DataVXJournal of Materials SciencePaper
journal article·2020-10Open access

New synthesis route of highly porous InxCo4Sb12 with strongly reduced thermal conductivity

N. Gostkowska-Lekner, B. Trawinski, A. Kosonowski, B. Bochentyn, M. Lapinski, T. Miruszewski, K. Wojciechowski, B. Kusz

Journal of Materials Science· Volume 55· Issue 28
Publisher pageOpen full text
Source abstract

Abstract

Abstract Highly porous, In-filled CoSb3 skutterudite materials with an attractive thermoelectric figure of merit (ZT ~ 1) and corresponding dense samples were fabricated through the cost-effective method of reduction in oxides in dry hydrogen and the pulsed electric current sintering (PECS) method, respectively. The reduction process was described in detail using in situ thermogravimetric analysis of Co2O3, Sb2O3 and In(NO3)3·5H2O separately and in a mixture. Two methods to synthesise the same material were examined: (a) free sintering of an initially reduced powder and (b) PECS. The free-sintered materials with higher porosities (up to ~ 40%) exhibited lower values of electrical conductivity than the dense PECS samples (porosity up to ~ 5%), but the benefit of an even sixfold reduction in thermal conductivity resulted in higher ZT values. The theoretical values of thermal conductivity for various effective media models considering randomly oriented spheroid pores are in good agreement with the experimental thermal conductivity data. The assumed distribution and shape of the pores correlated well with the scanning electron microscope analysis of the microstructure. The lowest value of thermal conductivity, equal to 0.5 W/m K, was measured at 523 K for In0.1Co4Sb12 with 41% porosity. The highest value of ZTmax = 1.0 at 673 K was found for the In0.2Co4Sb12 sample in which the porosity was 36%. Graphic abstract
Source: crossref · Quality: baseline

Research context

Ceramics & glasses

OpenAlex topics: Advanced Thermoelectric Materials and Devices · Phase-change materials and chalcogenides · Thermodynamic and Structural Properties of Metals and Alloys

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

References (77)

Show source-provided references
1. Tang Y, Hanus R, Chen SW, Snyder GJ (2015) Solubility design leading to high figure of merit in low-cost Ce-CoSb3 skutterudites. Nat Commun 6:1–7. https://doi.org/10.1038/ncomms858410.1038/ncomms8584 ↗
2. Morelli DT, Meisner GP, Chen B et al (1997) Cerium filling and doping of cobalt triantimonide. Phys Rev B Condens Matter Mater Phys 56:7376–7383. https://doi.org/10.1103/PhysRevB.56.737610.1103/PhysRevB.56.7376 ↗
3. Tang Y, Chen S, Snyder GJ (2015) Temperature dependent solubility of Yb in Yb–CoSb3 skutterudite and its effect on preparation, optimization and lifetime of thermoelectrics. J Mater 1:75–84. https://doi.org/10.1016/j.jmat.2015.03.00810.1016/j.jmat.2015.03.008 ↗
4. Jelínek M, Zeipl R, Kocourek T et al (2015) Study of Yb-doped CoSb3 thermoelectric thin films prepared by laser. Appl Mech Mater 749:46–50. https://doi.org/10.4028/www.scientific.net/AMM.749.4610.4028/www.scientific.net/AMM.749.46 ↗
5. Benyahia M, Ohorodniichuk V, Leroy E et al (2018) High thermoelectric figure of merit in mesostructured In0.25Co4Sb12 n-type skutterudite. J Alloys Compd 735:1096–1104. https://doi.org/10.1016/j.jallcom.2017.11.19510.1016/j.jallcom.2017.11.195 ↗
6. Sofo JO, Mahan GD (1998) Electronic structure of CoSb3: a narrow-band-gap semiconductor. Phys Rev B 58:15620–15623. https://doi.org/10.1103/PhysRevB.58.1562010.1103/PhysRevB.58.15620 ↗
7. Nolas GS, Morelli DT, Tritt TM (1999) SKUTTERUDITES: a phonon-glass-electron crystal approach to advanced thermoelectric energy conversion applications. Annu Rev Mater Sci 29:89–116. https://doi.org/10.1146/annurev.matsci.29.1.8910.1146/annurev.matsci.29.1.89 ↗
8. Pei YZ, Yang J, Chen LD et al (2009) Improving thermoelectric performance of caged compounds through light-element filling. Appl Phys Lett 95:10–13. https://doi.org/10.1063/1.318280010.1063/1.3182800 ↗
9. Zhang J, Xu B, Wang LM et al (2012) High-pressure synthesis of phonon-glass electron-crystal featured thermoelectric LixCo4Sb12. Acta Mater 60:1246–1251. https://doi.org/10.1016/j.actamat.2011.10.05910.1016/j.actamat.2011.10.059 ↗
10. Chen LD, Kawahara T, Tang XF et al (2001) Anomalous barium filling fraction and n-type thermoelectric performance of BayCo4Sb12. J Appl Phys 90:1864–1868. https://doi.org/10.1063/1.138816210.1063/1.1388162 ↗
11. Dahal T, Jie Q, Joshi G et al (2014) Thermoelectric property enhancement in Yb-doped n-type skutterudites YbxCo4Sb12. Acta Mater 75:316–321. https://doi.org/10.1016/j.actamat.2014.05.01910.1016/j.actamat.2014.05.019 ↗
12. Khovaylo VV, Korolkov TA, Voronin AI et al (2017) Rapid preparation of InxCo4Sb12 with a record-breaking ZT = 1.5: the role of the In overfilling fraction limit and Sb overstoichiometry. J Mater Chem A 5:3541–3546. https://doi.org/10.1039/c6ta09092c10.1039/c6ta09092c ↗
13. Yang J, Stabler FR (2009) Automotive applications of thermoelectric materials. J Electron Mater 38:1245–1251. https://doi.org/10.1007/s11664-009-0680-z10.1007/s11664-009-0680-z ↗
14. Yang J, Caillat T (2006) Thermoelectric materials for space and automotive power generation. MRS Bull 31:224–22910.1557/mrs2006.49 ↗
15. Bötner H Survey on status and trends of thermoelectrics in Europe. In: 3rd conference thermoelectrics goes automotive. Berlin
16. Leblanc S, Yee SK, Scullin ML et al (2014) Material and manufacturing cost considerations for thermoelectrics. Renew Sustain Energy Rev 32:313–327. https://doi.org/10.1016/j.rser.2013.12.03010.1016/j.rser.2013.12.030 ↗
17. LeBlanc S (2014) Thermoelectric generators: linking material properties and systems engineering for waste heat recovery applications. Sustain Mater Technol 1:26–35. https://doi.org/10.1016/j.susmat.2014.11.00210.1016/j.susmat.2014.11.002 ↗
18. Li G, Kurosaki K, Ohishi Y et al (2013) Thermoelectric properties of indium-added skutterudites InxCo4Sb12. J Electron Mater 42:1463–1468. https://doi.org/10.1007/s11664-012-2290-410.1007/s11664-012-2290-4 ↗
19. Sesselmann A, Dasgupta T, Kelm K et al (2011) Transport properties and microstructure of indium-added cobalt-antimony-based skutterudites. J Mater Res 26:1820–1826. https://doi.org/10.1557/jmr.2011.10210.1557/jmr.2011.102 ↗
20. Li H, Su X, Tang X et al (2017) Grain boundary engineering with nano-scale InSb producing high performance InxCeyCo4Sb12+z skutterudite thermoelectrics. J Mater 3:273–279. https://doi.org/10.1016/j.jmat.2017.07.00310.1016/j.jmat.2017.07.003 ↗
21. Alleno E, Chen L, Chubilleau C et al (2010) Thermal conductivity reduction in CoSb3–CeO2 nanocomposites. J Electron Mater 39:1966–1970. https://doi.org/10.1007/s11664-009-1043-510.1007/s11664-009-1043-5 ↗
22. Li H, Tang X, Zhang Q, Uher C (2008) Rapid preparation method of bulk nanostructured Yb0.3Co4Sb12+y compounds and their improved thermoelectric performance. Appl Phys Lett 93:2006–2009. https://doi.org/10.1063/1.305415810.1063/1.3054158 ↗
23. Biswas K, Muir S, Subramanian MA (2011) Rapid microwave synthesis of indium filled skutterudites: an energy efficient route to high performance thermoelectric materials. Mater Res Bull 46:2288–2290. https://doi.org/10.1016/j.materresbull.2011.08.05810.1016/j.materresbull.2011.08.058 ↗
24. Pourghahramani P, Forssberg E (2007) Reduction kinetics of mechanically activated hematite concentrate with hydrogen gas using nonisothermal methods. Thermochim Acta 454:69–77. https://doi.org/10.1016/j.tca.2006.12.02310.1016/j.tca.2006.12.023 ↗
25. Rodriguez JA, Hanson JC, Frenkel AI et al (2002) Experimental and theoretical studies on the reaction of H2 with NiO: role of O vacancies and mechanism for oxide reduction. J Am Chem Soc 124:346–354. https://doi.org/10.1021/ja012108010.1021/ja0121080 ↗
26. Juarez JC, Morales R (2008) Reduction kinetics of Ag2MoO4 by hydrogen. Metall Mater Trans B Process Metall Mater Process Sci 39:738–745. https://doi.org/10.1007/s11663-008-9173-310.1007/s11663-008-9173-3 ↗
27. Bochentyn B, Karczewski J, Miruszewski T, Kusz B (2015) Structure and thermoelectric properties of Bi–Te alloys obtained by novel method of oxide substrates reduction. J Alloys Compd 646:1124–1132. https://doi.org/10.1016/j.jallcom.2015.06.12710.1016/j.jallcom.2015.06.127 ↗
28. Trawiński B, Bochentyn B, Gostkowska N et al (2018) Structure and thermoelectric properties of bismuth telluride—carbon composites. Mater Res Bull 99:10–17. https://doi.org/10.1016/j.materresbull.2017.10.04310.1016/j.materresbull.2017.10.043 ↗
29. Bochentyn BM, Karczewski JL, Miruszewski T, Kusz B (2015) Novel method for metal—oxide glass composite fabrication for use in thermoelectric devices. Mater Res Bull 76:195–204. https://doi.org/10.1016/j.materresbull.2015.12.01810.1016/j.materresbull.2015.12.018 ↗
30. Bochentyn B, Miruszewski T, Karczewski J, Kusz B (2016) Thermoelectric properties of bismuth-antimony-telluride alloys obtained by reduction of oxide reagents. Mater Chem Phys 177:353–359. https://doi.org/10.1016/j.matchemphys.2016.04.03910.1016/j.matchemphys.2016.04.039 ↗
31. Lee G, Ha G (2014) Synthesis of Bi0.5Sb1.5Te3 thermoelectric powder using an oxide-reduction process. J Electron Mater 43:1697–1702. https://doi.org/10.1007/s11664-013-2846-y10.1007/s11664-013-2846-y ↗
32. Kusz B, Miruszewski T, Bochentyn B, Karczewski J (2016) Structure and thermoelectric properties of Te–Ag–Ge–Sb (TAGS) materials obtained by reduction of melted oxide substrates. J Electron Mater 45:2–4. https://doi.org/10.1007/s11664-015-4251-110.1007/s11664-015-4251-1 ↗
33. Lee G, Park B, Kim W et al (2010) Synthesis of Bi–Te–Se-based thermoelectric powder by an oxide-reduction process. Electron Mater Lett 6:123–127. https://doi.org/10.3365/eml.2010.09.12310.3365/eml.2010.09.123 ↗
34. Lim YS, Wi S, Lee G (2017) Synthesis of n-type Bi2Te1−xSex compounds through oxide reduction process and related thermoelectric properties. J Eur Ceram Soc 37:3361–3366. https://doi.org/10.1016/j.jeurceramsoc.2017.04.02010.1016/j.jeurceramsoc.2017.04.020 ↗
35. Gostkowska N, Miruszewski T, Trawiński B et al (2017) Structure and thermoelectric properties of Cs–Bi–Te alloys fabricated by different routes of reduction of oxide reagents. Solid State Sci 73:41–50. https://doi.org/10.1016/j.solidstatesciences.2017.07.01610.1016/j.solidstatesciences.2017.07.016 ↗
36. Khan A, Saleemi M, Johnsson M et al (2014) Fabrication, spark plasma consolidation, and thermoelectric evaluation of nanostructured CoSb3. J Alloys Compd 612:293–300. https://doi.org/10.1016/j.jallcom.2014.05.11910.1016/j.jallcom.2014.05.119 ↗
37. Kim SH, Kim MC, Kim MS et al (2016) Nanophase oxalate precursors of thermoelectric CoSb3 by controlled coprecipitation predicted by thermodynamic modeling. Adv Powder Technol 27:773–778. https://doi.org/10.1016/j.apt.2016.03.00610.1016/j.apt.2016.03.006 ↗
38. Wu CF, Wei TR, Sun FH, Li JF (2017) Nanoporous PbSe–SiO2 thermoelectric composites. Adv Sci. https://doi.org/10.1002/advs.20170019910.1002/advs.201700199 ↗
39. Yang H, Wen P, Zhou X et al (2019) Enhanced thermoelectric performance of Te-doped skutterudite with nano-micro-porous architecture. Scr Mater 159:68–71. https://doi.org/10.1016/j.scriptamat.2018.09.01510.1016/j.scriptamat.2018.09.015 ↗
40. Peng Z, Kong LX (2007) A thermal degradation mechanism of polyvinyl alcohol/silica nanocomposites. Polym Degrad Stab 92:1061–1071. https://doi.org/10.1016/j.polymdegradstab.2007.02.01210.1016/j.polymdegradstab.2007.02.012 ↗
41. LeBail A (2005) Whole powder pattern decomposition methods and applications. Powder Diffr 20:316–326. https://doi.org/10.1154/1.213531510.1154/1.2135315 ↗
42. Sabat KC, Paramguru RK, Pradhan S, Mishra BK (2015) Reduction of cobalt oxide (Co3O4) by low temperature hydrogen plasma. Plasma Chem Plasma Process 35:387–399. https://doi.org/10.1007/s11090-014-9602-910.1007/s11090-014-9602-9 ↗
43. Galleos NG, Porto Lopez JM (1988) Kinetic study of cobalt oxides reduction by hydrogen. Mater Chem Phys 19:431–44610.1016/0254-0584(88)90036-3 ↗
44. Bulavchenko OA, Cherepanova SV, Tsybulya SV (2009) In situ XRD investigation of Co3O4 reduction. Zeitschrift fur Krist Suppl 30:329–334. https://doi.org/10.1524/zksu.2009.004810.1524/zksu.2009.0048 ↗
45. Ishchenko AV, Bulavchenko OA, Cherepanova SV et al (2009) In situ XRD study of nanocrystalline cobalt oxide reduction. Kinet Catal 50:192–198. https://doi.org/10.1134/s002315840902008610.1134/s0023158409020086 ↗
46. Chernogorenko VB, Lynchak KA, Klimak ZA, Morozova RA (1978) Kinetics of antimony trioxide reduction by hydrogen. Effect of atomic hydrogen. Sov Powder Metall Met Ceram 17:419–421. https://doi.org/10.1007/BF0079579110.1007/BF00795791 ↗
47. Das R, Soni RK (2017) Synthesis and surface-enhanced Raman scattering of indium nanotriangles and nanowires. RSC Adv 7:32255–32263. https://doi.org/10.1039/C7RA03317F10.1039/C7RA03317F ↗
48. Detweiler ZM, Wulfsberg SM, Frith MG et al (2016) The oxidation and surface speciation of indium and indium oxides exposed to atmospheric oxidants. Surf Sci 648:188–195. https://doi.org/10.1016/J.SUSC.2015.10.02610.1016/J.SUSC.2015.10.026 ↗
49. Leszczyński J, Szczypka W, Candolfi C et al (2017) HPHT synthesis of highly doped InxCo4Sb12—experimental and theoretical study. J Alloys Compd 727:1178–1188. https://doi.org/10.1016/J.JALLCOM.2017.08.19410.1016/J.JALLCOM.2017.08.194 ↗
50. Zhao W, Wei P, Zhang Q et al (2015) Multi-localization transport behaviour in bulk thermoelectric materials. Nat Commun 6:6197. https://doi.org/10.1038/ncomms719710.1038/ncomms7197 ↗
51. Zhao W, Wei P, Zhang Q et al (2009) Enhanced thermoelectric performance in barium and indium double-filled skutterudite bulk materials via orbital hybridization induced by indium filler. J Am Chem Soc 131:3713–3720. https://doi.org/10.1021/ja808933410.1021/ja8089334 ↗
52. Dupin J, Gonbeau D, Benqlilou-Moudden H et al (2001) XPS analysis of new lithium cobalt oxide thin-films before and after lithium deintercalation. Thin Solid Films 384:23–32. https://doi.org/10.1016/S0040-6090(00)01802-210.1016/S0040-6090(00)01802-2 ↗
53. Grosvenor AP, Cavell RG, Mar A (2006) X-ray photoelectron spectroscopy study of the skutterudites LaFe4Sb12, CeFe4Sb12, CoSb3, and CoP3. Phys Rev B 74:125102. https://doi.org/10.1103/PhysRevB.74.12510210.1103/PhysRevB.74.125102 ↗
54. Anno H, Matsubara K, Caillat T, Fleurial JP (2000) Valence-band structure of the skutterudite compounds CoAs3, CoSb3, and RhSb3 studied by x-ray photoelectron spectroscopy. Phys Rev B Condens Matter Mater Phys 62:10737–10743. https://doi.org/10.1103/PhysRevB.62.1073710.1103/PhysRevB.62.10737 ↗
55. Eilertsen J, Li J, Rouvimov S, Subramanian MA (2011) Thermoelectric properties of indium-filled InxRh4Sb12 skutterudites. J Alloys Compd 509:6289–6295. https://doi.org/10.1016/j.jallcom.2011.03.05710.1016/j.jallcom.2011.03.057 ↗
56. Wang L, Cai KF, Wang YY et al (2009) Thermoelectric properties of indium-filled skutterudites prepared by combining solvothermal synthesis and melting. Appl Phys A Mater Sci Process 97:841–845. https://doi.org/10.1007/s00339-009-5329-510.1007/s00339-009-5329-5 ↗
57. Tang Y, Qiu Y, Xi L et al (2014) Phase diagram of In–Co–Sb system and thermoelectric properties of In-containing skutterudites. Energy Environ Sci 7:812–819. https://doi.org/10.1039/c3ee43240h10.1039/c3ee43240h ↗
58. Juretschke HJ, Landauer R, Swanson JA (1956) Hall effect and conductivity in porous media. J Appl Phys 27:838–83910.1063/1.1722496 ↗
59. Gayner C, Prakash D, Ballal A (2017) Influence of secondary phase dispersants and porosity on thermoelectric properties of β-Fe0.91Mn0.09Si2. J Alloys Compd 698:164–169. https://doi.org/10.1016/j.jallcom.2016.12.25310.1016/j.jallcom.2016.12.253 ↗
60. Hu C, Zeng X, Liu Y et al (2017) Effects of partial La filling and Sb vacancy defects on CoSb3 skutterudites. Phys Rev B 95:165204. https://doi.org/10.1103/PhysRevB.95.16520410.1103/PhysRevB.95.165204 ↗
61. Visnow E, Heinrich CP, Schmitz A et al (2015) On the true indium content of In-filled skutterudites. Inorg Chem 54:7818–7827. https://doi.org/10.1021/acs.inorgchem.5b0079910.1021/acs.inorgchem.5b00799 ↗
62. Cernuschi F, Ahmaniemi S, Vuoristo P, Mäntylä T (2004) Modelling of thermal conductivity of porous materials: application to thick thermal barrier coatings. J Eur Ceram Soc 24:2657–2667. https://doi.org/10.1016/j.jeurceramsoc.2003.09.01210.1016/j.jeurceramsoc.2003.09.012 ↗
63. Muta H, Kurosaki K, Uno M, Yamanaka S (2003) Thermoelectric properties of constantan/spherical SiO2 and Al2O3 particles composite. J Alloys Compd 359:326–329. https://doi.org/10.1016/S0925-8388(03)00295-010.1016/S0925-8388(03)00295-0 ↗
64. Chen T-G, Yu P, Chou R-H, Pan C-L (2010) Phonon thermal conductivity suppression of bulk silicon nanowire composites for efficient thermoelectric conversion. Opt Express 18:A467–A476. https://doi.org/10.1364/oe.18.00a46710.1364/oe.18.00a467 ↗
65. Umarji AM, Ordonez-Miranda J, Wu Y et al (2018) Particle size effect on the thermal conductivity reduction of silicon based thermoelectric composites. Sustain Energy Fuels 2:1764–1771. https://doi.org/10.1039/c8se00131f10.1039/c8se00131f ↗
66. Wu CA, Chang KC, Lin FH et al (2019) Low thermal conductivity and enhanced zT values of porous and nanostructured Cu1–xNix alloys. Chem Eng J 368:409–416. https://doi.org/10.1016/j.cej.2019.02.19810.1016/j.cej.2019.02.198 ↗
67. Landauer R (1978) Electrical conductivity in inhomogeneous media. In: AIP conference proceedings. AIP, pp 2–4510.1063/1.31150 ↗
68. McPherson R (1984) A model for the thermal conductivity of plasma-sprayed ceramic coatings. Thin Solid Films 112:89–95. https://doi.org/10.1016/0040-6090(84)90506-610.1016/0040-6090(84)90506-6 ↗
69. Schulz B (1981) Thermal conductivity of porous and highly porous materials. High Temp High Press 13:649–660
70. Cernuschi F, Bianchi P, Leoni M, Scardi P (1999) Thermal diffusivity/microstructure relationship in Y-PSZ thermal barrier coatings. J Therm Spray Technol 8:102–109. https://doi.org/10.1361/10599639977035062910.1361/105996399770350629 ↗
71. Scardi P, Leoni M, Cernuschi F, Figari A (2001) Microstructure and heat transfer phenomena in ceramic thermal barrier coatings. J Am Ceram Soc 84:827–835. https://doi.org/10.1111/j.1151-2916.2001.tb00748.x10.1111/j.1151-2916.2001.tb00748.x ↗
72. Bianchi P, Cernuschi F, Lorenzoni L, et al (2002) Thermophysical and microstructural characterization of modified thick yttria stabilised zirconia thermal barrier coatings. In: Lecomte-Beckers J, Carton M, Schubert F, Ennis PJ (eds) Materials for advanced power engineering 2002. Schriften des Forschungszentrum Julich, pp 449–463
73. Maxwell JC (1873) A treatise on electricity and magnetism, vol I. Macmillan and Co. Publishers, London
74. Bruggeman DAG (1937) Berechnung verschiedener physikalischer Konstanten von heterogenen Substanzen. III. Die elastischen Konstanten der quasiisotropen Mischkörper aus isotropen Substanzen. Ann Phys 421:160–178. https://doi.org/10.1002/andp.1937421020510.1002/andp.19374210205 ↗
75. Schulz B (1974) Die Abhängigkeit der Feideigemchaften zweiphasiger Werkstoffe von ihrem Gefiigeaufbal. Theoretische überlegungen und experimentelle Prühmg am Beispiel der Wärmeleitfähigkeit von Cermets. Report KfK, FRG
76. Meredith RE, Tobias CW (1962) Conduction in heterogenous systems. In: Advances in electrochemistry and electrochemical engineering. New York
77. Kosonowski A (2019) Bruggeman model visualization for porous materials. 1. https://doi.org/10.17632/R639F4G276.110.17632/R639F4G276.1 ↗