In2O3/InNbO4复合材料的热电性能研究

doi:10.15541/jim20210631

无机材料学报 ›› 2022, Vol. 37 ›› Issue (7): 724-730.DOI: 10.15541/jim20210631

所属专题：【能源环境】热电材料

In₂O₃/InNbO₄复合材料的热电性能研究

程成(), 李建波, 田震, 王鹏将, 康慧君(), 王同敏

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

收稿日期:2021-10-11 修回日期:2021-11-19 出版日期:2022-07-20 网络出版日期:2021-12-02
通讯作者: 康慧君, 教授. E-mail: kanghuijun@dlut.edu.cn
作者简介:程成(1996-), 男, 硕士研究生. E-mail: cc2019@mail.dlut.edu.cn
基金资助:
国家自然科学基金(51971052);国家自然科学基金(51774065);国家重点研发计划(2017YFA0403803);辽宁省“兴辽英才计划”(XLYC2007183);辽宁省“兴辽英才计划”(XLYC1808005);大连市科技创新基金(2020JJ25CY002);大连市科技创新基金(2020JJ26GX045)

Thermoelectric Property of In₂O₃/InNbO₄ Composites

CHENG Cheng(), LI Jianbo, TIAN Zhen, WANG Pengjiang, KANG Huijun(), WANG Tongmin

Key Laboratory of Solidification Control and Digital Preparation Technology (Liaoning Province), School of Materials Science and Engineering, Dalian University of Technology, Dalian 116024, China

Received:2021-10-11 Revised:2021-11-19 Published:2022-07-20 Online:2021-12-02
Contact: KANG Huijun, professor. E-mail: kanghuijun@dlut.edu.cn
About author:CHENG Cheng (1996-), male, Master candidate. E-mail: cc2019@mail.dlut.edu.cn
Supported by:
National Natural Science Foundation of China(51971052);National Natural Science Foundation of China(51774065);National Key Research and Development Program of China(2017YFA0403803);Liaoning Revitalization Talents Program(XLYC2007183);Liaoning Revitalization Talents Program(XLYC1808005);Innovation Foundation of Science and Technology of Dalian(2020JJ25CY002);Innovation Foundation of Science and Technology of Dalian(2020JJ26GX045)

摘要/Abstract

摘要：

In₂O₃作为一种良好的光电和气敏材料, 因高温下具有优异的热电性能在热电领域也获得广泛关注。本研究通过固相反应法结合放电等离子烧结(SPS)成功将原位自生的InNbO₄第二相引入到In₂O₃基体中, 优化了块体样品的制备工艺。同时, InNbO₄改善了样品的电输运性能, 使载流子浓度明显提高, 在1023 K时电导率最高可达1548 S·cm^-1, 高于大多数元素掺杂的样品。其中, 0.998In₂O₃/0.002InNbO₄样品的热电性能测试表明, 在1023 K时, 其功率因子可达到0.67 mW·m^-1·K^-2, 热电优值(ZT)达到最高值0.187。综上所述, 通过在In₂O₃中原位复合InNbO₄第二相可以很好地改善In₂O₃基热电陶瓷的电性能, 进而调控其高温热电性能。

关键词: 热电材料, In₂O₃, InNbO₄, 高温热电性能

Abstract:

As being a good photoelectric and gas sensitive material, In₂O₃ is of great interest to the thermoelectric community due to its excellent thermoelectric properties at high temperature. In this study, the second phase InNbO₄ was successfully induced into the In₂O₃ matrix in situ by solid-state reaction combined with spark plasma sintering (SPS) to optimize the preparation process of bulk samples. It is found that introducing InNbO₄ distinctly affects the electrical transport properties of the In₂O₃/InNbO₄ composite samples, and its carrier concentration is dramatically increased. The highest electrical conductivity is 1548 S·cm^-1 at 1023 K, which is higher than those of most element-doped samples. The power factor of 0.67 mW·m^-1·K^-2 and the highest ZT value of 0.187 are achieved for the 0.998In₂O₃/0.002InNbO₄ sample at 1023 K. In conclusion, the electrical properties of In₂O₃ ceramics can be effectively improved by introducing in-situ InNbO₄ second phase, and thus the thermoelectric property at high temperatures is further regulated.

Key words: thermoelectric materials, In₂O₃, InNbO₄, thermoelectric property at high temperature

中图分类号:

O472

程成, 李建波, 田震, 王鹏将, 康慧君, 王同敏. In₂O₃/InNbO₄复合材料的热电性能研究[J]. 无机材料学报, 2022, 37(7): 724-730.

CHENG Cheng, LI Jianbo, TIAN Zhen, WANG Pengjiang, KANG Huijun, WANG Tongmin. Thermoelectric Property of In₂O₃/InNbO₄ Composites[J]. Journal of Inorganic Materials, 2022, 37(7): 724-730.

图/表 9

图1 (1-x)In2O3/xInNbO4块体的XRD图谱

Fig. 1 XRD patterns for (1-x)In2O3/xInNbO4 samples

图2 0.998In2O3/0.002InNbO4样品的基体组织与成分

Fig. 2 Matrix structure and composition of 0.998In2O3/ 0.002InNbO4

图3 纯In2O3粉体样品(a), (1-x)In2O3/xInNbO4 (x=(b) 0, (c) 0.04)块体样品断口, (1-x)In2O3/xInNbO4(x=(d) 0.002, (e) 0.02, (f) 0.04)块体样品表面的SEM照片; (g, h) 0.96In2O3/0.04InNbO4高倍数下的Nb元素分布图

Fig. 3 SEM images of (a) pure In2O3 powder, fracture surface for (1-x)In2O3/xInNbO4 (x=(b) 0, (c) 0.04), surface SEM images for (1-x)In2O3/xInNbO4 (x=0.002 (d), x=0.02 (e), x=0.04 (f)); (g-h) elemental distributions of Nb at high magnification for 0.96In2O3/0.04InNbO4

表1 (1-x)In2O3/xInNbO4块体样品室温下的测试密度(ρm)、理论密度(ρth)、相对密度(ρr)、载流子浓度(n)和迁移率(μ)

Table 1 Measured densities(ρm), theoretical densities(ρth), relative densities (ρr), carrier concentrations (n) and carrier mobilities (μ) of (1-x)In2O3/xInNbO4 samples at room temperature

(1-x)In₂O₃/xInNbO₄	ρ_m/(g·cm^-3)	ρ_th/(g·cm^-3)	ρ_r/%	n/(×10¹⁹, cm^-3)	μ/(cm²·V^-1·s^-1)
x=0	6.969	7.120	97.9	0.46	94.26
x=0.002	7.016	7.119	98.6	0.78	76.22
x=0.006	6.811	7.117	95.7	5.90	38.21
x=0.01	6.658	7.116	93.6	9.80	38.43
x=0.02	6.598	7.112	92.8	20.88	40.22
x=0.04	6.547	7.100	92.2	45.24	39.86

图4 0.96In2O3/0.04InNbO4样品的(a)XPS全谱图, 以及(b) Nb3d、(c) In3d和(d) O1s轨道的XPS高分辨谱图

Fig. 4 (a) XPS total survey and high-resolution XPS spectra of (b) Nb3d, (c) In3d and (d) O1s core-level regions for 0.96In2O3/0.04InNbO4 sample

图5 (1-x)In2O3/xInNbO4(x=0, 0.002)样品的载流子浓度(n)和载流子迁移率(μ)随温度的变化曲线

Fig. 5 Temperature dependence of electrical carrier concentrations and mobilities of (1-x)In2O3/xInNbO4(x=0, 0.002)

图6 (1-x)In2O3/xInNbO4、In1.76(Zn0.12Ge0.12)O3[33]和In1.88V0.12O3[34]的(a) 电导率、(b) Seebeck系数和(c) 功率因子随温度的变化曲线

Fig. 6 Temperature dependence of (a) electrical conductivities, (b) Seebeck coefficients and (c) power factors of (1-x)In2O3/xInNbO4, In1.76(Zn0.12Ge0.12)O3[33] and In1.88V0.12O3[34]

图7 (1-x)In2O3/xInNbO4、In1.76(Zn0.12Ge0.12)O3[33]和In1.88V0.12O3[34]的(a)总热导率、(b)电子热导率和(c)晶格热导率随温度的变化曲线

Fig. 7 Temperature dependence of (a) total thermal conductivity, (b) electronic thermal conductivity and (c) lattice thermal conductivity of (1-x)In2O3/xInNbO4, In1.76(Zn0.12Ge0.12)O3[33] and In1.88V0.12O3[34]

图8 (1-x)In2O3/xInNbO4、In1.76(Zn0.12Ge0.12)O3[33]和In1.88V0.12O3[34]的热电优值ZT随温度的变化曲线

Fig. 8 Temperature dependence of ZT for (1-x)In2O3/xInNbO4, In1.76(Zn0.12Ge0.12)O3[33] and In1.88V0.12O3[34]

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In₂O₃/InNbO₄复合材料的热电性能研究

Thermoelectric Property of In₂O₃/InNbO₄ Composites

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