La掺杂P型CeyFe3CoSb12 热电材料及涂层的热电性能

doi:10.11900/0412.1961.2021.00215

金属学报

2023, Vol. 59

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

研究论文

本期目录 | 过刊浏览

La掺杂P型Ce_yFe₃CoSb₁₂ 热电材料及涂层的热电性能

李斗, 徐长江, 李旭光, 李双明(

), 钟宏

西北工业大学凝固技术国家重点实验室西安 710072

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

引用本文:

李斗, 徐长江, 李旭光, 李双明, 钟宏. La掺杂P型Ce_yFe₃CoSb₁₂ 热电材料及涂层的热电性能[J]. 金属学报, 2023, 59(2): 237-247.
Dou LI, Changjiang XU, Xuguang LI, Shuangming LI, Hong ZHONG. Thermoelectric Properties of P-Type Ce_yFe₃CoSb₁₂ Thermoelectric Materials and Coatings Doped with La[J]. Acta Metall Sin, 2023, 59(2): 237-247.

全文: PDF(4223 KB) HTML

摘要:

采用熔融-退火-放电等离子烧结工艺合成P型CoSb₃基热电材料，研究Ce掺杂量对CoSb₃基热电材料显微组织和热电性能的影响，以及La掺杂对解耦热电关系的作用。结果表明，掺杂元素La和Ce降低了热导率，使La_0.1Ce_0.8Fe₃CoSb₁₂在整个测温区间的热导率保持在1 W/(m·K)左右，对应的最高热电优值在723 K时达到0.45。以磁控溅射法制备Al-Ni涂层，通过对溅射Al-Ni防护涂层的P型La_0.1Ce_0.8Fe₃CoSb₁₂材料热电性能进行测试，发现涂层的介入并未造成材料热电性能的衰退，且涂层与基底结合良好，元素分布均匀。以钎料Ag₄₀Cu₆₀对P型热电元件La_0.1Ce_0.8Fe₃CoSb₁₂与电极片Mo₅₀Cu₅₀接头进行焊接行为研究，发现界面处宏观结合效果良好。

关键词 ： CoSb₃, 热电材料, Al-Ni涂层, 热导率, 电导率

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

收稿日期: 2021-05-19

ZTFLH:

TQ174

基金资助:国家自然科学基金项目(51774239)

作者简介: 李斗，男，1993年生，博士生

	服务

	把本文推荐给朋友
	加入引用管理器
	E-mail Alert
	RSS
	作者相关文章
	李斗
	徐长江
	李旭光
	李双明
	钟宏
44.8K

链接本文:

https://www.ams.org.cn/CN/10.11900/0412.1961.2021.00215 或 https://www.ams.org.cn/CN/Y2023/V59/I2/237

图1 LaxCeyFe3CoSb12热电材料放电等离子烧结(SPS)前后的XRD谱

图2 La0.1Ce0.8Fe3CoSb12块体热电材料SPS后的SEM像和EDS面扫描图

表1 图2a中点1~4的EDS分析结果 (atomic fraction / %)

图3 LaxCeyFe3CoSb12块体热电材料的电性能测试曲线

表2 室温下LaxCeyFe3CoSb12块体热电材料的电学性质

图4 LaxCeyFe3CoSb12块体热电材料热输运性能曲线

图5 La0.1Ce0.8Fe3CoSb12块体热电材料TEM分析

图6 LaxCeyFe3CoSb12块体热电材料热电优值

图7 La0.1Ce0.8Fe3CoSb12块体热电材料添加Al-Ni涂层后的表征和分析

图8 La0.1Ce0.8Fe3CoSb12块体热电材料溅射Al-Ni涂层前后热电性能曲线

图9 La0.1Ce0.8Fe3CoSb12块体热电材料焊接后接头区域SEM像和元素分布的线扫描

图10 La0.1Ce0.8Fe3CoSb12块体热电材料焊接后焊接区域SEM像和元素面分布图

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
4	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
16	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

[1]	刘志愿, 王永贵, 赵成玉, 杨婷, 夏爱林. p型方钴矿热电材料纳米-介观尺度微结构调控[J]. 金属学报, 2022, 58(8): 979-991.
[2]	曾小勤, 王杰, 应韬, 丁文江. 镁及其合金导热研究进展[J]. 金属学报, 2022, 58(4): 400-411.
[3]	周丽君, 位松, 郭敬东, 孙方远, 王新伟, 唐大伟. 基于飞秒激光时域热反射法的微尺度Cu-Sn金属间化合物热导率研究[J]. 金属学报, 2022, 58(12): 1645-1654.
[4]	赵立东, 王思宁, 肖钰. 热电材料的载流子迁移率优化[J]. 金属学报, 2021, 57(9): 1171-1183.
[5]	周洪宇, 冉珉瑞, 李亚强, 张卫冬, 刘俊友, 郑文跃. 颗粒尺寸对金刚石/Al封装基板热物性的影响[J]. 金属学报, 2021, 57(7): 937-947.
[6]	崔洋, 李寿航, 应韬, 鲍华, 曾小勤. 基于第一性原理的金属导热性能研究[J]. 金属学报, 2021, 57(3): 375-384.
[7]	宋贵宏,李贵鹏,刘倩男,杜昊,胡方. 溅射沉积Mg₂(Sn, Si)薄膜组织结构与导电性能[J]. 金属学报, 2019, 55(11): 1469-1476.
[8]	张荻, 苑孟颖, 谭占秋, 熊定邦, 李志强. 金刚石/Cu复合界面导热改性及其纳米化研究进展[J]. 金属学报, 2018, 54(11): 1586-1596.
[9]	刘晓云,王文广,王东,肖伯律,倪丁瑞,陈礼清,马宗义. 片层石墨尺寸对片层石墨/Al复合材料的强度和热导率的影响[J]. 金属学报, 2017, 53(7): 869-878.
[10]	孙洪元,李双明,冯松科,傅恒志. Co-Sb合金定向凝固组织与相选择[J]. 金属学报, 2013, 49(6): 682-688.
[11]	项建英陈树海黄继华赵兴科张华. 等离子喷涂La₂(Zr_0.7Ce_0.3)₂O₇热障涂层的抗热震性能[J]. 金属学报, 2012, 48(8): 965-970.
[12]	厉英,丁玉石,崔绍刚,王常珍. 掺杂Sc的CaZrO₃的制备及电学性能[J]. 金属学报, 2012, 48(5): 575-578.
[13]	宋鲁男刘嘉斌黄六一曾跃武孟亮. 强变形对Cu-Cr合金组织性能的影响[J]. 金属学报, 2012, 48(12): 1459-1466.
[14]	厉英马北越王臻明姜茂发. Na_1.4Co₂O₄基热电材料的溶胶-凝胶法制备及表征[J]. 金属学报, 2011, 47(1): 109-114.
[15]	李贵茂王恩刚张林左小伟赫冀成. 强磁场对Cu-25%Ag合金析出相及性能的影响[J]. 金属学报, 2010, 46(9): 1128-1132.

Viewed

Full text

Abstract

Cited

Shared

Discussed