具有钛空位的碳氧化钛的热力学及热电性能

张宝; 肖九三; 焦树强; 朱鸿民

doi:10.1007/s12613-022-2421-8

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文章导航 > 矿物冶金与材料学报（英文） > 2022 > 29(4): 787-795

Bao Zhang, Jiusan Xiao, Shuqiang Jiao, and Hongmin Zhu, Thermodynamic and thermoelectric properties of titanium oxycarbide with metal vacancy, Int. J. Miner. Metall. Mater., 29(2022), No. 4, pp. 787-795. https://doi.org/10.1007/s12613-022-2421-8

Cite this article as:

Bao Zhang, Jiusan Xiao, Shuqiang Jiao, and Hongmin Zhu, Thermodynamic and thermoelectric properties of titanium oxycarbide with metal vacancy, Int. J. Miner. Metall. Mater., 29(2022), No. 4, pp. 787-795. https://doi.org/10.1007/s12613-022-2421-8

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研究论文

具有钛空位的碳氧化钛的热力学及热电性能

1)
北京科技大学钢铁冶金新技术国家重点实验室, 北京 100083, 中国
2)
北京理工大学材料学院, 北京 100081, 中国
3)
南方海洋科学与工程广东省实验室(珠海)海洋工程材料与腐蚀控制创新团队, 广东 519080, 中国
4)
Tohoku University, Sendai 980-8579, Japan

通讯作者:
肖九三 E-mail: jsxiao@ustb.edu.cn

朱鸿民 E-mail: hzhu@ustb.edu.cn

文章亮点

(1) 研究了钛空位对碳氧化钛电子结构的影响。

(2) 研究了含钛空位碳氧化钛合成过程的热力学。

(3) 研究了钛空位对碳氧化钛电和热输运性能的影响。

中文摘要

常规的碳氧化钛具有良好的导电性，然而高载流子浓度导致塞贝克系数偏低，限制了其在热电领域的发展。本文旨在探究金属空位对碳氧化钛热电性能的影响。首先，基于密度泛函理论计算预测了钛空位对碳氧化钛电子结构的影响，结果表明钛空位的存在将削弱穿过费米能级电子的态密度，降低载流子浓度的同时提高载流子迁移率。利用碳化钛与二氧化钛在900℃下的反应合成了含钛空位的碳氧化钛，并采用差示扫描量热法研究了反应过程的热力学。通过放电等离子烧结分别制备了常规碳氧化钛（TiC_0.5O_0.5）和含钛空位的碳氧化钛（Ti_0.86C_0.63O_0.37），通过电导率、塞贝克系数和热导率测试结合显微结构表征研究了钛空位对碳氧化钛热电性能的影响。结果表明，钛空位的引入使载流子浓度从TiC_0.5O_0.5的1.71×10²¹ cm⁻³降低到Ti_0.86C_0.63O_0.37的4.5 × 10²⁰ cm⁻³。此外，空位富集区和常规碳氧化钛晶体区域形成的半相干界面有效提高了内部电子散射几率，使电子迁移率从1.65 cm⁻²·V⁻¹·s⁻¹提高至4.22 cm⁻²·V⁻¹·s⁻¹，既维持了高导电性又改善了塞贝克系数，在1073 K达到−64 μV·K⁻¹。最终，Ti_0.86C_0.63O_0.37的热电优值ZT相较于TiC_0.5O_0.5在1073 K时增加了五个数量级，达到2.11 × 10⁻²。本文通过空位工程的方式实现类金属陶瓷材料中载流子浓度和迁移率的调节，在维持其高导电性优势的同时提升了塞贝克系数，为实现该类材料在热电领域的应用提供了策略和方向。

关键词:

Research Article

Thermodynamic and thermoelectric properties of titanium oxycarbide with metal vacancy

+ Author Affiliations

1)
State Key Laboratory of Advanced Metallurgy, University of Science and Technology Beijing, Beijing 100083, China
2)
School of Materials Science and Engineering, Beijing Institute of Technology, Beijing 100081, China
3)
Innovation Group of Marine Engineering Materials and Corrosion Control, Southern Marine Science and Engineering Guangdong Laboratory, Zhuhai 519080, China
4)
Tohoku University, Sendai 980-8579, Japan

Corresponding authors:
Jiusan Xiao E-mail: jsxiao@ustb.edu.cn

Hongmin Zhu E-mail: hzhu@ustb.edu.cn
Received: 30 September 2021; Revised: 12 January 2022; Accepted: 17 January 2022; Available online: 19 January 2022

Abstract

Abstract

Normal titanium oxycarbide exhibits an excellent electrical conductivity and a high carrier concentration of approximately 10²¹ cm⁻³; however, the low Seebeck coefficient limits the thermoelectric application. In this study, first-principle calculations demonstrate that the metal vacancy of titanium oxycarbide weakens the density of state passing through the valence band at the Fermi level, impairing the carrier concentration and enhancing carrier mobility. Thermodynamic analysis justifies the formation of titanium oxycarbide with metal vacancy through solid-state reaction. Transmission electron microscopic images demonstrate the segregation of metal vacancy based on the observation of the defect-rich and single-crystal face-centered cubic regions. Metal vacancy triggers the formation of vacancy-rich and single-crystal face-centered cubic regions. The aggregation of metal vacancy leads to the formation of the vacancy-rich region and other regions with a semi-coherent interface, suppressing the carrier concentration from 1.71 × 10²¹ to 4.5 × 10²⁰ cm⁻³ and resulting in the Seebeck coefficient from −11 μV/K of TiC_0.5O_0.5 to −64 μV/K at 1073 K. Meanwhile, vacancies accelerate electron migration from 1.65 to 4.22 cm⁻²·V⁻¹·s⁻¹, maintaining high conductivity. The figure of merit （ZT） increases more than five orders of magnitude via the introduction of metal vacancy, with the maximum figure of 2.11 × 10⁻² at 1073 K. These results indicate the potential thermoelectric application of metal-oxycarbide materials through vacancy engineering.
- titanium oxycarbide;
- metal vacancy;
- thermoelectric;
- first-principle calculation;
- thermodynamics

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