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Magnetoelectric interaction and transport behaviours in magnetic nanocomposite thermoelectric materials

Nature Nanotechnology volume 12, pages 55–60 (2017)Cite this article

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Abstract

How to suppress the performance deterioration of thermoelectric materials in the intrinsic excitation region remains a key challenge. The magnetic transition of permanent magnet nanoparticles from ferromagnetism to paramagnetism provides an effective approach to finding the solution to this challenge. Here, we have designed and prepared magnetic nanocomposite thermoelectric materials consisting of BaFe12O19 nanoparticles and Ba0.3In0.3Co4Sb12 matrix. It was found that the electrical transport behaviours of the nanocomposites are controlled by the magnetic transition of BaFe12O19 nanoparticles from ferromagnetism to paramagnetism. BaFe12O19 nanoparticles trap electrons below the Curie temperature (TC) and release the trapped electrons above the TC, playing an ‘electron repository’ role in maintaining high figure of merit ZT. BaFe12O19 nanoparticles produce two types of magnetoelectric effect—electron spiral motion and magnon-drag thermopower—as well as enhancing phonon scattering. Our work demonstrates that the performance deterioration of thermoelectric materials in the intrinsic excitation region can be suppressed through the magnetic transition of permanent magnet nanoparticles.

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Figure 1: Effect of BaM-NPs on microstructures.
Figure 2: Hall measurement data in the temperature range 300–775 K.
Figure 3: Electrical and thermal transport properties in the range 300–850 K.
Figure 4: Curie temperature of BaM-NPs.
Figure 5: Electrical transport properties before and after magnetization.

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References

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

    CAS  Google Scholar 

  2. Snyder, G. J. & Toberer, E. S. Complex thermoelectric materials. Nat. Mater. 7, 105–114 (2008).

    CAS  Google Scholar 

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

    CAS  Google Scholar 

  4. Hsu, K. F. et al. Cubic AgPbmSbTe2+m bulk thermoelectric materials with high figure of merit. Science 303, 818–821 (2004).

    CAS  Google Scholar 

  5. Dresselhaus, M. S. et al. New directions for low-dimensional thermoelectric materials. Adv. Mater. 19, 1043–1053 (2007).

    CAS  Google Scholar 

  6. Poudel, B. et al. High-thermoelectric performance of nanostructured bismuth antimony telluride bulk alloys. Science 320, 634–638 (2008).

    CAS  Google Scholar 

  7. Zhu, T. et al. High efficiency half-Heusler thermoelectric materials for energy harvesting. Adv. Energy Mater. 5, 1500588 (2015).

    Google Scholar 

  8. Sales, B. C., Mandrus, D. & Williams, R. K. Filled skutterudite antimonides: a new class of thermoelectric materials. Science 272, 1325–1328 (1996).

    CAS  Google Scholar 

  9. Siemens, M. E. et al. Quasi-ballistic thermal transport from nanoscale interfaces observed using ultrafast coherent soft X-ray beams. Nat. Mater. 9, 26–30 (2010).

    CAS  Google Scholar 

  10. Hu, Y. et al. Spectral mapping of thermal conductivity through nanoscale ballistic transport. Nat. Nanotech. 10, 701–706 (2015).

    CAS  Google Scholar 

  11. Zhao, W. Y. et al. Enhanced thermoelectric performance via randomly arranged nanopores: excellent transport properties of YbZn2Sb2 nanoporous materials. Acta Mater. 60, 1741–1746 (2012).

    CAS  Google Scholar 

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

    Google Scholar 

  13. Delaire, O. et al. Giant anharmonic phonon scattering in PbTe. Nat. Mater. 10, 614–619 (2011).

    CAS  Google Scholar 

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

    CAS  Google Scholar 

  15. Liu, W. et al. Convergence of conduction bands as a means of enhancing thermoelectric performance of n-type Mg2Si1−xSnx solid solutions. Phys. Rev. Lett. 108, 166601 (2012).

    Google Scholar 

  16. Zhao, L. D. et al. Ultrahigh power factor and thermoelectric performance in hole-doped single-crystal SnSe. Science 351, 141–144 (2015).

    Google Scholar 

  17. Rhyee, J. S. et al. Peierls distortion as a route to high thermoelectric performance in In4Se3−δ crystals. Nature 459, 965–968 (2009).

    CAS  Google Scholar 

  18. Luo, Y. et al. Enhancement of the thermoelectric performance of polycrystalline In4Se2.5 by copper intercalation and bromine substitution. Adv. Energy Mater. 4, 1300599 (2014).

    Google Scholar 

  19. Heremans, J. P. et al. Enhancement of thermoelectric efficiency in PbTe by distortion of the electronic density of states. Science 321, 554–557 (2008).

    CAS  Google Scholar 

  20. Zhou, J., Yang, R. G., Chen, G. & Dresselhaus, M. S. Optimal bandwidth for high efficiency thermoelectric. Phys. Rev. Lett. 107, 226601 (2011).

    Google Scholar 

  21. Zhao, W. Y. et al. Multi-localization transport behaviour in bulk thermoelectric materials. Nat. Commun. 6, 6197 (2015).

    CAS  Google Scholar 

  22. Pappas, P. T. The original ampere force and Biot-Savart and Lorentz forces. Il Nuovo Cimento 76, 189–197 (1983).

    Google Scholar 

  23. Nolas, G. S., Cohn, J. L. & Slack, G. A. Effect of partial void filling on the lattice thermal conductivity of skutterudites. Phys. Rev. B 58, 164 (1998).

    CAS  Google Scholar 

  24. Meisner, G. P. et al. Structure and lattice thermal conductivity of fractionally filled skutterudites: solid solutions of fully filled and unfilled end members. Phys. Rev. Lett. 80, 3551–3554 (1998).

    CAS  Google Scholar 

  25. Rogl, G. et al. High-pressure torsion, a new processing route for thermoelectrics of high ZTs by means of severe plastic deformation. Acta Mater. 60, 2146–2157 (2012).

    CAS  Google Scholar 

  26. Kim, H. et al. Structural order–disorder transitions and phonon conductivity of partially filled skutterudites. Phys. Rev. Lett. 105, 265901 (2010).

    Google Scholar 

  27. Pei, Y. Z. et al. Improving thermoelectric performance of caged compounds through light-element filling. Appl. Phys. Lett. 95, 042101 (2009).

    Google Scholar 

  28. Qiu, Y. T. et al. Charge-compensated compound defects in Ga-containing thermoelectric skutterudites. Adv. Funct. Mater. 23, 3194–3203 (2013).

    CAS  Google Scholar 

  29. Li, H., Tang, X. F., Zhang, Q. J. & Uher, C. High performance InxCeyCo4Sb12 thermoelectric materials with in situ forming nanostructured InSb phase. Appl. Phys. Lett. 94, 102114 (2009).

    Google Scholar 

  30. Shi, X. et al. Multiple-filled skutterudites: high thermoelectric figure of merit through separately optimizing electrical and thermal transports. J. Am. Chem. Soc. 133, 7837–7846 (2011).

    CAS  Google Scholar 

  31. Zhao, W. Y. et al. Enhanced thermoelectric performance in barium and indium double-filled skutterudite bulk materials via orbital hybridization induced by indium filler. J. Am. Chem. Soc. 131, 3713–3720 (2009).

    CAS  Google Scholar 

  32. Ravinder, D., Shalini, P., Mahesh, P. & Boyanov, B. S. High temperature thermoelectric power studies of cobalt and titanium substituted barium hexagonal ferrites. J. Magn. Magn. Mater. 268, 154–158 (2004).

    CAS  Google Scholar 

  33. Nolas, G. S., Kendziora, C. A. & Takizawa, H. Polarized Raman-scattering study of Ge and Sn-filled CoSb3 . J. Appl. Phys. 94, 7440–7443 (2003).

    CAS  Google Scholar 

  34. Caillat, T., Borshchevsky, A. & Fleurial, J. P. Properties of single crystalline semiconducting CoSb3 . J. Appl. Phys. 80, 4442 (1996).

    CAS  Google Scholar 

  35. Pei, Y. Z. et al. Stabilizing the optimal carrier concentration for high thermoelectric efficiency. Adv. Mater. 23, 5674–5678 (2011).

    CAS  Google Scholar 

  36. Kajikawa, Y. Analysis of high-temperature thermoelectric properties of p-type CoSb3 within a two-valence-band and two-conduction-band model. J. Appl. Phys. 115, 203716 (2014).

    Google Scholar 

  37. Julian, C. L. Theory of heat conduction in rare-gas crystals. Phys. Rev. 137, A128–A137 (1965).

    Google Scholar 

  38. Dho, J., Lee, E. K., Park, J. Y. & Hur, N. H. Effects of the grain boundary on the coercivity of barium ferrite BaFe12O19 . J. Magn. Magn. Mater. 285, 164–168 (2005).

    CAS  Google Scholar 

  39. Chen, L. D. et al. Anomalous barium filling fraction and n-type thermoelectric performance of BayCo4Sb12 . J. Appl. Phys. 90, 1864–1868 (2001).

    CAS  Google Scholar 

  40. Fonda, E. et al. Negative differential magnetization for Ni nanoparticles in Al. Phys. Rev. B 71, 184411 (2005).

    Google Scholar 

  41. Costache, M. V., Bridoux, G., Neumann, I. & Valenzuela, S. O. Magnon-drag thermopile. Nat. Mater. 11, 199–202 (2012).

    CAS  Google Scholar 

  42. Grannemann, G. N. & Berger, L. Magnon-drag Peltier effect in a Ni-Cu alloy. Phys. Rev. B 13, 2072–2079 (1976).

    CAS  Google Scholar 

  43. Morin, F. J. & Maita, J. P. Conductivity and Hall effect in the intrinsic range of germanium. Phys. Rev. 94, 1525–1529 (1954).

    CAS  Google Scholar 

  44. Zhao, W. Y. et al. Synthesis and high temperature transport properties of barium and indium double-filled skutterudites BaxInyCo4Sb12−z . J. Appl. Phys. 102, 113708 (2007).

    Google Scholar 

  45. Dyck, J. S. et al. Thermoelectric properties of the n-type filled skutterudite Ba0.3Co4Sb12 doped with Ni. J. Appl. Phys. 91, 3698–3705 (2002).

    CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by the National Natural Science Foundation of China (nos. 51620105014, 11274248, 51572210 and 51521001), the National Basic Research Program of China (973 Program) no. 2013CB632505. XRD, DSC, FESEM, HRTEM and EPMA experiments were performed at the Center for Materials Research and Testing of Wuhan University of Technology. Hall measurements were performed at the State Key Lab of Advanced Technology for Materials Synthesis and Processing of Wuhan University of Technology. X-ray photoemission spectra were recorded at the Key Laboratory of Catalysis and Materials Science of the State Ethnic Affair Commission & Ministry of Education of South-Central University for Nationalities. The measurements of static magnetic properties and low-temperature α were performed at the School of Physics and Technology of Wuhan University. The Curie temperature was measured at the Institute of Physics, Chinese Academy of Sciences. The authors thank S.B. Mu, W.Y. Chen, M.J. Yang, X.L. Nie, C.H. Shen, X.Q. Liu and Y.Y. Qi for their help with structure characterization, K. Jin, X.L. Dong, J. Yuan and Y.L. Huang for help with measuring the Curie temperature of BaM-NPs. The authors also thank S.Q. Xia and X.Y. Zhou for help with the high-temperature Hall measurements, and H.J. Liu for discussions on the role of BaM-NPs in adjusting TE properties.

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Authors and Affiliations

  1. State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan, 430070, China

    Wenyu Zhao, Zhiyuan Liu, Ping Wei, Qingjie Zhang, Wanting Zhu, Xianli Su & Xinfeng Tang

  2. Department of Materials Science and Engineering, University of Washington, Seattle, 98195, Washington, USA

    Jihui Yang

  3. School of Physics and Technology, Wuhan University, Wuhan, 430072, China

    Yong Liu & Jing Shi

  4. Energy Materials Laboratory, School of Chemistry, University of East Anglia, Norwich Research Park, Norwich, NR4 7TJ, UK

    Yimin Chao

  5. School of Materials Science and Engineering, Tongji University, Shanghai, 200092, China

    Siqi Lin & Yanzhong Pei

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Contributions

W.-Y.Z. and Q.Z. designed a magnetic nanocomposite thermoelectric material for this work. Z.L. synthesized the samples. Z.L., X.S., X.T., Y.C., S.L. and Y.P. carried out the thermoelectric properties and Hall measurements. Z.L., W.-T.Z. and Y.L. performed the electron microscopy analysis and XPS experiments. W.-Y.Z., P.W. and J.S. performed the magnetic measurements. W.-Y.Z., Z.L., Q.Z. and J.Y. conceived the experiments, analysed the results and wrote the manuscript. All authors discussed the results and commented on the manuscript.

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Correspondence to Qingjie Zhang or Jihui Yang.

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Zhao, W., Liu, Z., Wei, P. et al. Magnetoelectric interaction and transport behaviours in magnetic nanocomposite thermoelectric materials. Nature Nanotech 12, 55–60 (2017). https://doi.org/10.1038/nnano.2016.182

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