AI Chat Paper
Note: Please note that the following content is generated by AMiner AI. SciOpen does not take any responsibility related to this content.
{{lang === 'zh_CN' ? '文章概述' : 'Summary'}}
{{lang === 'en_US' ? '中' : 'Eng'}}
Chat more with AI
View PDF
Submit Manuscript AI Chat Paper
Show Outline
Show full outline
Hide outline
Show full outline
Hide outline
Research Article | Open Access

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

Zhiyuan Liua,b( )Yonggui WangbTing YangbZuju Mac( )Huiyan Zhanga,bHailing Lia,bAilin Xiaa,b
Key Laboratory of Green Fabrication and Surface Technology of Advanced Metal Materials, Ministry of Education, Anhui University of Technology, Maanshan 243002, China
School of Materials Science and Engineering, Anhui University of Technology, Maanshan 243002, China
School of Environmental and Materials Engineering, Yantai University, Yantai 264005, China
Show Author Information

Graphical 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 CeFe3.8Co0.2Sb12 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 CeFe3.5Ni0.3Co0.2Sb12 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 CeFe3.5Ni0.3Co0.2Sb12 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.

Electronic Supplementary Material

Download File(s)
JAC0702_ESM.pdf (725.2 KB)


Bell LE. Cooling, heating, generating power, and recovering waste heat with thermoelectric systems. Science 2008, 321: 1457–1461.
Zhao WY, Liu ZY, Sun ZG, et al. Superparamagnetic enhancement of thermoelectric performance. Nature 2017, 549: 247–251.
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.
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.
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.
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)
Soufiane EO, Kogut I, Benyahia M, et al. High power density thermoelectric generators with skutterudites. Adv Energy Mater 2021, 11: 2100580.
Liu ZY, Yang T, Wang YG, et al. Energy band and charge-carrier engineering in skutterudite thermoelectric materials. Chin Phys B 2022, 31: 107303.
Zhang L, Rogl G, Grytsiv A, et al. Mechanical properties of filled antimonide skutterudites. Mater Sci Eng B 2010, 170: 26–31.
Rogl G, Rogl P. Mechanical properties of skutterudites. Sci Adv Mat 2011, 3: 517–538.
Zhu JL, Liu ZY, Tong X, et al. Synergistic optimization of electrical-thermal-mechanical properties of the In-filled CoSb3 material by introducing Bi0.5Sb1.5Te3 nanoparticles. ACS Appl Mater Interfaces 2021, 13: 23894–23904.
Zhao WY, Liu ZY, Wei P, et al. Magnetoelectric interaction and transport behaviours in magnetic nanocomposite thermoelectric materials. Nat Nanotechnol 2017, 12: 55–60.
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.
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.
Liu ZY, Zhu JL, Tong X, et al. A review of CoSb3-based skutterudite thermoelectric materials. J Adv Ceram 2020, 9: 647–673.
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.
Rogl G, Grytsiv A, Heinrich P, et al. New bulk p-type skutterudites DD0.7Fe2.7Co1.3Sb12–xXx (X = Ge, Sn) reaching ZT > 1.3. Acta Mater 2015, 91: 227–238.
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.
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.
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.
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.
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.
Rogl G, Grytsiv A, Rogl P, et al. Dependence of thermoelectric behaviour on severe plastic deformation parameters: A case study on p-type skutterudite DD0.60Fe3CoSb12. Acta Mater 2013, 61: 6778–6789.
Bérardan D, Alleno E, Godart C, et al. Improved thermoelectric properties in double-filled Cey/2Yby/2Fe4−x(Co/Ni)xSb12 skutterudites. J Appl Phys 2005, 98: 033710.
Rogl G, Grytsiv A, Bauer E, et al. Thermoelectric properties of novel skutterudites with didymium: DDy(Fe1−xCox)4Sb12 and DDy(Fe1−xNix)4Sb12. Intermetallics 2010, 18: 57–64.
Tan GJ, Wang SY, Yan YG, et al. Effects of cobalt substitution for Fe on the thermoelectric properties of p-type CeFe4−xCoxSb12 skutterudites. J Electron Mater 2012, 41: 1147–1152.
Carlini R, Khan AU, Ricciardi R, et al. Synthesis, characterization and thermoelectric properties of Sm filled Fe4−xNixSb12 skutterudites. J Alloys Compd 2016, 655: 321–326.
Wang BY, Jin HB, Yi W, et al. Ni substitution improves the high-temperature thermoelectric performance of electronegative element Se-filled skutterudite Se0.05NixCo4−xSb12. J Alloys Compd 2022, 909: 164733.
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.
Perdew JP, Burke K, Ernzerhof M. Generalized gradient approximation made simple. Phys Rev Lett 1996, 77: 3865–3868.
Blöchl PE. Projector augmented-wave method. Phys Rev B Condens Matter 1994, 50: 17953–17979.
Monkhorst HJ, Pack JD. Special points for brillouin-zone integrations. Phys Rev B 1976, 13: 5188–5192.
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.
Nolas GS, Kendziora CA, Takizawa H. Polarized Raman-scattering study of Ge and Sn-filled CoSb3. J Appl Phys 2003, 94: 7440–7444.
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.
Feldman JL, Singh DJ. Lattice dynamics of skutterudites: First-principles and model calculations for CoSb3. Phys Rev B 1996, 53: 6273–6282.
Peng JY, Yang JY, Zhang TJ, et al. Effect of partial void filling on the Raman spectra and thermal transport property of skutterudite compounds LayCo3.5Fe0.5Sb12. Mater Chem Phys 2006, 100: 15–18.
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.
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.
Fröhlich H. Electrons in lattice fields. Adv Phys 1954, 3: 325–361.
Kim H, Kim MH, Kaviany M. Lattice thermal conductivity of UO2 using ab-initio and classical molecular dynamics. J Appl Phys 2014, 115: 123510.
Shi XY, Pei YZ, Snyder GJ, et al. Optimized thermoelectric properties of Mo3Sb7−xTex with significant phonon scattering by electrons. Energy Environ Sci 2011, 4: 4086–4095.
Cutler M, Leavy JF, Fitzpatrick RL. Electronic transport in semimetallic cerium sulfide. Phys Rev 1964, 133: A1143–A1152.
Anno H, Matsubara K, Notohara Y, et al. Effects of doping on the transport properties of CoSb3. J Appl Phys 1999, 86: 3780–3786.
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.
Ashcroft NW, Mermin ND. Solid State Physics Thomson Learning. New York: Harcourt College Publishers, 1976.
Callaway J, von Baeyer HC. Effect of point imperfections on lattice thermal conductivity. Phys Rev 1960, 120: 1149–1154.
Bhandari CM, Rowe DM. Thermal Conduction in Semiconductors. John Wiley & Sons, 1988.
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.
Tan GJ, Wang SY, Tang XF. Thermoelectric performance optimization in p-type CeyFe3CoSb12 skutterudites. J Electron Mater 2014, 43: 1712–1717.
Tan GJ, Zheng Y, Yan YG, et al. Preparation and thermoelectric properties of p-type filled skutterudites CeyFe4−xNixSb12. J Alloys Compd 2014, 584: 216–221.
Park KH, Lee S, Seo WS, et al. Synthesis and thermoelectric properties of CezFe4−xCoxSb12 skutterudites. J Korean Phys Soc 2014, 64: 84–88.
Zhang L, Grytsiv A, Kerber M, et al. Thermoelectric performance of mischmetal skutterudites MmyFe4−xCoxSb12 at elevated temperatures. J Alloys Compd 2010, 490: 19–25.
Liu RH, Qiu PF, Chen XH, et al. Composition optimization of p-type skutterudites CeyFexCo4−xSb12 and YbyFexCo4−xSb12. J Mater Res 2011, 26: 1813–1819.
Liu RH, Yang J, Chen XH, et al. p-type skutterudites RxMyFe3CoSb12 (R, M= Ba, Ce, Nd, and Yb): Effectiveness of double-filling for the lattice thermal conductivity reduction. Intermetallics 2011, 19: 1747–1751.
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.
Journal of Advanced Ceramics
Pages 539-552
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.








Web of Science






Received: 21 August 2022
Revised: 29 November 2022
Accepted: 02 December 2022
Published: 15 February 2023
© The Author(s) 2022.

Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made.

The images or other third party material in this article are included in the article’s Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder.

To view a copy of this licence, visit