Alloying engineering for thermoelectric performance enhancement in p-type skutterudites with synergistic carrier concentration optimization and thermal conductivity reduction

Zhiyuan Liu; Yonggui Wang; Ting Yang; Zuju Ma; Huiyan Zhang; Hailing Li; Ailin Xia

doi:10.26599/JAC.2023.9220702

Journal of Advanced Ceramics 2023, 12(3): 539-552 https://doi.org/10.26599/JAC.2023.9220702

Research Article |

Open Access | Issue | Published: 15 February 2023

Alloying engineering for thermoelectric performance enhancement in p-type skutterudites with synergistic carrier concentration optimization and thermal conductivity reduction

Show Author's Information Hide Author's Information Zhiyuan Liu^{^a^,^b}(

), Yonggui Wang^{^b}, Ting Yang^{^b}, Zuju Ma^{^c}(

), Huiyan Zhang^{^a^,^b}, Hailing Li^{^a^,^b}, Ailin Xia^{^a^,^b}

aKey Laboratory of Green Fabrication and Surface Technology of Advanced Metal Materials, Ministry of Education, Anhui University of Technology, Maanshan 243002, China

bSchool of Materials Science and Engineering, Anhui University of Technology, Maanshan 243002, China

cSchool of Environmental and Materials Engineering, Yantai University, Yantai 264005, China

Keywords:

synergistic optimization, Ni doping, p-type skutterudite materials, thermoelectric (TE) properties

Cite this article:

Liu Z, Wang Y, Yang T, et al. Alloying engineering for thermoelectric performance enhancement in p-type skutterudites with synergistic carrier concentration optimization and thermal conductivity reduction. Journal of Advanced Ceramics, 2023, 12(3): 539-552. https://doi.org/10.26599/JAC.2023.9220702

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Abstract Full text Electronic supplementary material About this article

Abstract

The enhancements in thermoelectric (TE) performances of p-type skutterudites are usually limited due to the relatively low Seebeck coefficients owing to the higher carrier concentration and more impurity phases induced by inherent structural instability of a Fe-based skutterudite. As shown in this study, alloying engineering of Ni doping at Fe sites in a p-type CeFe_3.8Co_0.2Sb₁₂ skutterudite can not only reduce the impurity phases with high thermal conductivity but also regulate the carrier concentration, and thus significantly increase the Seebeck coefficient. The thermal conductivity was largely suppressed due to the enhanced point defect phonon scattering and decreased hole concentration. As a result, a TE figure of merit ZT of the CeFe_3.5Ni_0.3Co_0.2Sb₁₂ sample reached 0.8, which is approximately 50% higher than that of a Ni-free sample. Appropriate Ni doping can maintain a high ZT at a high temperature by controlling the reduction in a band gap. Therefore, a high average ZT close to 0.8 at 650–800 K for CeFe_3.5Ni_0.3Co_0.2Sb₁₂ was obtained, which was comparable to or even higher than those of the reported Ce-filled Fe-based skutterudites due to the synergistic optimization of electrical and thermal performances. This study provides a strategy to synergistically optimize electrical–thermal performances of the p-type skutterudites by alloying engineering.

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About this article

Alloying engineering for thermoelectric performance enhancement in p-type skutterudites with synergistic carrier concentration optimization and thermal conductivity reduction

Show Author's information Hide Author's Information Zhiyuan Liu^{^a^,^b}(

), Yonggui Wang^{^b}, Ting Yang^{^b}, Zuju Ma^{^c}(

), Huiyan Zhang^{^a^,^b}, Hailing Li^{^a^,^b}, Ailin Xia^{^a^,^b}

aKey Laboratory of Green Fabrication and Surface Technology of Advanced Metal Materials, Ministry of Education, Anhui University of Technology, Maanshan 243002, China

bSchool of Materials Science and Engineering, Anhui University of Technology, Maanshan 243002, China

cSchool of Environmental and Materials Engineering, Yantai University, Yantai 264005, China

Abstract

Keywords: synergistic optimization, Ni doping, p-type skutterudite materials, thermoelectric (TE) properties

References(56)

[1]

Bell LE. Cooling, heating, generating power, and recovering waste heat with thermoelectric systems. Science 2008, 321: 1457–1461.

DOI Google Scholar

[2]

Zhao WY, Liu ZY, Sun ZG, et al. Superparamagnetic enhancement of thermoelectric performance. Nature 2017, 549: 247–251.

DOI Google Scholar

[3]

Jing HM, Tong X, Zhu JL, et al. Microstructural analysis and thermoelectric properties of skutterudite CoSb₃ materials produced by melt spinning and spark plasma sintering. Ceram Int 2021, 47: 24916–24923.

DOI Google Scholar

[4]

Yu J, Ma SF, Xie XX, et al. Unique surface structure resulting in the excellent long-term thermal stability of Fe₄Sb₁₂-based filled skutterudites. J Eur Ceram Soc 2022, 42: 1007–1013.

DOI Google Scholar

[5]

Zheng YP, Zou MC, Zhang WY, et al. Electrical and thermal transport behaviours of high-entropy perovskite thermoelectric oxides. J Adv Ceram 2021, 10: 377–384.

DOI Google Scholar

[6]

Liu ZY, Wang YG, Zhao CY, et al. Nano-mesoscopic scale microstructure regulation for p-type skutterudite thermoelectric materials. Acta Metall Sin 2022, 58: 979–991. (in Chinese)

Google Scholar

[7]

Soufiane EO, Kogut I, Benyahia M, et al. High power density thermoelectric generators with skutterudites. Adv Energy Mater 2021, 11: 2100580.

DOI Google Scholar

[8]

Liu ZY, Yang T, Wang YG, et al. Energy band and charge-carrier engineering in skutterudite thermoelectric materials. Chin Phys B 2022, 31: 107303.

DOI Google Scholar

[9]

Zhang L, Rogl G, Grytsiv A, et al. Mechanical properties of filled antimonide skutterudites. Mater Sci Eng B 2010, 170: 26–31.

DOI Google Scholar

[10]

Rogl G, Rogl P. Mechanical properties of skutterudites. Sci Adv Mat 2011, 3: 517–538.

DOI Google Scholar

[11]

Zhu JL, Liu ZY, Tong X, et al. Synergistic optimization of electrical-thermal-mechanical properties of the In-filled CoSb₃ material by introducing Bi_0.5Sb_1.5Te₃ nanoparticles. ACS Appl Mater Interfaces 2021, 13: 23894–23904.

DOI Google Scholar

[12]

Zhao WY, Liu ZY, Wei P, et al. Magnetoelectric interaction and transport behaviours in magnetic nanocomposite thermoelectric materials. Nat Nanotechnol 2017, 12: 55–60.

DOI Google Scholar

[13]

Zhang QH, Huang XY, Bai SQ, et al. Thermoelectric devices for power generation: Recent progress and future challenges. Adv Eng Mater 2016, 18: 194–213.

DOI Google Scholar

[14]

Tong X, Liu ZY, Zhu JL, et al. Research progress of p-type Fe-based skutterudite thermoelectric materials. Front Mater Sci 2021, 15: 317–333.

DOI Google Scholar

[15]

Liu ZY, Zhu JL, Tong X, et al. A review of CoSb₃-based skutterudite thermoelectric materials. J Adv Ceram 2020, 9: 647–673.

DOI Google Scholar

[16]

Rogl G, Grytsiv A, Rogl P, et al. N-type skutterudites (R, Ba, Yb)_yCo₄Sb₁₂ (R = Sr, La, Mm, DD, SrMm, SrDD) approaching ZT ≈ 2.0. Acta Mater 2014, 63: 30–43.

DOI Google Scholar

[17]

Rogl G, Grytsiv A, Heinrich P, et al. New bulk p-type skutterudites DD_0.7Fe_2.7Co_1.3Sb_12–xX_x (X = Ge, Sn) reaching ZT > 1.3. Acta Mater 2015, 91: 227–238.

DOI Google Scholar

[18]

Prado-Gonjal J, Vaqueiro P, Nuttall C, et al. Enhancing the thermoelectric properties of single and double filled p-type skutterudites synthesized by an up-scaled ball-milling process. J Alloys Compd 2017, 695: 3598–3604.

DOI Google Scholar

[19]

Jie Q, Wang HZ, Liu WS, et al. Fast phase formation of double-filled p-type skutterudites by ball-milling and hot-pressing. Phys Chem Chem Phys 2013, 15: 6809–6816.

DOI Google Scholar

[20]

Guo LJ, Wang GW, Peng KL, et al. Melt spinning synthesis of p-type skutterudites: Drastically speed up the process of high performance thermoelectrics. Scripta Mater 2016, 116: 26–30.

DOI Google Scholar

[21]

Tan GJ, Liu W, Wang SY, et al. Rapid preparation of CeFe₄Sb₁₂ skutterudite by melt spinning: Rich nanostructures and high thermoelectric performance. J Mater Chem A 2013, 1: 12657–12668.

DOI Google Scholar

[22]

Li XG, Liu WD, Li SM, et al. Impurity removal leading to high-performance CoSb₃-based skutterudites with synergistic carrier concentration optimization and thermal conductivity reduction. ACS Appl Mater Interfaces 2021, 13: 54185–54193.

DOI Google Scholar

[23]

Rogl G, Grytsiv A, Rogl P, et al. Dependence of thermoelectric behaviour on severe plastic deformation parameters: A case study on p-type skutterudite DD_0.60Fe₃CoSb₁₂. Acta Mater 2013, 61: 6778–6789.

DOI Google Scholar

[24]

Bérardan D, Alleno E, Godart C, et al. Improved thermoelectric properties in double-filled Ce_y/2Yb_y/2Fe_4−x(Co/Ni)_xSb₁₂ skutterudites. J Appl Phys 2005, 98: 033710.

DOI Google Scholar

[25]

Rogl G, Grytsiv A, Bauer E, et al. Thermoelectric properties of novel skutterudites with didymium: DD_y(Fe_1−xCo_x)₄Sb₁₂ and DD_y(Fe_1−xNi_x)₄Sb₁₂. Intermetallics 2010, 18: 57–64.

DOI Google Scholar

[26]

Tan GJ, Wang SY, Yan YG, et al. Effects of cobalt substitution for Fe on the thermoelectric properties of p-type CeFe_4−xCo_xSb₁₂ skutterudites. J Electron Mater 2012, 41: 1147–1152.

DOI Google Scholar

[27]

Carlini R, Khan AU, Ricciardi R, et al. Synthesis, characterization and thermoelectric properties of Sm filled Fe_4−xNi_xSb₁₂ skutterudites. J Alloys Compd 2016, 655: 321–326.

DOI Google Scholar

[28]

Wang BY, Jin HB, Yi W, et al. Ni substitution improves the high-temperature thermoelectric performance of electronegative element Se-filled skutterudite Se_0.05Ni_xCo_4−xSb₁₂. J Alloys Compd 2022, 909: 164733.

DOI Google Scholar

[29]

Kresse G, Furthmüller J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys Rev B Condens Matter 1996, 54: 11169–11186.

DOI Google Scholar

[30]

Perdew JP, Burke K, Ernzerhof M. Generalized gradient approximation made simple. Phys Rev Lett 1996, 77: 3865–3868.

DOI Google Scholar

[31]

Blöchl PE. Projector augmented-wave method. Phys Rev B Condens Matter 1994, 50: 17953–17979.

DOI Google Scholar

[32]

Monkhorst HJ, Pack JD. Special points for brillouin-zone integrations. Phys Rev B 1976, 13: 5188–5192.

DOI Google Scholar

[33]

Liu ZY, Zhu WT, Nie XL, et al. Effects of sintering temperature on microstructure and thermoelectric properties of Ce-filled Fe₄Sb₁₂ skutterudites. J Mater Sci Mater Electron2019, 30: 12493–12499.

DOI Google Scholar

[34]

Nolas GS, Kendziora CA, Takizawa H. Polarized Raman-scattering study of Ge and Sn-filled CoSb₃. J Appl Phys 2003, 94: 7440–7444.

DOI Google Scholar

[35]

Lu PX, Shen ZG, Hu X. Effects of the voids filling on the lattice vibrations for the CoSb₃-based thermoelectric materials—Raman scattering spectra and theoretical study. Phys B Condens Matter 2010, 405: 2589–2592.

DOI Google Scholar

[36]

Feldman JL, Singh DJ. Lattice dynamics of skutterudites: First-principles and model calculations for CoSb₃. Phys Rev B 1996, 53: 6273–6282.

DOI Google Scholar

[37]

Peng JY, Yang JY, Zhang TJ, et al. Effect of partial void filling on the Raman spectra and thermal transport property of skutterudite compounds La_yCo_3.5Fe_0.5Sb₁₂. Mater Chem Phys 2006, 100: 15–18.

DOI Google Scholar

[38]

Deng L, Li DN, Qin JM, et al. Effect of Pb filling and synthesis pressure regulation on the thermoelectric properties of CoSb₃. Inorg Chem 2019, 58: 4033–4037.

DOI Google Scholar

[39]

Settipalli M, Proshchenko VS, Neogi S. The effect of electron–phonon and electron–impurity scattering on the electronic transport properties of silicon/germanium superlattices. J Mater Chem C 2022, 10: 7525–7542.

DOI Google Scholar

[40]

Fröhlich H. Electrons in lattice fields. Adv Phys 1954, 3: 325–361.

DOI Google Scholar

[41]

Kim H, Kim MH, Kaviany M. Lattice thermal conductivity of UO₂ using ab-initio and classical molecular dynamics. J Appl Phys 2014, 115: 123510.

DOI Google Scholar

[42]

Shi XY, Pei YZ, Snyder GJ, et al. Optimized thermoelectric properties of Mo₃Sb_7−xTe_x with significant phonon scattering by electrons. Energy Environ Sci 2011, 4: 4086–4095.

DOI Google Scholar

[43]

Cutler M, Leavy JF, Fitzpatrick RL. Electronic transport in semimetallic cerium sulfide. Phys Rev 1964, 133: A1143–A1152.

DOI Google Scholar

[44]

Anno H, Matsubara K, Notohara Y, et al. Effects of doping on the transport properties of CoSb₃. J Appl Phys 1999, 86: 3780–3786.

DOI Google Scholar

[45]

Zhao LD, Lo SH, He JQ, et al. High performance thermoelectrics from earth-abundant materials: Enhanced figure of merit in PbS by second phase nanostructures. J Am Chem Soc 2011, 133: 20476–20487.

DOI Google Scholar

[46]

Ashcroft NW, Mermin ND. Solid State Physics Thomson Learning. New York: Harcourt College Publishers, 1976.

[47]

Callaway J, von Baeyer HC. Effect of point imperfections on lattice thermal conductivity. Phys Rev 1960, 120: 1149–1154.

DOI Google Scholar

[48]

Bhandari CM, Rowe DM. Thermal Conduction in Semiconductors. John Wiley & Sons, 1988.

[49]

Fu LW, Yang JY, Jiang QH, et al. Thermoelectric performance enhancement of CeFe₄Sb₁₂ p-type skutterudite by disorder on the Sb₄ rings induced by Te doping and nanopores. J Electron Mater2016, 45: 1240–1244.

DOI Google Scholar

[50]

Tan GJ, Wang SY, Tang XF. Thermoelectric performance optimization in p-type Ce_yFe₃CoSb₁₂ skutterudites. J Electron Mater 2014, 43: 1712–1717.

DOI Google Scholar

[51]

Tan GJ, Zheng Y, Yan YG, et al. Preparation and thermoelectric properties of p-type filled skutterudites Ce_yFe_4−xNi_xSb₁₂. J Alloys Compd 2014, 584: 216–221.

DOI Google Scholar

[52]

Park KH, Lee S, Seo WS, et al. Synthesis and thermoelectric properties of Ce_zFe_4−xCo_xSb₁₂ skutterudites. J Korean Phys Soc 2014, 64: 84–88.

DOI Google Scholar

[53]

Zhang L, Grytsiv A, Kerber M, et al. Thermoelectric performance of mischmetal skutterudites Mm_yFe_4−xCo_xSb₁₂ at elevated temperatures. J Alloys Compd 2010, 490: 19–25.

DOI Google Scholar

[54]

Liu RH, Qiu PF, Chen XH, et al. Composition optimization of p-type skutterudites Ce_yFe_xCo_4−xSb₁₂ and Yb_yFe_xCo_4−xSb₁₂. J Mater Res 2011, 26: 1813–1819.

Google Scholar

[55]

Liu RH, Yang J, Chen XH, et al. p-type skutterudites R_xM_yFe₃CoSb₁₂ (R, M= Ba, Ce, Nd, and Yb): Effectiveness of double-filling for the lattice thermal conductivity reduction. Intermetallics 2011, 19: 1747–1751.

DOI Google Scholar

[56]

Sharma V, Singh SP, Mudahar GS, et al. Synthesis and characterization of cadmium containing sodium borate glasses. New J Glass Ceram 2012, 2: 128–132.

DOI Google Scholar

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Publication history

Received: 21 August 2022

Revised: 29 November 2022

Accepted: 02 December 2022

Published: 15 February 2023

Issue date: March 2023

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (Grant Nos. 51872006, and 22273081) and Anhui Province Natural Science Foundation for Excellent Youth Scholars (Grant No. 2208085Y17).

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