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Enhanced thermoelectric properties and electrical stability for Cu1.8S-based alloys: Entropy engineering and Cu vacancy engineering

Cu1.8S基合金的热电性能和电稳定性增强: 熵工程和 Cu空位工程

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Abstract

Cu1.8S-based thermoelectric (TE) materials have garnered considerable interest due to their pollution-free, low-cost, and superior performance characteristics. However, high Cu vacancy and Cu migration inhibit their performance and electrical stability improvement. Through mechanical alloying and spark plasma sintering, a series of Cu1.8S and MnxCu1.8-S0.5Se0.5 (0.01 ≤ x ≤ 0.06) bulk samples were prepared in this study. With Se alloying and Mn doping, the configuration entropy of MnxCu1.8S0.5Se0.5 increases from low-entropy 0.4R* for pristine Cu1.8S to medium-entropy 1.2R* for MnxCu1.8S0.5-Se0.5. MnxCu1.8S0.5Se0.5 subsequently crystallized in a cubic phase with enhanced symmetry and Mn solid solubility. High solubility enables the filling of excessive Cu vacancies, the reduction of carrier concentration, the adjustment of band structure, the enhancement of the Cu migration energy barrier, and the inhibition of Cu migration. Even at current densities exceeding 25 A cm−2 at 750 K, the resistance of Mn0.03Cu1.8S0.5Se0.5 remained hardly changed, indicating a vastly improved electrical stability. In addition, the ultralow thermal conductivity of the lattice is achieved by decreasing the sound velocity and softening the lattice. At 773 K, the bulk ZT of Mn0.06Cu1.8S0.5Se0.5 reaches a maximum of 0.79, which is twice that of pure Cu1.8S. The results indicate that combining entropy engineering and Cu vacancy engineering is an effective strategy for developing high-performance Cu1.8S TE materials.

摘要

无污染、低成本和高性能Cu1.8S基类液态热电材料受到关注. 但 是, 其过高的本征Cu空位和Cu离子迁移特性限制了其性能和电稳定性 的进一步提升. 本研究采用机械合金化结合放电等离子体烧结制备了 一系列Cu1.8S和MnxCu1.8S0.5Se0.5 (0.01 ≤ x ≤ 0.06)块体热电材料. 随着 Se和Mn的引入, 体系由低熵Cu1.8S (0.4R*)转变为中熵MnxCu1.8S0.5Se0.5 (1.2R*). 构型熵的增加不仅提高了体系的结构对称性, MnxCu1.8S0.5Se0.5 室温下呈立方相结构, 还增大了Mn的固溶度. 高浓度Mn固溶有效填补 了过高的本征Cu空位, 降低了载流子浓度, 优化了能带结构, 提升了电 输运性能. 熵工程一方面增大了Cu离子迁移势垒, 抑制Cu离子迁移. 750 K下, 即使电流密度达到24 A cm−2, Mn0.03Cu1.8S0.5Se0.5的电阻也几 乎没有变化, 显示出优异的电稳定性; 同时可降低声速, 软化晶格, 降 低晶格热导率. Mn0.06Cu1.8S0.5Se0.5的块体样品在773 K时获得最大ZT值 0.79, 相较于初始样品提高了两倍. 结果表明熵工程结合Cu空位工程是 提升Cu1.8S基热电材料性能的有效策略.

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Acknowledgements

This work was supported by the National Key R&D Program of China (2018YFB0703603) and the State Key Laboratory of New Ceramic and Fine Processing Tsinghua University (KF202111).

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  1. These authors contributed equally to this work.

Authors and Affiliations

  1. Beijing Municipal Key Laboratory of New Energy Materials and Technologies, School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing, 100083, China

    Wei Zhou  (周炜), Zhihang Shan  (单帜航), Rui Zhang  (张瑞), Shikuo Lu  (卢士阔), Jun Pei  (裴俊) & Boping Zhang  (张波萍)

  2. National Institute for Materials Science (NIMS), Tsukuba, 3050047, Japan

    Hezhang Li  (李和章)

  3. Faculty of Materials Science and Engineering, Kunming University of Science and technology, Kunming, 650093, China

    Zhenhua Ge  (葛振华)

  4. Key Laboratory of Cryogenics, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing, 100190, China

    Min Zhou  (周敏)

  5. Wuhan Joule Yacht Science & Technology Co., Ltd., Wuhan, 430070, China

    Yuanbing Wang  (王愿兵)

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  1. Wei Zhou  (周炜)
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The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript.

Corresponding authors

Correspondence to Hezhang Li  (李和章), Jun Pei  (裴俊) or Boping Zhang  (张波萍).

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The authors declare that they have no conflict of interest.

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Experimental details and supporting data are available in the online version of the paper.

Wei Zhou received his Bachelor’s degree in materials science and engineering from the University of Science and Technology Beijing (USTB) in 2018. He is currently a Master’s degree candidate at USTB, China. His research interests mainly focus on the preparation of thermoelectric materials, with an emphasis on Cu2−xS-based thermoelectric materials.

Hezhang Li received his BS degree in materials science and engineering from USTB in 2016. He received his MS and PhD degrees from Tohoku University, Japan. He works as a postdoctoral at the National Institute for Materials Science, Japan His research interests mainly focus on the preparation of thermoelectric materials, with an emphasis on Heusler thermoelectric materials.

Jun Pei obtained his PhD degree with Prof. Boping Zhang from USTB in 2019. In 2019–2022, he undertook postdoctoral research under the supervision of Prof. Jingfeng Li at Tsinghua University. His current research focuses on thermoelectric materials and devices.

Boping Zhang obtained her BS at Huazhong University of Science and Technology in 1984. She received her MD and PhD at Tohoku University in 1990 and 1993, respectively. She was a researcher of Tohoku University and the Northeast Institute of Industrial Technology of Japan, respectively. Now she works as a professor at USTB since 2003. Her research interests mainly focus on lead-free piezoelectric ceramics, thermoelectric materials and devices.

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Enhanced thermoelectric properties and electrical stability for Cu1.8S-based alloys: Entropy engineering and Cu vacancy engineering

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Zhou, W., Li, H., Shan, Z. et al. Enhanced thermoelectric properties and electrical stability for Cu1.8S-based alloys: Entropy engineering and Cu vacancy engineering. Sci. China Mater. 66, 2051–2060 (2023). https://doi.org/10.1007/s40843-022-2306-4

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