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Highly stabilized and efficient thermoelectric copper selenide

Nature Materials volume 23, pages 527–534 (2024)Cite this article

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Abstract

The liquid-like feature of thermoelectric superionic conductors is a double-edged sword: the long-range migration of ions hinders the phonon transport, but their directional segregation greatly impairs the service stability. We report the synergetic enhancement in figure of merit (ZT) and stability in Cu1.99Se-based superionic conductors enabled by ion confinement effects. Guided by density functional theory and nudged elastic band simulations, we elevated the activation energy to restrict ion migrations through a cation–anion co-doping strategy. We reduced the carrier concentration without sacrificing the low thermal conductivity, obtaining a ZT of ∼3.0 at 1,050 K. Notably, the fabricated device module maintained a high conversion efficiency of up to ∼13.4% for a temperature difference of 518 K without obvious degradation after 120 cycles. Our work could be generalized to develop electrically and thermally robust functional materials with ionic migration characteristics.

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Fig. 1: Ion confinement effect leading to high thermoelectric ZT and conversion efficiency.
Fig. 2: Structure characterization at the atomic level.
Fig. 3: Electrical transport properties.
Fig. 4: Thermal transport properties, ZT values and service stability.

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All data are available in the main text or Supplementary Information. Source data are provided with this paper.

References

  1. Bell, L. E. Cooling, heating, generating power, and recovering waste heat with thermoelectric systems. Science 321, 1457–1461 (2008).

    Article  CAS  PubMed  Google Scholar 

  2. Tan, G., Zhao, L. D. & Kanatzidis, M. G. Rationally designing high-performance bulk thermoelectric materials. Chem. Rev. 116, 12123–12149 (2016).

    Article  CAS  PubMed  Google Scholar 

  3. Mao, J. et al. High thermoelectric cooling performance of n-type Mg3Bi2-based materials. Science 365, 495–498 (2019).

    Article  CAS  PubMed  Google Scholar 

  4. Wei, T.-R., Wu, C.-F., Li, F. & Li, J.-F. Low-cost and environmentally benign selenides as promising thermoelectric materials. J. Materiomics 4, 304–320 (2018).

    Article  Google Scholar 

  5. Pei, Y. et al. Convergence of electronic bands for high performance bulk thermoelectrics. Nature 473, 66–69 (2011).

    Article  CAS  PubMed  Google Scholar 

  6. Zhao, W. et al. Superparamagnetic enhancement of thermoelectric performance. Nature 549, 247–251 (2017).

    Article  CAS  PubMed  Google Scholar 

  7. Biswas, K. et al. High-performance bulk thermoelectrics with all-scale hierarchical architectures. Nature 489, 414–418 (2012).

    Article  CAS  PubMed  Google Scholar 

  8. Jiang, B. et al. High-entropy-stabilized chalcogenides with high thermoelectric performance. Science 371, 830–834 (2021).

    Article  CAS  PubMed  Google Scholar 

  9. Liu, H. et al. Copper ion liquid-like thermoelectrics. Nat. Mater. 11, 422–425 (2012).

    Article  PubMed  Google Scholar 

  10. Zhang, Z. et al. Cu2Se-based liquid-like thermoelectric materials: looking back and stepping forward. Energy Environ. Sci. 13, 3307–3329 (2020).

    Article  CAS  Google Scholar 

  11. Yang, D. et al. Blocking ion migration stabilizes the high thermoelectric performance in Cu2Se composites. Adv. Mater. 32, e2003730 (2020).

    Article  PubMed  Google Scholar 

  12. Olvera, A. A. et al. Partial indium solubility induces chemical stability and colossal thermoelectric figure of merit in Cu2Se. Energy Environ. Sci. 10, 1668–1676 (2017).

    Article  CAS  Google Scholar 

  13. Qiu, P. et al. Suppression of atom motion and metal deposition in mixed ionic electronic conductors. Nat. Commun. 9, 2910 (2018).

    Article  PubMed  PubMed Central  Google Scholar 

  14. Lee, J.-W., Tan, S., Seok, S. I., Yang, Y. & Park, N.-G. Rethinking the A cation in halide perovskites. Science 375, eabj1186 (2022).

    Article  CAS  PubMed  Google Scholar 

  15. Zhao, Y. et al. Suppressing ion migration in metal halide perovskite via interstitial doping with a trace amount of multivalent cations. Nat. Mater. 21, 1396–1402 (2022).

    Article  CAS  PubMed  Google Scholar 

  16. Nazrul Islam, S. M. K. et al. Copper diffusion rates and hopping pathways in superionic Cu2Se. Acta Mater. 215, 117026 (2021).

    Article  CAS  Google Scholar 

  17. Gao, Y. et al. Classical and emerging characterization techniques for investigation of ion transport mechanisms in crystalline fast ionic conductors. Chem. Rev. 120, 5954–6008 (2020).

    Article  CAS  PubMed  Google Scholar 

  18. Liu, W. et al. Ag doping induced abnormal lattice thermal conductivity in Cu2Se. J. Mater. Chem. C 6, 13225–13231 (2018).

    Article  CAS  Google Scholar 

  19. Zhao, K. et al. Enhanced thermoelectric performance through tuning bonding energy in Cu2Se1–xSx liquid-like materials. Chem. Mater. 29, 6367–6377 (2017).

    Article  CAS  Google Scholar 

  20. Day, T. W. et al. Influence of compensating defect formation on the doping efficiency and thermoelectric properties of Cu2-ySe1–xBrx. Chem. Mater. 27, 7018–7027 (2015).

    Article  CAS  Google Scholar 

  21. Bailey, T. P. et al. Enhanced ZT and attempts to chemically stabilize Cu2Se via Sn doping. J. Mater. Chem. A 4, 17225–17235 (2016).

    Article  CAS  Google Scholar 

  22. Yang, L. et al. Te-doped Cu2Se nanoplates with a high average thermoelectric figure of merit. J. Mater. Chem. A 4, 9213–9219 (2016).

    Article  CAS  Google Scholar 

  23. Jin, Z. et al. Thermoelectric properties and service stability of Ag-containing Cu2Se. Mater. Today Phys. 21, 100550 (2021).

    Article  CAS  Google Scholar 

  24. Nazrul Islam, S. M. K. et al. Giant enhancement of the figure-of-merit over a broad temperature range in nano-boron incorporated Cu2Se. J. Mater. Chem. A 6, 18409–18416 (2018).

    Article  CAS  Google Scholar 

  25. Lei, J. et al. High thermoelectric performance in Cu2Se superionic conductor with enhanced liquid-like behaviour by dispersing SiC. J. Mater. Chem. A 7, 7006–7014 (2019).

    Article  CAS  Google Scholar 

  26. Nunna, R. et al. Ultrahigh thermoelectric performance in Cu2Se-based hybrid materials with highly dispersed molecular CNTs. Energy Environ. Sci. 10, 1928–1935 (2017).

    Article  CAS  Google Scholar 

  27. Hu, X. et al. Power generation from nanostructured PbTe-based thermoelectrics: comprehensive development from materials to modules. Energy Environ. Sci. 9, 517–529 (2016).

    Article  CAS  Google Scholar 

  28. Jiang, B. et al. Realizing high-efficiency power generation in low-cost PbS-based thermoelectric materials. Energy Environ. Sci. 13, 579–591 (2020).

    Article  CAS  Google Scholar 

  29. Xing, T. et al. High efficiency GeTe-based materials and modules for thermoelectric power generation. Energy Environ. Sci. 14, 995–1003 (2021).

    Article  CAS  Google Scholar 

  30. Zhang, Q. et al. Realizing high-performance thermoelectric power generation through grain boundary engineering of skutterudite-based nanocomposites. Nano Energy 41, 501–510 (2017).

    Article  CAS  Google Scholar 

  31. Nie, G. et al. High performance thermoelectric module through isotype bulk heterojunction engineering of skutterudite materials. Nano Energy 66, 104193 (2019).

    Article  CAS  Google Scholar 

  32. Chu, J. et al. Electrode interface optimization advances conversion efficiency and stability of thermoelectric devices. Nat. Commun. 11, 2723 (2020).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  33. Yu, J. et al. Half-Heusler thermoelectric module with high conversion efficiency and high power density. Adv. Energy Mater. 10, 2000888 (2020).

    Article  CAS  Google Scholar 

  34. Xing, Y. et al. A device-to-material strategy guiding the ‘double-high’ thermoelectric module. Joule 4, 2475–2483 (2020).

    Article  CAS  Google Scholar 

  35. Fu, Y. et al. Mg3(Bi,Sb)2-based thermoelectric modules for efficient and reliable waste-heat utilization up to 750 K. Energy Environ. Sci. 15, 3265–3274 (2022).

    Article  CAS  Google Scholar 

  36. Bu, Z. et al. An over 10% module efficiency obtained using non-Bi2Te3 thermoelectric materials for recovering heat of <600 K. Energy Environ. Sci. 14, 6506–6513 (2021).

    Article  CAS  Google Scholar 

  37. Ying, P. et al. Towards tellurium-free thermoelectric modules for power generation from low-grade heat. Nat. Commun. 12, 1121 (2021).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  38. Bu, Z. et al. A record thermoelectric efficiency in tellurium-free modules for low-grade waste heat recovery. Nat. Commun. 13, 237 (2022).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  39. Qiu, P. et al. High-efficiency and stable thermoelectric module based on liquid-like materials. Joule 3, 1538–1548 (2019).

    Article  CAS  Google Scholar 

  40. Li, F. et al. Giant piezoelectricity of Sm-doped Pb (Mg1/3Nb2/3)O3–PbTiO3 single crystals. Science 364, 264–268 (2019).

    Article  CAS  PubMed  Google Scholar 

  41. Zhu, Y., Zhou, W., Sunarso, J., Zhong, Y. & Shao, Z. Phosphorus-doped perovskite oxide as highly efficient water oxidation electrocatalyst in alkaline solution. Adv. Funct. Mater. 26, 5862–5872 (2016).

    Article  CAS  Google Scholar 

  42. Yang, T. et al. One-stone-for-two-birds strategy to attain beyond 25% perovskite solar cells. Nat. Commun. 14, 839 (2023).

    Article  PubMed  PubMed Central  Google Scholar 

  43. Gahtori, B. et al. Giant enhancement in thermoelectric performance of copper selenide by incorporation of different nanoscale dimensional defect features. Nano Energy 13, 36–46 (2015).

    Article  CAS  Google Scholar 

  44. Dong, J. et al. Medium-temperature thermoelectric GeTe: vacancy suppression and band structure engineering leading to high performance. Energy Environ. Sci. 12, 1396–1403 (2019).

    Article  CAS  Google Scholar 

  45. Yu, B. et al. Thermoelectric properties of copper selenide with ordered selenium layer and disordered copper layer. Nano Energy 1, 472–478 (2012).

    Article  CAS  Google Scholar 

  46. Kresse, G. & Hafner, J. Ab initio molecular dynamics for liquid metals. Phys. Rev. B 47, 558–561 (1993).

    Article  CAS  Google Scholar 

  47. Henkelman, G. & Jónsson, H. Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points. J. Chem. Phys. 113, 9978–9985 (2000).

    Article  CAS  Google Scholar 

  48. Dudarev, S. L. et al. Electron-energy-loss spectra and the structural stability of nickel oxide: an LSDA + U study. Phys. Rev. B 57, 1505–1509 (1998).

    Article  CAS  Google Scholar 

  49. Momma, K. & Izumi, F. VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data. J. Appl. Crystallogr. 44, 1272–1276 (2011).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by a Basic Science Center Project of the National Natural Science Foundation of China (52388201) and the National Key R&D Program of China (2023YFB3809400). J.Y. gratefully acknowledges financial support from the International Postdoctoral Exchange Fellowship Program (Talent-Introduction Program) (YJ20220135) and Shuimu Tsinghua Scholar Program.

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Author notes

  1. These authors contributed equally: Haihua Hu, Yiwei Ju.

Authors and Affiliations

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

    Haihua Hu, Yiwei Ju, Jincheng Yu, Zechao Wang, Jun Pei, Hao-Cheng Thong, Jing-Wei Li, Zhanran Han, Bin Su, Hua-Lu Zhuang, Yilin Jiang, Qian Li, Huijuan Zhao, Jing Zhu & Jing-Feng Li

  2. National Center of Electron Microscopy in Beijing, School of Materials Science and Engineering, Tsinghua University, Beijing, China

    Yiwei Ju, Zechao Wang, Huijuan Zhao & Jing Zhu

  3. Ji Hua Laboratory, Foshan, China

    Yiwei Ju, Zechao Wang, Huijuan Zhao & Jing Zhu

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

    Jun Pei & Bo-Ping Zhang

  5. Guangxi Pilot Free Trade Zone Jianju Technology Co., Ltd, Qinzhou, China

    Bowen Cai & Fengming Liu

  6. Department of Precision Instrument, Tsinghua University, Beijing, China

    Hezhang Li

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Contributions

H.H., J.Y. and J.-F.L. designed this work. H.H. prepared the samples and carried out the thermoelectric property measurements. Y. Ju, Z.W., H.Z. and J.Z. conducted the STEM observations and analysis. J.P., H.-C.T., Z.H. and B.-P.Z. carried out the DFT calculations. H.H. and J.Y. carried out the stability test. H.H., J.-W.L., B.C., F.L., H.-L.Z. and B.S. built the thermoelectric devices and performed the energy conversion efficiency measurements. H.-L.Z., B.S., H.L. and Q.L. provided helpful discussions. H.H. and Y. Jiang carried out the Hall measurements. All authors conceived the experiments, analysed the results and co-edited the manuscript.

Corresponding authors

Correspondence to Jincheng Yu, Jing Zhu or Jing-Feng Li.

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Nature Materials thanks Pengfei Qiu and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Note, Figs. 1–21, Tables 1–3 and refs. 1 and 2.

Supplementary Data 1

Atomic coordinates of the computational models.

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Hu, H., Ju, Y., Yu, J. et al. Highly stabilized and efficient thermoelectric copper selenide. Nat. Mater. 23, 527–534 (2024). https://doi.org/10.1038/s41563-024-01815-1

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