Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Article
  • Published:

Large electrocaloric effects in oxide multilayer capacitors over a wide temperature range

Abstract

Heat pumps based on magnetocaloric and electrocaloric working bodies—in which entropic phase transitions are driven by changes of magnetic and electric field, respectively—use displaceable fluids to establish relatively large temperature spans between loads to be cooled and heat sinks1,2. However, the performance of prototypes is limited because practical magnetocaloric working bodies driven by permanent magnets3,4,5 and electrocaloric working bodies driven by voltage6,7,8,9,10,11,12,13,14,15,16 display temperature changes of less than 3 kelvin. Here we show that high-quality multilayer capacitors of PbSc0.5Ta0.5O3 display large electrocaloric effects over a wide range of starting temperatures when the first-order ferroelectric phase transition is driven supercritically (as verified by Landau theory) above the Curie temperature of 290 kelvin by electric fields of 29.0 volts per micrometre. Changes of temperature in the large central area of the capacitor peak at 5.5 kelvin near room temperature and exceed 3 kelvin for starting temperatures that span 176 kelvin (complete thermalization would reduce these values from 5.5 to 3.3 kelvin and from 176 to 73 kelvin). If magnetocaloric working bodies were to be replaced with multilayer capacitors of PbSc0.5Ta0.5O3, then the established design principles behind magnetocaloric heat pumps could be repurposed for better performance without bulky and expensive permanent magnets.

This is a preview of subscription content, access via your institution

Access options

Rent or buy this article

Prices vary by article type

from$1.95

to$39.95

Prices may be subject to local taxes which are calculated during checkout

Fig. 1: MLC structure.
Fig. 2: Indirect EC measurements.
Fig. 3: Direct EC measurements.
Fig. 4: Large EC effects over a wide range of operating temperatures.

Similar content being viewed by others

Data availability

Source data for Figs. 24 are provided with the paper. All other relevant data are available within the paper and its Supplementary Information files.

References

  1. Brown, G. V. Magnetic heat pumping near room temperature. J. Appl. Phys. 47, 3673–3680 (1976).

    Article  ADS  CAS  Google Scholar 

  2. Moya, X., Kar-Narayan, S. & Mathur, N. D. Caloric materials near ferroic phase transitions. Nat. Mater. 13, 439–450 (2014).

    Article  ADS  CAS  Google Scholar 

  3. Yu, B., Liu, M., Egolf, P. W. & Kitanovski, A. A review of magnetic refrigerator and heat pump prototypes built before the year 2010. Int. J. Refrig. 33, 1029–1060 (2010).

    Article  CAS  Google Scholar 

  4. Bjørk, R., Bahl, C. R. H. & Nielsen, K. K. The lifetime cost of a magnetic refrigerator. Int. J. Refrig. 63, 48–62 (2016).

    Article  Google Scholar 

  5. Tura, A. & Rowe, A. Concentric Halbach cylinder magnetic refrigerator cost optimization. Int. J. Refrig. 37, 106–116 (2014).

    Article  Google Scholar 

  6. Sinyavsky, Y. V., Pashkov, N. D., Gorovoy, Y. M., Lugansky, G. E. & Shebanov, L. The optical ferroelectric ceramic as working body for electrocaloric refrigeration. Ferroelectrics 90, 213–217 (1989).

    Article  Google Scholar 

  7. Sinyavsky, Y. & Brodyansky, V. M. Experimental testing of electrocaloric cooling with transparent ferroelectric ceramic as working body. Ferroelectrics 131, 321–325 (1992).

    Article  CAS  Google Scholar 

  8. Sinyavskii, Y. V. Electrocaloric refrigerators: a promising alternative to current low-temperature apparatus. Chem. Petrol. Eng. 31, 295–306 (1995).

    Article  Google Scholar 

  9. Gu, H. et al. A chip scale electrocaloric effect based cooling device. Appl. Phys. Lett. 102, 122904 (2013).

    Article  ADS  Google Scholar 

  10. Plaznik, U. et al. Bulk relaxor ferroelectric ceramics as a working body for an electrocaloric cooling device. Appl. Phys. Lett. 106, 043903 (2015).

    Article  ADS  Google Scholar 

  11. Wang, Y. D. et al. A heat-switch-based electrocaloric cooler. Appl. Phys. Lett. 107, 134103 (2015).

    Article  ADS  Google Scholar 

  12. Sette, D. et al. Electrocaloric cooler combining ceramic multi-layer capacitors and fluid. APL Mater. 4, 091101 (2016).

    Article  ADS  Google Scholar 

  13. Blumenthal, P., Molin, C., Gebhardt, S. & Raatz, A. Active electrocaloric demonstrator for direct comparison of PMN-PT bulk and multilayer samples. Ferroelectrics 497, 1–8 (2016).

    Article  CAS  Google Scholar 

  14. Zhang, T., Qian, X.-S., Gu, H., Hou, Y. & Zhang, Q. M. An electrocaloric refrigerator with direct solid to solid regeneration. Appl. Phys. Lett. 110, 243503 (2017).

    Article  ADS  Google Scholar 

  15. Ma, R. et al. Highly efficient electrocaloric cooling with electrostatic actuation. Science 357, 1130–1134 (2017).

    Article  ADS  CAS  Google Scholar 

  16. Defay, E. et al. Enhanced electrocaloric efficiency via energy recovery. Nat. Commun. 9, 1827 (2018).

    Article  ADS  CAS  Google Scholar 

  17. Qian, S. et al. Performance enhancement of a compressive thermoelastic cooling system using multi-objective optimization and novel designs. Int. J. Refrig. 57, 62–76 (2015).

    Article  Google Scholar 

  18. Lloveras, P. et al. Colossal barocaloric effects near room temperature in plastic crystals of neopentylglycol. Nat. Commun. 10, 1803 (2019).

    Article  ADS  CAS  Google Scholar 

  19. Crossley, S., Nair, B., Whatmore, R. W., Moya, X. & Mathur, N. D. Electrocaloric cooling cycles in lead scandium tantalate with true regeneration via field variation. Phys. Rev. X 9, 041002 (2019).

    Google Scholar 

  20. Crossley, S. et al. Direct electrocaloric measurement of 0.9Pb(Mg1/3Nb2/3)O3–0.1PbTiO3 films using scanning thermal microscopy. Appl. Phys. Lett. 108, 032902 (2016).

    Article  ADS  Google Scholar 

  21. Kar-Narayan, S. & Mathur, N. D. Predicted cooling powers for multilayer capacitors based on various electrocaloric and electrode materials. Appl. Phys. Lett. 95, 242903 (2009).

    Article  ADS  Google Scholar 

  22. Usui, T. et al. Effect of inactive volume on thermocouple measurements of electrocaloric temperature change in multilayer capacitors of 0.9Pb(Mg1/3Nb2/3)O3–0.1PbTiO3. J. Phys. D 50, 424002 (2017).

    Article  Google Scholar 

  23. Shebanovs, L., Sternberg, A., Lawless, W. N. & Borman, K. Isomorphous ion substitutions and order–disorder phenomena in highly electrocaloric lead-scandium tantalate solid solutions. Ferroelectrics 184, 239–242 (1996).

    Article  CAS  Google Scholar 

  24. Shebanovs, L., Borman, K., Lawless, W. N. & Kalvane, A. Electrocaloric effect in some perovskite ferroelectric ceramics and multilayer capacitors. Ferroelectrics 273, 137–142 (2002).

    Article  CAS  Google Scholar 

  25. Stenger, C. G. F. & Burggraaf, A. J. Order–disorder reactions in the ferroelectric perovskites Pb(Sc1/2Nb1/2)O3 and Pb(Sc1/2Ta1/2)O3. Phys. Status Solidi A 61, 653–664 (1980).

    Article  ADS  CAS  Google Scholar 

  26. Setter, N. & Cross, L. E. The contribution of structural disorder to diffuse phase transitions in ferroelectrics. J. Mater. Sci. 15, 2478–2482 (1980).

    Article  ADS  CAS  Google Scholar 

  27. Imry, Y. & Wortis, M. Influence of quenched impurities on first-order phase transitions. Phys. Rev. B 19, 3580–3585 (1979).

    Article  ADS  CAS  Google Scholar 

  28. Hirose, S. et al. Progress on electrocaloric multilayer ceramic capacitor development. APL Mater. 4, 064105 (2016).

    Article  ADS  Google Scholar 

  29. Bahl, C. R. H. & Nielsen, K. K. The effect of demagnetization on the magnetocaloric properties of gadolinium. J. Appl. Phys. 105, 013916 (2009).

    Article  ADS  Google Scholar 

  30. Moya, X., Defay, E., Heine, V. & Mathur, N. D. Too cool to work. Nat. Phys. 11, 202–205 (2015).

    Article  CAS  Google Scholar 

  31. Lloveras, P. et al. Giant barocaloric effects at low pressure in ferrielectric ammonium sulphate. Nat. Commun. 6, 8801 (2015).

    Article  ADS  CAS  Google Scholar 

  32. Liu, J., Gottschall, T., Skokov, K. P., Moore, J. D. & Gutfleisch, O. Giant magnetocaloric effect driven by structural transitions. Nat. Mater. 11, 620–626 (2012).

    Article  ADS  CAS  Google Scholar 

  33. Whatmore, R. W. et al. Modified lead scandium tantalate for uncooled LWIR detection and thermal imaging. Proc. 8th IEEE International Symposium on Applications of Ferroelectrics (ISAF), 202–205 (IEEE, 1992).

  34. Crossley, S. Electrocaloric Materials and Devices. PhD thesis, Univ. Cambridge (2013); http://www.repository.cam.ac.uk/handle/1810/245063.

  35. Höhne, G. W. H., Hemminger, W. F. & Flammersheim, H.-J. Differential Scanning Calorimetry, 121–126 (Springer, 2003).

Download references

Acknowledgements

We thank C. Minami, Y. Kojima, N. Furusawa, K. Yamamoto, Y. Inoue and K. Honda for their assistance in fabricating MLCs, and we thank R. Whatmore, À. Torelló and E. Defay for discussions. B.N. is grateful for support from Gates Cambridge, the Winton Programme for the Physics of Sustainability, and Trinity College Cambridge. X.M. is grateful for support from UK EPSRC grant EP/M003752/1, ERC starting grant no. 680032, and the Royal Society. G.G.G.-V. is grateful for support from the Vice-Rectory for Research (project no. B9194) and the Office of International Affairs at the University of Costa Rica, and Churchill College at the University of Cambridge. X.M. and G.G.G.-V. are grateful for support from the Royal Society International Exchanges programme (IES\R3\170025).

Author information

Authors and Affiliations

Authors

Contributions

N.D.M. and X.M. conceived the study and led the project together with B.N. and S.H. T.U. and S.H. were responsible for the fabrication and optimization of the high-quality MLCs. S.C. constructed and commissioned the bespoke apparatus used for electrical and thermal measurements. B.N. performed all of the measurements, except that S.K. performed the X-ray diffraction and obtained the optical images. G.G.G.-V. performed the Landau theory. N.D.M wrote the manuscript and supplementary file, with input and feedback from B.N., X.M., S.H., S.C. and G.G.G.-V.

Corresponding authors

Correspondence to X. Moya, S. Hirose or N. D. Mathur.

Ethics declarations

Competing interests

The authors declare no competing interests.

Additional information

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Peer review information Nature thanks Brahim Dkhil, Bai-Xiang Xu and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

Supplementary information

Supplementary Information

.This file contains Supplementary Notes 1-17 and References

Source data

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Nair, B., Usui, T., Crossley, S. et al. Large electrocaloric effects in oxide multilayer capacitors over a wide temperature range. Nature 575, 468–472 (2019). https://doi.org/10.1038/s41586-019-1634-0

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41586-019-1634-0

This article is cited by

Comments

By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.

Search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing