, B. C.; Mandrus, D.; Williams, R. K. Science 1996, 272, 1325-1328 10.1126/science.272.5266.1325
Heremans, J. P.; Jovovic, V.; Toberer, E. S.; Saramat, A.; Kurosaki, K.; Charoenphakdee, A.; Yamanaka, S.; Snyder, G. J. Science 2008, 321, 554-558 10.1126/science.1159725
Zhao, L.-D.; Lo, S.-H.; Zhang, Y.; Sun, H.; Tan, G.; Uher, C.; Wolverton, C.; Dravid, V. P.; Kanatzidis, M. G. Nature 2014, 508, 373-377 10.1038/nature13184
Nolas, G. S.; Morelli, D. T.; Tritt, T. M. Annu. Rev. Mater. Sci. 1999, 29, 89-116 10.1146/annurev.matsci.29.1.89
Uher, C. Semiconductors Semimetals; Academic Press: San Diego, 2001; Vol. 69, pp 139-253
Morelli, D. T.; Meisner, G. P. J. Appl. Phys. 1995, 77, 3777-3781 10.1063/1.358552
Kawaharada, Y.; Kurosaki, K.; Uno, M.; Yamanaka, S. J. Alloys Compd. 2001, 315, 193-197 10.1016/S0925-8388(00)01275-5
Keppens, V.; Mandrus, D.; Sales, B. C.; Chakoumakos, B. C.; Dai, P.; Coldea, R.; Maple, M. B.; Gajewsk, D. A.; Freeman, E. J.; Bennington, S. Nature 1998, 395, 876-878 10.1038/27625
Schmøkel, M. S.; Bjerk, L.; Overgaard, J.; Larsen, F. K.; Madsen, G. K. H.; Sugimoto, K.; Takata, M.; Ibersen, B. B. Angew. Chem., Int. Ed. 2013, 52, 1503-1506 10.1002/anie.201206065
Schmøkel, M. S.; Bjerg, L.; Larsen, F. K.; Overgaard, J.; Cenedese, S.; Christensen, M.; Madsen, G. H. K.; Gatti, C.; Nishibori, E.; Sugimoto, K.; Takata, M.; Ibersen, B. B. Acta Crystallogr., Sect. A: Found. Crystallogr. 2013, 69, 570-582 10.1107/S0108767313024458
Mi, J.-L.; Christensen, M.; Nishibori, E.; Kuznetsov, V.; Rowe, D. M.; Ibersen, B. B. J. Appl. Phys. 2010, 107, 113507 10.1063/1.3428435
Mi, J.-L.; Christensen, M.; Nishibori, E.; Iversen, B. B. Phys. Rev. B: Condens. Matter Mater. Phys. 2011, 84, 064114 10.1103/PhysRevB.84.064114
Christensen, M.; Iversen, B. B.; Bertini, L.; Toprak, M.; Muhammed, M.; Nishibori, E. J. Appl. Phys. 2004, 96, 3148-3157 10.1063/1.1781762
Jeitschko, W.; Braun, D. Acta Crystallogr., Sect. B: Struct. Crystallogr. Cryst. Chem. 1977, 33, 3401-3406 10.1107/S056774087701108X
Braun, D. J.; Jeitschko, W. J. Less-Common Met. 1980, 72, 147-156 10.1016/0022-5088(80)90260-X
Nolas, G. S.; Cohn, J. L.; Slack, G. A. Phys. Rev. B: Condens. Matter Mater. Phys. 1998, 58, 164-170 10.1103/PhysRevB.58.164
Morelli, D. T.; Meisner, G. P.; Chen, B. X.; Hu, S. Q.; Uher, C. Phys. Rev. B: Condens. Matter Mater. Phys. 1997, 56, 7376-7383 10.1103/PhysRevB.56.7376
Lamberton, G. A.; Bhattacharya, S.; Littleton, R. T.; Kaeser, M. A.; Tedstrom, R. H.; Tritt, T. M.; Yang, J.; Nolas, G. S. Appl. Phys. Lett. 2002, 80, 598-600 10.1063/1.1433911
Kuznetsov, V. L.; Kuznetsova, L. A.; Rowe, D. M. J. Phys.: Condens. Matter 2003, 15, 5035-5048 10.1088/0953-8984/15/29/315
Chen, L. D.; Kawahara, T.; Tang, X. F.; Goto, T.; Hirai, T.; Dyck, J. S.; Chen, W.; Uher, C. J. Appl. Phys. 2001, 90, 1864-1868 10.1063/1.1388162
Puyet, M.; Lenoir, B.; Dauscher, A.; Dehmas, M.; Stiewe, C.; Müller, E. J. Appl. Phys. 2004, 95, 4852-4855 10.1063/1.1688463
Zhao, X. Y.; Shi, X.; Chen, L. D.; Zhang, W. Q.; Zhang, W. B.; Pei, Y. Z. J. Appl. Phys. 2006, 99, 053711/1-4 10.1063/1.2172705
Pei, Y. Z.; Chen, L. D.; Zhang, W.; Shi, X.; Bai, S. W.; Zhao, X. Y.; Mei, Z. G.; Li, X. Y. Appl. Phys. Lett. 2006, 89, 221107/1-4 10.1063/1.2397538
Pei, Y. Z.; Yang, J.; Chen, L. D.; Zhang, W.; Salvador, J. R.; Yang, J. Appl. Phys. Lett. 2009, 95, 042101/1-3 10.1063/1.3182800
Sellinschegg, H.; Stuckmeyer, S. L.; Hornbostel, M. D.; Johnson, D. C. Chem. Mater. 1998, 10, 1096-1101 10.1021/cm970678m
Nolas, G. S.; Takizawa, H.; Endo, T.; Sellinschegg, H.; Johnson, D. C. Appl. Phys. Lett. 2000, 77, 52-54 10.1063/1.126874
Nolas, G. S.; Yang, J.; Takizawa, H. Appl. Phys. Lett. 2004, 84, 5210-5212 10.1063/1.1765205
Liang, Y.; Borrmann, H.; Baenitz, M.; Schnelle, W.; Budnyk, S.; Zhao, J. T.; Grin, Yu. Inorg. Chem. 2008, 47, 9489-9496 10.1021/ic801154a
Fukuoka, H.; Yamanaka, S. Chem. Mater. 2010, 22, 47-51 10.1021/cm901594q
Tang, Y.; Qiu, Y.; Xi, L.; Shi, X.; Zhang, W.; Chen, L.; Tseng, S.-M.; Chen, S.-W.; Snyder, G. J. Energy Environ. Sci. 2014, 7, 812-819 10.1039/C3EE43240H
Shi, X.; Yang, J.; Salvador, J. R.; Chi, M.; Cho, J. Y.; Wang, H.; Bai, S.; Yang, J.; Zhang, W.; Chen, L. J. Am. Chem. Soc. 2011, 133, 7837-7846 10.1021/ja111199y
Hermann, R. P.; Jin, R. J.; Schweika, W.; Grandjean, F.; Mandrus, D.; Sales, B. C.; Long, G. J. Phys. Rev. Lett. 2003, 90, 135505/1-4 10.1103/PhysRevLett.90.135505
Shi, X.; Kong, H.; Li, C.-P; Uher, C.; Yang, J.; Salvador, J.; Wang, H.; Chen, L.; Zhang, W. Appl. Phys. Lett. 2008, 92, 182101/1-3 10.1063/1.2920210
Rogl, G.; Grytsiv, A.; Rogl, P.; Peranio, N.; Bauer, E.; Zehetbauer, M.; Eibl, O. Acta Mater. 2014, 63, 30-43 10.1016/j.actamat.2013.09.039
Xi, L.; Yang, J.; Lu, C.; Mei, Z.; Zhang, W.; Chen, L. Chem. Mater. 2010, 22, 2384-2394 10.1021/cm903717w
Toprak, M. S.; Stiewe, C.; Platzek, D.; Williams, S.; Bertini, L.; Müller, E.; Gatti, C.; Zhang, Y.; Rowe, M.; Muhammed, M. Adv. Funct. Mater. 2004, 14, 1189-1196 10.1002/adfm.200400109
Li, H.; Tang, X.; Zhang, Q.; Uher, C. Appl. Phys. Lett. 2009, 94, 102114/1-3 10.1063/1.3099804
Li, X.; Chen, L.; Fan, J.; Zhang, W.; Kawahara, T.; Hirai, T. J. Appl. Phys. 2005, 98, 083702/1-7
Liu, W.-S.; Zhang, B.-P; Li, J.-F.; Zhang, H.-L.; Zhao, L.-D. J. Appl. Phys. 2007, 102, 103717/1-8 10.1063/1.2815671
Yang, J.; Chen, Y.; Zhu, W.; Peng, J.; Bao, S.; Fan, X. A.; Duan, X. J. Solid State Chem. 2006, 179, 212-216 10.1016/j.jssc.2005.10.029
Li, Q.; Lin, Z.; Zhou, J. J. Electron. Mater. 2009, 38, 1268-1272 10.1007/s11664-008-0628-8
Biswas, K.; Muir, S.; Subramanian, M. Mater. Res. Bull. 2011, 46, 2288-2290 10.1016/j.materresbull.2011.08.058
Liang, T.; Su, X.; Yan, Y.; Zheng, G.; Zhang, Q.; Chi, H.; Tang, X.; Uher, C. J. Mater. Chem. A 2014, 2, 17914-17918 10.1039/C4TA02780A
Zhang, J.; Xu, B.; Wang, L.-M.; Yu, D.; Yang, J.; Yu, F.; Liu, Z.; He, J.; Wen, B.; Tian, Y. Acta Mater. 2012, 60, 1246-1251 10.1016/j.actamat.2011.10.059
Liu, W.-S.; Zhang, B.-P; Li, J.-F; Zhao, L.-D. J. Phys. D: Appl. Phys. 2007, 40, 566-572 10.1088/0022-3727/40/2/035
Okamoto, H. J. Phase Equilib. Diffus. 2005, 26, 198 10.1007/s11669-005-0156-7
Sesselmann, A. J. Ph.D. Dissertation, Universität Augsburg, 2012.
Liu, W.-S.; Zhang, B.-P.; Li, J.-F; Zhao, L.-D. J. Phys. D: Appl. Phys. 2007, 40, 6784-6790 10.1088/0022-3727/40/21/044
He, T.; Chen, J.; Rosenfeld, H. D.; Subramanian, M. A. Chem. Mater. 2006, 18, 759-762 10.1021/cm052055b
Du, Y.; Cai, K. F.; Chen, S.; Qin, Z.; Shen, S. Z. J. Electron. Mater. 2011, 40, 1215-1220 10.1007/s11664-011-1603-3
Li, G.; Kurosaki, K.; Ohishi, Y.; Muta, H.; Yamanaka, S. J. Electron. Mater. 2013, 42, 1463-1468 10.1007/s11664-012-2290-4
Sesselmann, A. J.; Dasgupta, T.; Kelm, K.; Müller, E.; Perlt, S.; Zastrow, S. J. Mater. Res. 2011, 26, 1820-1826 10.1557/jmr.2011.102
Sharp, J. W.; Jones, E. C.; Williams, R. K.; Martin, P. M.; Sales, B. C. J. Appl. Phys. 1995, 78, 1013-1018 10.1063/1.360402
Smalley, A. L. E.; Kim, S.; Johnson, D. C. Chem. Mater. 2003, 15, 3847-3851 10.1021/cm030315o
Coelho, A. Topas Academic, Version 4.1; Coelho Software, Brisbane, 2007.
Cheary, V.; Coelho, A. J. Appl. Crystallogr. 1992, 25, 109-121 10.1107/S0021889891010804
de Boor, J.; Stiewe, C.; Ziolkowski, P.; Dasgupta, T.; Karpinski, G.; Lenz, E.; Edler, F.; Müller, E. J. Electron. Mater. 2013, 42, 1711-1718 10.1007/s11664-012-2404-z
de Boor, J.; Müller, E. Rev. Sci. Instrum. 2013, 84, 065102 10.1063/1.4807697
Platzek, D.; Karpinski, G.; Drasar, C.; Müller, E. Mater. Sci. Forum 2005, 492-493, 587-592 10.4028/www.scientific.net/MSF.492-493.587
Ishida, K.; Nishizawa, T. J. Phase Equilib. 1990, 11 (3) 243-248 10.1007/BF03029292
Lu, Z. Q. J.; Lowhorn, N. D.; Wong-Ng, W.; Zhang, W.; Thomas, E. L.; Otani, M.; Green, M. L.; Tran, T. N.; Dilley, N. R.; Downey, A.; Edwards, B.; Elsner, N.; Ghamaty, S.; Hogan, T.; Jie, Q.; Li, Q.; Martin, J.; Nolas, G.; Obara, H.; Sharp, J.; Venkatasubramanian, R.; Willigan, R.; Yang, J.; Tritt, T. J. Res. Natl. Inst. Stand. Technol. 2009, 114, 37-55 10.6028/jres.114.004
Kjekshus, A.; Nicholson, D. G.; Rakke, T.; Jalonen, H.; Lüning, B.; Swahn, C. G. Acta Chem. Scand. 1973, 27, 1315-1320 10.3891/acta.chem.scand.27-1315
Lefebvre-Devos, I.; Lassalle, M.; Wallart, X.; Olivier-Fourcade, J.; Monconduit, L.; Jumas, J. Phys. Rev. B: Condens. Matter Mater. Phys. 2001, 63, 125110/1-7 10.1103/PhysRevB.63.125110
Devos, I.; Womes, M.; Heilemann, M.; Olivier-Fourcade, J.; Jumas, J.-C.; Tirado, J.-L. J. Mater. Chem. 2004, 14, 1759-1767 10.1039/b312618h
Figueireîdoa, C. A.; Gallasa, M. R.; Zorzic, E.; Perottonia, C. A. J. Alloys Compd. 2014, 598, 266-271 10.1016/j.jallcom.2014.01.215
Grytsiv, A.; Rogl, P.; Michor, H.; Bauer, E.; Giester, G. J. Electron. Mater. 2013, 42, 2940-2952 10.1007/s11664-013-2679-8
Tang, Y.; Qiu, Y.; Xi, L.; Shi, X.; Zhang, W.; Chen, L.; Tseng, S.-M.; Chen, S. W.; Snyder, G. J. Energy Environ. Sci. 2014, 7, 812-819 10.1039/C3EE43240H
Jeitschko, W.; Foecker, A. J.; Paschke, D.; Dewalsky, M. V.; Evers, C. B. H.; Künnen, B.; Lang, A.; Kotzyba, G.; Rodewald, U.; Möller, M. H. Z. Anorg. Allg. Chem. 2000, 626, 1112-1120 10.1002/(SICI)1521-3749(200005)626:5<1112::AID-ZAAC1112>3.3.CO;2-5