Thermoelectric Properties of P-Type CeyFe3CoSb12 Thermoelectric Materials and Coatings Doped with La

doi:10.11900/0412.1961.2021.00215

Acta Metall Sin

2023, Vol. 59

Issue (2): 237-247 DOI: 10.11900/0412.1961.2021.00215

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Thermoelectric Properties of P-Type Ce_yFe₃CoSb₁₂ Thermoelectric Materials and Coatings Doped with La

LI Dou, XU Changjiang, LI Xuguang, LI Shuangming(

), ZHONG Hong

State Key Laboratory of Solidification Processing, Northwestern Polytechnical University, Xi'an 710072, China

Cite this article:

LI Dou, XU Changjiang, LI Xuguang, LI Shuangming, ZHONG Hong. Thermoelectric Properties of P-Type Ce_yFe₃CoSb₁₂ Thermoelectric Materials and Coatings Doped with La. Acta Metall Sin, 2023, 59(2): 237-247.

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Abstract

During the use of fossil fuels, about two-thirds of the energy that is discharged into the environment in the form of waste heat are barely utilized and cause considerable environmental pollution and intense CO₂ emission. Thermoelectric materials directly convert heat energy to electricity, thus, improving the utilization efficiency of fossil energy and reducing environmental pollution. Skutterudite CoSb₃ has been widely studied as one of the materials for thermoelectric applications in the middle-temperature region. CoSb₃-based skutterudites are narrow bandgap semiconductors with a high-electrical conductivity and Seebeck coefficient. Meanwhile, thermoelectric performance of bulk CoSb₃ has been considerably improved via doping and design of nano structures. Herein, P-type CoSb₃ was synthesized via melt-annealing-spark plasma sintering process. The effect of Ce-doping content on microstructure and thermoelectric properties of CoSb₃ and the effect of La doping on decoupled thermoelectric performance were studied. Compared with Ce_0.8Fe₃CoSb₁₂, the Seebeck coefficient of La_0.1Ce_0.8Fe₃CoSb₁₂ increased with temperature, electrical resistivity decreased from 25 μΩ·m to 15 μΩ·m at 300 K, and power factor simultaneously increased from 480 μW/(m·K²) to 642 μW/(m·K²) at 673 K. The La_0.1Ce_0.8Fe₃CoSb₁₂ thermal conductivity decreased with La or Ce doping to ~1 W/(m·K), and the corresponding thermoelectric figure of merit reached 0.45 at 723 K in the temperature range from 300 K to 723 K. Al-Ni coating was deposited on the sintered bulk skutterudite via magnetron sputtering method. It was demonstrated that the coating did not degrade the thermoelectric performance, while the coating elements were uniformly distributed across the sintered bulk La_0.1Ce_0.8Fe₃CoSb₁₂. The welding behavior of P-type La_0.1Ce_0.8Fe₃CoSb₁₂ was studied using a Ag₄₀Cu₆₀ solder and a Mo₅₀Cu₅₀ electrode sheet. The interface of this thermoelectric material was prone to cracking and pore formation, while the elements at the interface have not demonstrated remarkable diffusion. This indicates an efficiency of the interface bonding, which may be used in the fabrication technologies of thermoelectric devices.

Key words: CoSb₃ thermoelectric material Al-Ni coating thermal conductivity electrical conductivity

Received: 19 May 2021

ZTFLH:

TQ174

Fund: National Natural Science Foundation of China(51774239)

About author: LI Shuangming, professor, Tel: (029)88493264, E-mail: lsm@nwpu.edu.cn

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	Dou LI
	Changjiang XU
	Xuguang LI
	Shuangming LI
	Hong ZHONG

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https://www.ams.org.cn/EN/10.11900/0412.1961.2021.00215 OR https://www.ams.org.cn/EN/Y2023/V59/I2/237

Fig.1 XRD spectra of La_xCe_yFe₃CoSb₁₂ thermoelectric material before (a) and after (b) spark plasma sintering (SPS)

Fig.2 SEM image (a) and corresponding EDS maps (b-f) of the SPSed bulk La_0.1Ce_0.8Fe₃CoSb₁₂ thermoelectric material

Table 1 EDS analysis results of points 1-4 in Fig.2a

Fig.3 Electrical performance curves of the SPSed bulk La_xCe_yFe₃CoSb₁₂ thermoelectric material
(a) Seebeck coefficient
(b) electrical resistivity
(c) power factor

Table 2 Electrical properties of the SPSed bulk La_xCe_y-Fe₃CoSb₁₂ thermoelectrical material at room temperature

Fig.4 Heat transport performance curves of the SPSed bulk La_xCe_yFe₃CoSb₁₂thermoelectric material
(a) total thermal conductivity (K_t) (b) lattice thermal conductivity (K_L)
(c) carrier thermal conductivity (K_e) (d) the ratio of K_L / K_t

Fig.5 TEM analyses of the SPSed bulk La_0.1Ce_0.8Fe₃CoSb₁₂ thermoelectric material
(a) low-magnification bright-field TEM image (b) enlarged view of boxed region b in Fig.5a
(c) bright-field TEM image of grain boundary (d) EDS maps of element distribution for Fig.5c
(e) HRTEM image corresponding to region e in Fig.1a (Inset shows the SAED pattern)
(f) inverse fast Fourier transformation (IFFT) image using the satellite spots in the inset of Fig.5e (CeSb/(

0 1 ˉ 1

))
(g) IFFT image using the satellite spots in the inset of Fig.5e (CoSb₃/(

1 ˉ 1 1 ˉ

))

Fig.6 Thermoelectric figure of merit (ZT) of the SPSed bulk La_xCe_yFe₃CoSb₁₂ thermoelectric material

Fig.7 Characterizations and analyses of the SPSed bulk La_0.1Ce_0.8Fe₃CoSb₁₂thermoelectric material with sputtering Al-Ni coating
(a) photo before and after sputtering Al-Ni coating
(b) OM image of substrate and coating
(c) SEM image of coating (d, e) EDS maps of elements Al (d) and Ni (e) of rectangle area in Fig.7c (f) SEM image of substrate and coating (g) line scan result along line EF in Fig.7f

Fig.8 Thermoelectric properties curves of the SPSed bulk La_0.1Ce_0.8Fe₃CoSb₁₂ thermoelectric material before and after sputtering Al-Ni coating
(a) Seebeck coefficient (b) electrical resistivity
(c) thermal conductivity (d) thermoelectric figure of merit

Fig.9 SEM image of the SPSed bulk La_0.1Ce_0.8Fe₃CoSb₁₂ thermoelectric material joint (a) and the line scan result along line AB in Fig.9a (b)

Fig.10 SEM image of the SPSed bulk La_0.1Ce_0.8Fe₃CoSb₁₂ thermoelectric material after welding and corresponding elements distribution

1	Suarez F, Parekh D P, Ladd C, et al. Flexible thermoelectric generator using bulk legs and liquid metal interconnects for wearable electronics[J]. Appl. Energy, 2017, 202: 736 doi: 10.1016/j.apenergy.2017.05.181
2	Siddique A R M, Rabari R, Mahmud S, et al. Thermal energy harvesting from the human body using flexible thermoelectric generator (FTEG) fabricated by a dispenser printing technique[J]. Energy, 2016, 115: 1081 doi: 10.1016/j.energy.2016.09.087
3	Kuroki T, Kabeya K, Makino K, et al. Thermoelectric generation using waste heat in steel works[J]. J. Electron. Mater., 2014, 43: 2405 doi: 10.1007/s11664-014-3094-5
4	Sun H Y, Li S M, Feng S K, et al. Microstructure and phase selection in directional solidification of Co-Sb alloy[J]. Acta Metall. Sin., 2013, 49: 682 doi: 10.3724/SP.J.1037.2012.00735
	孙洪元, 李双明, 冯松科等. Co-Sb合金定向凝固组织与相选择[J]. 金属学报, 2013, 49: 682 doi: 10.3724/SP.J.1037.2012.00735
5	Yang B, Li S M, Li X, et al. Ultralow thermal conductivity and enhanced thermoelectric properties of SnTe based alloys prepared by melt spinning technique[J]. J. Alloys Compd., 2020, 837: 155568 doi: 10.1016/j.jallcom.2020.155568
6	Zheng Z H, Li F, Luo J T, et al. Thermoelectric properties and micro-structure characteristics of nano-sized CoSb₃ thin films prefabricating by co-sputtering[J]. J. Alloys Compd., 2018, 732: 958 doi: 10.1016/j.jallcom.2017.10.207
7	Tang Y L, Chen S W, Snyder G J. Temperature dependent solubility of Yb in Yb-CoSb₃ skutterudite and its effect on preparation, optimization and lifetime of thermoelectrics[J]. J. Materiomics, 2015, 1: 75 doi: 10.1016/j.jmat.2015.03.008
8	Li X H, Zhang Q, Kang Y L, et al. High pressure synthesized Ca-filled CoSb₃ skutterudites with enhanced thermoelectric properties[J]. J. Alloys Compd., 2016, 677: 61 doi: 10.1016/j.jallcom.2016.03.239
9	Tang Y L, Gibbs Z M, Agapito L A, et al. Convergence of multi-valley bands as the electronic origin of high thermoelectric performance in CoSb₃ skutterudites[J]. Nat. Mater., 2015, 14: 1223 doi: 10.1038/nmat4430
10	Zhou Z X, Li J L, Fan Y C, et al. Uniform dispersion of SiC in Yb-filled skutterudite nanocomposites with high thermoelectric and mechanical performance[J]. Scr. Mater., 2019, 162: 166 doi: 10.1016/j.scriptamat.2018.11.015
11	Zhou X Y, Wang G W, Guo L J, et al. Hierarchically structured TiO₂ for Ba-filled skutterudite with enhanced thermoelectric performance[J]. J. Mater. Chem., 2014, 2A: 20629
12	Tang Y L, Qiu Y T, Xi L L, et al. Phase diagram of In-Co-Sb system and thermoelectric properties of In-containing skutterudites[J]. Energy Environ. Sci., 2014, 7: 812 doi: 10.1039/C3EE43240H
13	Meng X F, Liu Z H, Cui B, et al. Grain boundary engineering for achieving high thermoelectric performance in n-type skutterudites[J]. Adv. Energy Mater., 2017, 7: 1602582 doi: 10.1002/aenm.201602582
14	Akasaka M, Iida T, Sakuragi G, et al. Effects of post-annealing on thermoelectric properties of p-type CoSb₃ grown by the vertical Bridgman method[J]. J. Alloys Compd., 2005, 386: 228 doi: 10.1016/j.jallcom.2004.04.144
15	Furuyama S, Iida T, Matsui S, et al. Thermoelectric properties of undoped p-type CoSb₃ prepared by vertical Bridgman crystal growth and spark plasma sintering[J]. J. Alloys Compd., 2006, 415: 251 doi: 10.1016/j.jallcom.2005.07.057
16	Yang L, Wu J S, Zhang L T. Study of grain growth and spark plasma sintering of a Skutterudite compound[J]. Acta Metall. Sin., 2003, 39: 785
	杨磊, 吴建生, 张澜庭. Skutterudite类化合物晶粒长大规律和放电等离子体烧结的研究[J]. 金属学报, 2003, 39: 785
17	Rogl G, Setman D, Schafler E, et al. High-pressure torsion, a new processing route for thermoelectrics of high ZTs by means of severe plastic deformation[J]. Acta Mater., 2012, 60: 2146 doi: 10.1016/j.actamat.2011.12.023
18	Ballikaya S, Uher C. Enhanced thermoelectric performance of optimized Ba, Yb filled and Fe substituted skutterudite compounds[J]. J. Alloys Compd., 2014, 585: 168 doi: 10.1016/j.jallcom.2013.09.124
19	Geng H Y, Ochi T, Suzuki S, et al. Thermoelectric properties of multifilled skutterudites with La as the main filler[J]. J. Electron. Mater., 2013, 42: 1999 doi: 10.1007/s11664-013-2501-7
20	Tan G J, Liu W, Wang S Y, et al. Rapid preparation of CeFe₄Sb₁₂ skutterudite by melt spinning: Rich nanostructures and high thermoelectric performance[J]. J. Mater. Chem., 2013, 1A: 12657
21	Tan G J, Zheng Y, Tang X F. High thermoelectric performance of nonequilibrium synthesized CeFe₄Sb₁₂ composite with multi-scaled nanostructures[J]. Appl. Phys. Lett., 2013, 103: 183904 doi: 10.1063/1.4827555
22	Rogl G, Grytsiv A, Rogl P, et al. Nanostructuring of p- and n-type skutterudites reaching figures of merit of approximately 1.3 and 1.6, respectively[J]. Acta Mater., 2014, 76: 434 doi: 10.1016/j.actamat.2014.05.051
23	Bae S H, Lee K H, Choi S M. Effective role of filling fraction control in p-type Ce_xFe₃CoSb₁₂ skutterudite thermoelectric materials[J]. Intermetallics, 2019, 105: 44 doi: 10.1016/j.intermet.2018.11.010
24	Park K H, Lee S, Seo W S, et al. Thermoelectric properties of La-filled CoSb₃ skutterudites[J]. J. Korean Phys. Soc., 2014, 64: 1004 doi: 10.3938/jkps.64.1004
25	Liu K G, Dong X, Zhang J X. The effects of La on thermoelectric properties of La_xCo₄Sb₁₂ prepared by MA-SPS[J]. Mater. Chem. Phys., 2006, 96: 371 doi: 10.1016/j.matchemphys.2005.07.068
26	Ballikaya S, Wang G Y, Sun K, et al. Thermoelectric properties of triple-filled Ba_xYb_y In _zCo₄Sb₁₂ Skutterudites[J]. J. Electron. Mater., 2011, 40: 570 doi: 10.1007/s11664-010-1454-3
27	Shi X, Zhang W, Chen L D, et al. Filling fraction limit for intrinsic voids in crystals: Doping in skutterudites[J]. Phys. Rev. Lett., 2005, 95: 185503 doi: 10.1103/PhysRevLett.95.185503
28	Wojciechowski K T, Zybala R, Mania R. High temperature CoSb₃-Cu junctions[J]. Microelectron. Reliab., 2011, 51: 1198 doi: 10.1016/j.microrel.2011.03.033
29	Feng H B, Zhang L X, Zhang J L, et al. Metallization and diffusion bonding of CoSb₃-based thermoelectric materials[J]. Materials, 2020, 13: 1130 doi: 10.3390/ma13051130

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