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

URL:

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

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