变价稀土元素Eu掺杂BiCuSeO热电性能的研究

doi:10.15541/jim20190570

无机材料学报 ›› 2020, Vol. 35 ›› Issue (9): 1041-1046.DOI: 10.15541/jim20190570

所属专题：能源材料论文精选(三)：热电与燃料电池(2020)；【虚拟专辑】热电材料(2020~2021)

变价稀土元素Eu掺杂BiCuSeO热电性能的研究

康慧君¹(),张校影¹,王燕遐²,李建波¹,杨雄¹,刘达权¹,杨泽荣¹,王同敏¹()

1.大连理工大学材料科学与工程学院辽宁省凝固控制与数字化制备技术重点实验室, 大连 116024
2.大连理工大学三束材料改性重点实验室, 大连 116024

收稿日期:2019-11-08 修回日期:2019-12-16 出版日期:2020-09-20 网络出版日期:2020-01-15
作者简介:康慧君(1982-), 男, 博士, 副教授. E-mail: kanghuijun@dlut.edu.cn
KANG Huijun(1982-), male, PhD, associate professor. E-mail:kanghuijun@dlut.edu.cn
基金资助:
国家自然科学基金面上项目(51971052);国家自然科学基金面上项目(51774065);国家自然科学基金杰出青年基金项目(51525401);辽宁省 “兴辽英才计划”(XLYC1808005);大连市高层次人才创新支持计划(2017RQ026)

Effect of Rare-earth Variable-valence Element Eu doping on Thermoelectric Property of BiCuSeO

KANG Huijun¹(),ZHANG Xiaoying¹,WANG Yanxia²,LI Jianbo¹,YANG Xiong¹,LIU Daquan¹,YANG Zerong¹,WANG Tongmin¹()

1. Key Laboratory of Solidification Control and Digital Preparation Technology (Liaoning Province), School of Materials Science and Engineering, Dalian University of Technology, Dalian 116024, China
2. Key Laboratory of Material Modification by Laser, Ion and Electron Beams, Ministry of Education, Dalian University of Technology, Dalian 116024, China

Received:2019-11-08 Revised:2019-12-16 Published:2020-09-20 Online:2020-01-15
Supported by:
National Natural Science Foundation of China(51971052);National Natural Science Foundation of China(51774065);National Science Fund for Distinguished Young Scholars(51525401);Liaoning Revitalization Talents Program(XLYC1808005);Dalian High Level Talents Innovation Support Plan(2017RQ026)

摘要/Abstract

摘要：

作为一种适于中温下使用的极具发展前景的新型热电材料, BiCuSeO由于本征热导率低且Seebeck系数较高而广受关注。本研究探索了变价稀土元素Eu替换Bi位对BiCuSeO热电材料微观组织和热电性能的影响。实验结果显示, 样品中同时存在Eu²⁺和Eu³⁺两种价态的离子, 掺杂Eu元素不仅可以增加样品的载流子浓度, 还可以调整样品的能带结构, 进而改善样品的电输运性能, Bi_0.85Eu_0.15CuSeO电导率显著提升, 在823 K时达到了98 S·cm^-1, 相比于未掺杂样品提升了将近6倍。在温度为823 K时, Bi_0.975Eu_0.025CuSeO的功率因子可达0.32 mW·m^-1·K^-2, ZT值为0.49。本研究表明, 掺杂变价稀土元素可以有效改善BiCuSeO热电材料的性能。

关键词: 热电材料, BiCuSeO, 变价元素掺杂

Abstract:

As a new promising thermoelectrical material in the range of intermediate temperature, BiCuSeO attracts much attention due to the combination of low intrinsic thermal conductivity and relatively high Seebeck coefficient. In this study, the effects of substituting variable-valence rare-earth element Eu for Bi site on the microstructure and thermoelectric performance of BiCuSeO-based material were investigated. The results indicate that ions of two valence states, Eu²⁺ and Eu³⁺, coexist in the doped BiCuSeO samples. The doping of Eu not only improves the concentration of the carriers, but also modifies the band structure of BiCuSeO matrix, resulting in effective improvement of electrical transport properties. The electrical conductivity of Bi_0.85Eu_0.15CuSeO reaches 98 S·cm^-1 at 823 K, which is 6 times as high as that of the undoped sample. The power factor of 0.32 mW·m^-1·K^-2 and ZT of 0.49 can be achieved at 823 K for Bi_0.975Eu_0.025CuSeO sample. This study shows that the doping of variable-valence rare-earth elements can effectively improve the thermoelectric properties of BiCuSeO.

Key words: thermoelectric materials, BiCuSeO, variable-valence element doping

中图分类号:

O472

康慧君,张校影,王燕遐,李建波,杨雄,刘达权,杨泽荣,王同敏. 变价稀土元素Eu掺杂BiCuSeO热电性能的研究[J]. 无机材料学报, 2020, 35(9): 1041-1046.

KANG Huijun,ZHANG Xiaoying,WANG Yanxia,LI Jianbo,YANG Xiong,LIU Daquan,YANG Zerong,WANG Tongmin. Effect of Rare-earth Variable-valence Element Eu doping on Thermoelectric Property of BiCuSeO[J]. Journal of Inorganic Materials, 2020, 35(9): 1041-1046.

图/表 10

图1 Bi1-xEuxCuSeO块体的XRD图谱

Fig. 1 XRD patterns for Bi1-xEuxCuSeO samples

表1 Bi1-xEuxCuSeO样品晶格参数

Table 1 Lattice parameters of Bi1-xEuxCuSeO samples

	a/nm	c/nm
BiCuSeO	0.39354	0.89413
Bi_0.975Eu_0.025CuSeO	0.39358	0.89423
Bi_0.925Eu_0.075CuSeO	0.39355	0.89436
Bi_0.85Eu_0.15CuSeO	0.39354	0.89442

图2 Bi1-xEuxCuSeO 样品的断口SEM形貌

Fig. 2 SEM images of the fracture surface of Bi1-xEuxCuSeO (a) x=0; (b) x=0.025; (c) x=0.075; (d) x=0.15

表2 Bi1-xEuxCuSeO块体密度测试结果

Table 1 Densities of Bi1-xEuxCuSeO bulk samples

Bi_1-_xEu_xCuSeO	x=0	x=0.025	x=0.075	x=0.15
Density/(g·cm^-3)	6.888	8.421	8.43	8.257
Relative density	77.3%	94.5%	94.6%	92.6%

图3 Bi0.975Eu0.025CuSeO样品的XPS(a)全谱和(b)Eu2+/Eu+3谱图

Fig. 3 XPS (a) total survey and (b) spectra of valence state of Eu2+/Eu3+ for Bi0.975Eu0.025CuSeO sample

图4 Bi1-xEuxCuSeO样品的能带结构及带隙变化图

Fig. 4 Electronic bands and band gaps of Bi1-xEuxCuSeO (a) x=0; (b) x=0.025; (c) x=0.075; (d) x=0.15

图5 室温下Bi1-xEuxCuSeO载流子浓度和载流子迁移率的变化曲线

Fig. 5 Carrier concentrations and mobilities of Bi1-xEuxCuSeO samples varied with x at room temperature

图6 Bi1-xEuxCuSeO样品的电输运性能随温度的变化曲线

Fig. 6 Temperature dependence of electrical transport properties of Bi1-xEuxCuSeO samples (a) Electrical conductivity; (b) Seebeck coefficient; (c) Power factor

图7 Bi1-xEu1-xCuSeO块体样品的热输运性能随温度的变化曲线

Fig. 7 Temperature dependence of thermal transport properties of Bi1-xEu1-xCuSeO samples (a) Total thermal conductivity; (b) Lattice thermal conductivity

图8 Bi1-xEuxCuSeO的热电优值ZT随温度的变化曲线

Fig. 8 Temperature dependences for ZT of Bi1-xEuxCuSeO samples

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变价稀土元素Eu掺杂BiCuSeO热电性能的研究

Effect of Rare-earth Variable-valence Element Eu doping on Thermoelectric Property of BiCuSeO

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