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Enhanced thermoelectric performance of Cu12Sb4S13−δ tetrahedrite via nickel doping

Ni掺杂提高Cu12Sb4S13−δ黝铜矿热电性能

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Abstract

Cu12Sb4S13 tetrahedrite has received great attention as an earth-abundant and environmental-friendly thermoelectric material. This work aims to uncover the thermoelectric performance-enhancing effect and the mechanism of nickel doping on tetrahedrite. A series of Cu12−xNixSb4S13−δ (x = 0.5, 0.7, 1.0, 1.5 and 2.0) compounds were synthesized by mechanical alloying combined with spark plasma sintering. It is found that the thermal conductivity sharply reduces with increasing Ni content over the entire temperature range, < 0.9 W m−1 K−1, accompanied with an enhanced thermoelectric power factor. The model predicted that the reduced lattice thermal conductivity is attributed to mid-frequency phonon scattering, caused by precipitates and dislocations resulting from Ni doping. Consequently, a high ZT value up to 0.95 at 723 K was achieved for Cu11NiSb4S13−δ, corresponding to a ∼46% increase over non-doped Cu12Sb4S13−δ. Furthermore, the cyclic measurement showed that the Ni-doped tetrahedrites displayed high chemical stability.

摘要

Cu12Sb4S13是一种储量丰富、 环境友好的天然矿物, 被热电领域普遍关注. 本研究旨在揭示Ni掺杂提高黝铜矿材料热电性能的机理. 采用机械合金化(MA)结合放电等离子体烧结(SPS)的方法制备出Cu12−xNixSb4S13−δ (x = 0.5, 0.7, 1.0, 1.5, 2.0)样品. 实验结果表明, 在测量温度范围内(323–723 K), 随着Ni含量的增加, 样品的热导率急剧下降(< 0.9 W m−1 K−1), 同时热电功率因子逐渐增加. 理论模型计算表明, 晶格热导率的降低主要来源于Ni掺杂引起的析出相及位错对中频声子的强散射作用. 由于较低的热导率和较高的功率因子, Cu11NiSb4S13−δ 样品在723 K时获得最高ZT值0.95, 相对于未掺杂样品, 其热电性能提高了46%. 同时, 热循环测试表明, 通过Ni掺杂提高了黝铜矿热电材料的化学稳定性.

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Acknowledgements

This work was supported by the Basic Science Center Project of National Natural Science Foundation of China (51788104 and 11474176), as well as Shenzhen Science and Technology Plan (JCYJ20150827165038323).

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Authors and Affiliations

  1. State Key Laboratory of New Ceramics and Fine Processing, School of Materials Science and Engineering, Tsinghua University, Beijing, 100084, China

    Fu-Hua Sun  (孙富华), Jinfeng Dong  (董金峰),  Asfandiyar, Chao-Feng Wu  (吴超峰), Yu Pan  (潘瑜), Huaichao Tang  (唐怀超) & Jing-Feng Li  (李敬锋)

  2. School of Materials Science and Engineering, University of New South Wales, Sydney, NSW, 2052, Australia

    Shaugath Dey

  3. Advanced Materials Institute, Graduate School at Shenzhen, Tsinghua University, Shenzhen, 518055, China

    Jing-Feng Li  (李敬锋)

Authors
  1. Fu-Hua Sun  (孙富华)
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  2. Jinfeng Dong  (董金峰)
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  3. Shaugath Dey
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  5. Chao-Feng Wu  (吴超峰)
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  6. Yu Pan  (潘瑜)
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  7. Huaichao Tang  (唐怀超)
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  8. Jing-Feng Li  (李敬锋)
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Correspondence to Jing-Feng Li  (李敬锋).

Additional information

Fu-Hua Sun is a PhD candidate at the School of Materials Science and Engineering, Tsinghua University. His current research focuses on the synthesis of nano-bulk composites and their applications in thermoelectric.

Jinfeng Dong is a PhD candidate at the School of Materials Science and Engineering, Tsinghua University. His current research focuses on the synthesis of manganese-based materials and their applications in thermoelectric.

Jing-Feng Li is a professor of Tsinghua University, China. He graduated from Huazhong University of Science and Technology (China) in 1984, and obtained his doctor degree from Tohoku University (Japan) in 1991. After working in Tohoku University as an assistant professor from 1992 to 1997 and an associate professor from 1997 to 2002, he joined Tsinghua University as full professor in 2002. His research interests include piezoelectric ceramics, composites and films for MEMS applications, thermoelectric materials and devices, materials microfabrication, ceramic processing and mechanical properties.

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Sun, FH., Dong, J., Dey, S. et al. Enhanced thermoelectric performance of Cu12Sb4S13−δ tetrahedrite via nickel doping. Sci. China Mater. 61, 1209–1217 (2018). https://doi.org/10.1007/s40843-018-9241-x

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