Journal Home > Volume 8 , Issue 1

To achieve a better material for thermoelectric power generation device, filled skutterudite Yb0.3Co4Sb12 samples were fabricated by melting-quenching-annealing-spark plasma sintering (SPS) method. Two sets of samples, before and after SPS, were investigated. In both the two sets of samples, the average grain size of the samples increases monotonously with the increase of annealing time, while Yb filling fraction firstly increases and then decreases. Yb not filling into the skutterudite remains at the grain boundaries in the form of Yb2O3 after SPS, which could be quantified by the spatially difference method of energy dispersive spectra. Step distribution of Yb filling fraction was observed in the samples annealed for 1 h, which was caused by the microstructural evolution from the peritectic phases to the skutterudite phase. The sample annealed for 3 days and SPS sintered possesses the maximum value of Yb filling fraction 0.249 and the maximum ZT value of 1.24 at 850 K. These results are helpful to better understand the microstructural evolution and Yb filling behavior in skutterudite materials.


menu
Abstract
Full text
Outline
About this article

Step distribution of Yb filling fraction during microstructural evolution in skutterudites

Show Author's information Jing MEIaZheng YAObShuya ZHUaDongli HUaYing JIANGaJuanjuan XINGa( )Hui GUaLidong CHENb
School of Materials Science and Engineering and Materials Genome Institute, Shanghai University, Shanghai 200444, China
State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China

Abstract

To achieve a better material for thermoelectric power generation device, filled skutterudite Yb0.3Co4Sb12 samples were fabricated by melting-quenching-annealing-spark plasma sintering (SPS) method. Two sets of samples, before and after SPS, were investigated. In both the two sets of samples, the average grain size of the samples increases monotonously with the increase of annealing time, while Yb filling fraction firstly increases and then decreases. Yb not filling into the skutterudite remains at the grain boundaries in the form of Yb2O3 after SPS, which could be quantified by the spatially difference method of energy dispersive spectra. Step distribution of Yb filling fraction was observed in the samples annealed for 1 h, which was caused by the microstructural evolution from the peritectic phases to the skutterudite phase. The sample annealed for 3 days and SPS sintered possesses the maximum value of Yb filling fraction 0.249 and the maximum ZT value of 1.24 at 850 K. These results are helpful to better understand the microstructural evolution and Yb filling behavior in skutterudite materials.

Keywords: microstructure, skutterudite, ytterbium filling fraction, step distribution

References(42)

[1]
BC Sales, D Mandrus, RK Williams. Filled skutterudite antimonides: A new class of thermoelectric materials. Science 1996, 272: 1325-1328.
[2]
X Shi, H Kong, C-P Li, et al. Low thermal conductivity and high thermoelectric figure of merit in n-type BaxYbyCo4Sb12 double-filled skutterudites. Appl Phys Lett 2008, 92: 182101.
[3]
A Leithe-Jasper, D Kaczorowski, P Rogl, et al. Synthesis, crystal-structure determination and physical properties of YbFe4Sb12. Solid State Commun 1999, 109: 395-400.
[4]
GS Nolas, M Kaeser, RT Littleton, et al. High figure of merit in partially filled ytterbium skutterudite materials. Appl Phys Lett 2000, 77: 1855-1857.
[5]
NR Dilley, ED Bauer, MB Maple, et al. Thermoelectric properties of chemically substituted skutterudites YbyCo4SnxSb12−x. J Appl Phys 2000, 88: 1948-1951.
[6]
Y-S Park, T Thompson, Y Kim, et al. Protective enamel coating for n- and p-type skutterudite thermoelectric materials. J Mater Sci 2015, 50: 1500-1512.
[7]
T Zhu, Y Liu, C Fu, et al. Compromise and synergy in high-efficiency thermoelectric materials. Adv Mater 2017, 29: 1605884
[8]
BC Sales, D Mandrus, BC Chakoumakos, et al. Filled skutterudite antimonides: Electron crystals and phonon glasses. Phys Rev B 1997, 56: 15081-15089.
[9]
D Mandrus, BC Sales, V Keppens, et al. Filled skutterudite antimonides: Validation of the electron-crystal phonon-glass approach to new thermoelectric materials. MRS Proceedings 1997, 478: 199.
[10]
G Sheet, H Rosner, S Wirth, et al. High spin polarization in the ferromagnetic filled skutterudites KFe4Sb12 and NaFe4Sb12. Phys Rev B 2005, 72: 180407.
[11]
YZ Pei, LD Chen, W Zhang, et al. Synthesis and thermoelectric properties of KyCo4Sb12. Appl Phys Lett 2006, 89: 221107.
[12]
XY Zhao, X Shi, LD Chen, et al. Synthesis and thermoelectric properties of Sr-filled skutterudite SryCo4Sb12. J Appl Phys 2006, 99: 053711.
[13]
LD Chen, T Kawahara, XF Tang, et al. Anomalous barium filling fraction and n-type thermoelectric performance of BayCo4Sb12. J Appl Phys 2001, 90: 1864-1868.
[14]
Y Kang, F Yu, C Chen, et al. High pressure synthesis and thermoelectric properties of Ba-filled CoSb3 skutterudites. J Mater Sci: Mater Electron 2017, 28: 8771-8776.
[15]
MM Koza, MR Johnson, R Viennois, et al. Breakdown of phonon glass paradigm in La- and Ce-filled Fe4Sb12 skutterudites. Nat Mater 2008, 7: 805-810.
[16]
JL Feldman, DJ Singh, C Kendziora, et al. Lattice dynamics of filled skutterudites: La(Fe, Co)4Sb12. Phys Rev B 2003, 68: 094301.
[17]
PN Alboni, X Ji, J He, et al. Thermoelectric properties of La0.9CoFe3Sb12-CoSb3 skutterudite nanocomposites. J Appl Phys 2008, 103: 113707.
[18]
XF Tang, LD Chen, T Goto, et al. Synthesis and thermoelectric properties of filled skutterudite compounds CeyFexCo4−xSb12 by solid state reaction. J Mater Sci 2001, 36: 5435-5439.
[19]
YZ Pei, SQ Bai, XY Zhao, et al. Thermoelectric properties of EuyCo4Sb12 filled skutterudites. Solid State Sci 2008, 10: 1422-1428.
[20]
GA Lamberton Jr., S Bhattacharya, IV RT Littleton, et al. High figure of merit in Eu-filled CoSb3-based skutterudites. Appl Phys Lett 2002, 80: 598-600.
[21]
Q Zhang, C Chen, Y Kang, et al. Structural and thermoelectric characterizations of samarium filled CoSb3 skutterudites. Mater Lett 2015, 143: 41-43.
[22]
C Artini, G Zanicchi, GA Costa, et al. Correlations between structural and electronic properties in the filled skutterudite Smy(FexNi1-x)4Sb12. Inorg Chem 2016, 55: 2574-2583.
[23]
G Rogl, A Grytsiv, E Bauer, et al. Thermoelectric properties of novel skutterudites with didymium: DDy(Fe1−xCox)4Sb12 and DDy(Fe1−xNix)4Sb12. Intermetallics 2010, 18: 57-64.
[24]
TA Sayles, RE Baumbach, WM Yuhasz, et al. Superconductivity and crystalline electric field effects in the filled skutterudite PrRu4As12. Phys Rev B 2010, 82: 104513.
[25]
X Shi, J Yang, LD Chen, et al. Materials genome approach to accelerate thermoelectric material performance optimization. Sci Technol Rev 2015, 33: 60-63.
[26]
X Shi, W Zhang, LD Chen, et al. Filling fraction limit for intrinsic voids in crystals: Doping in skutterudites. Phys Rev Lett 2005, 95: 185503.
[27]
XY Zhao, X Shi, LD Chen, et al. Synthesis of YbyCo4Sb12/Yb2O3 composites and their thermoelectric properties. Appl Phys Lett 2006, 89: 092121.
[28]
JR Salvador, J Yang, X Shi, et al. Transport and mechanical properties of Yb-filled skutterudites. Philos Mag 2009, 89: 1517-1534.
[29]
Y Wang, J Mao, Q Jie, et al. Filling fraction of Yb in CoSb3 skutterudite studied by electron microscopy. Appl Phys Lett 2017, 110: 163901.
[30]
J-K Lee, S-M Choi, W-S Seo, et al. Thermoelectric properties of spark plasma sintered InxYbyLa0.3-x-yCo4Sb12 skutterudite system. Renew Energ 2012, 42: 36-40.
[31]
T Dahal, Q Jie, G Joshi, et al. Thermoelectric property enhancement in Yb-doped n-type skutterudites YbxCo4Sb12. Acta Mater 2014, 75: 316-321.
[32]
S Ballikaya, C Uher. Enhanced thermoelectric performance of optimized Ba, Yb filled and Fe substituted skutterudite compounds. J Alloys Compd 2014, 585: 168-172.
[33]
G Son, KH Lee, S-M Choi. Enhanced thermoelectric properties of melt-spun p-type Yb0.9Fe3CoSb12. J Electron Mater 2017, 46: 2839-2843.
[34]
GS Nolas, G Fowler, J Yang. Assessing the role of filler atoms on the thermal conductivity of filled skutterudites. J Appl Phys 2006, 100: 043705.
[35]
DM Rowe. Thermoelectrics Handbook: Macro to Nano. CRC Press, 2005.
[36]
C Artini, R Carlini. Influence of composition and thermal treatments on microhardness of the filled skutterudite Smy(FexNi1−x)4Sb12. J Nanosci Nanotechno 2017, 17: 1634-1639.
[37]
Z Yao, XY Li, YS Tang, et al. Genomic effects of the quenching process on the microstructure and thermoelectric properties of Yb0.3Co4Sb12. J Electron Mater 2015, 44: 1890-1895.
[38]
J Xing, H Gu, A Gloter, et al. Bismuth nanoprecipitation at grain boundaries during microstructural evolution in (Sr, Ba)TiO3 ceramics. Acta Mater 2007, 55: 5323-5332.
[39]
H Gu, T Nagano, G-D Zhan, et al. Dynamic evolution of grain-boundary films in liquid-phase-sintered ultrafine silicon carbide material. J Am Ceram Soc 2003, 86: 1753-1760.
[40]
Z Yao, P-F Qiu, X-Y Li, et al. Investigation on quick fabrication of n-type filled skutterudites. J Inorg Mater 2016, 31: 1375-1382.
[41]
J Ding, H Gu, P Qiu, et al. Creation of Yb2O3 nanoprecipitates through an oxidation process in bulk Yb-filled skutterudites. J Electron Mater 2013, 42: 382-388.
[42]
M Zebarjadi, K Esfarjani, MS Dresselhaus, et al. Perspectives on thermoelectrics: From fundamentals to device applications. Energy Environ Sci 2012, 5: 5147-5162.
Publication history
Copyright
Acknowledgements
Rights and permissions

Publication history

Received: 05 March 2018
Revised: 21 June 2018
Accepted: 23 July 2018
Published: 13 March 2019
Issue date: March 2019

Copyright

© The author(s) 2019

Acknowledgements

This work was financially supported by the National Natural Science Foundation of China under Grant Nos. 51532006 and 11704238, Shanghai Municipal Science and Technology Commission of Shanghai Municipality under Grant No. 16DZ2260601, and State Administration of Foreign Experts Affairs of China 111 Project under Grant No. D16002.

Rights and permissions

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 http://creativecommons.org/licenses/by/4.0/.

Return