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:

Photo-enhanced ionic conductivity across grain boundaries in polycrystalline ceramics

Nature Materials volume 21, pages 438–444 (2022)Cite this article

Subjects

This article has been updated

Abstract

Grain boundary conductivity limitations are ubiquitous in material science. We show that illumination with above-bandgap light can decrease the grain boundary resistance in solid ionic conductors. Specifically, we demonstrate the increase of the grain boundary conductance of a 3 mol% Gd-doped ceria thin film by a factor of approximately 3.5 at 250 °C and the reduction of its activation energy from 1.12 to 0.68 eV under illumination, while light-induced heating and electronic conductivity could be excluded as potential sources for the observed opto-ionic effect. The presented model predicts that photo-generated electrons decrease the potential barrier heights associated with space charge zones depleted in charge carriers between adjacent grains. The discovered opto-ionic effect could pave the way for the development of new electrochemical storage and conversion technologies operating at lower temperatures and/or higher efficiencies and could be further used for fast and contactless control or diagnosis of ionic conduction in polycrystalline solids.

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

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

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

Fig. 1: General grain boundary characteristics and the impact of UV illumination.
Fig. 2: Temperature dependance of the opto-ionic effect.
Fig. 3: SFITs in light and dark phases.
Fig. 4: Frequency-dependent optical modulation of resistance response by IMPS.
Fig. 5: Suggested mechanism of the opto-ionic effect and the consequences for potential distribution and charge carrier concentrations.

Similar content being viewed by others

Data availability

Source data are provided with this paper. Source data for Figs. 1–4 and Supplementary Figs. 9–11 are available from the online data repository Figshare with identifier https://doi.org/10.6084/m9.figshare.c.5707109.v4. Remaining data that support the findings of this study are available from the corresponding authors upon reasonable request.

Change history

  • 03 March 2022

    In the version of this article initially published, the address for IREC was imprecisely written and has now been updated in the HTML and PDF versions of the article.

References

  1. Kreuer, K. D. Proton conducting oxides. Annu. Rev. Mater. Res. 33, 333–359 (2003).

    Article  CAS  Google Scholar 

  2. Tuller, H. L. & Nowick, A. S. Doped ceria as a solid oxide electrolyte. J. Electrochem. Soc. 122, 255–259 (1975).

    Article  CAS  Google Scholar 

  3. Skinner, S. J. & Kilner, J. A. Oxygen ion conductors. Mater. Today 6, 30–37 (2003).

    Article  CAS  Google Scholar 

  4. Hu, Y.-S. Batteries: getting solid. Nat. Energy 1, 16042 (2016).

    Article  CAS  Google Scholar 

  5. Garbayo, I. et al. Glass-type polyamorphism in Li-garnet thin film solid state battery conductors. Adv. Energy Mater. 8, 1702265 (2018).

    Article  Google Scholar 

  6. Pfenninger, R., Struzik, M., Garbayo, I., Stilp, E. & Rupp, J. L. M. A low ride on processing temperature for fast lithium conduction in garnet solid-state battery films. Nat. Energy 4, 475–483 (2019).

    Article  CAS  Google Scholar 

  7. Whittingham, M. S. Lithium batteries and cathode materials. Chem. Rev. 104, 4271–4301 (2004).

    Article  CAS  Google Scholar 

  8. Pagani, F. et al. Epitaxial thin films as a model system for Li-ion conductivity in Li4Ti5O12. ACS Appl. Mater. Interfaces 10, 44494–44500 (2018).

    Article  CAS  Google Scholar 

  9. Janek, J. & Zeier, W. G. A solid future for battery development. Nat. Energy 1, 16141 (2016).

    Article  Google Scholar 

  10. Brett, D. J. L., Atkinson, A., Brandon, N. P. & Skinner, S. J. Intermediate temperature solid oxide fuel cells. Chem. Soc. Rev. 37, 1568–1578 (2008).

    Article  CAS  Google Scholar 

  11. Adler, S. B. Factors governing oxygen reduction in solid oxide fuel cell cathodes. Chem. Rev. 104, 4791–4843 (2004).

    Article  CAS  Google Scholar 

  12. Gao, Z., Mogni, L. V., Miller, E. C., Railsback, J. G. & Barnett, S. A. A perspective on low-temperature solid oxide fuel cells. Energy Environ. Sci. 9, 1602–1644 (2016).

    Article  CAS  Google Scholar 

  13. Mai, A., Haanappel, V. A. C., Uhlenbruck, S., Tietz, F. & Stöver, D. Ferrite-based perovskites as cathode materials for anode-supported solid oxide fuel cells. Part I. Variation of composition. Solid State Ion. 176, 1341–1350 (2005).

    Article  CAS  Google Scholar 

  14. Takamura, H., Okumura, K., Koshino, Y., Kamegawa, A. & Okada, M. Oxygen permeation properties of ceria-ferrite-based composites. J. Electroceram. 13, 613–618 (2004).

    Article  CAS  Google Scholar 

  15. Meng, Y. et al. Review: recent progress in low-temperature proton-conducting ceramics. J. Mater. Sci. 54, 9291–9312 (2019).

    Article  CAS  Google Scholar 

  16. Knauth, P. Inorganic solid Li ion conductors: an overview. Solid State Ion. 180, 911–916 (2009).

    Article  CAS  Google Scholar 

  17. Kerman, K., Luntz, A., Viswanathan, V., Chiang, Y.-M. & Chen, Z. Review—practical challenges hindering the development of solid state Li ion batteries. J. Electrochem. Soc. 164, A1731–A1744 (2017).

    Article  CAS  Google Scholar 

  18. Rahaman, M. N. Ceramic Processing and Sintering 2nd edn (CRC Press, 2003).

  19. Pergolesi, D. et al. High proton conduction in grain-boundary-free yttrium-doped barium zirconate films grown by pulsed laser deposition. Nat. Mater. 9, 846–852 (2010).

    Article  CAS  Google Scholar 

  20. Gregori, G., Merkle, R. & Maier, J. Ion conduction and redistribution at grain boundaries in oxide systems. Prog. Mater. Sci. 89, 252–305 (2017).

    Article  CAS  Google Scholar 

  21. Kim, S., Kim, S. K., Khodorov, S., Maier, J. & Lubomirsky, I. On determining the height of the potential barrier at grain boundaries in ion conducting oxide. Phys. Chem. Chem. Phys. 18, 3023–3031 (2016).

    Article  CAS  Google Scholar 

  22. Kim, S. & Maier, J. On the conductivity mechanism of nanocrystalline ceria. J. Electrochem. Soc. 149, J73 (2002).

    Article  CAS  Google Scholar 

  23. Wu, J. F. & Guo, X. Origin of the low grain boundary conductivity in lithium ion conducting perovskites: Li3xLa0.67–xTiO3. Phys. Chem. Chem. Phys. 19, 5880–5887 (2017).

    Article  CAS  Google Scholar 

  24. Ma, C. et al. Atomic-scale origin of the large grain-boundary resistance in perovskite Li-ion conducting solid electrolytes. Energy Environ. Sci. 7, 1638–1642 (2014).

    Article  CAS  Google Scholar 

  25. Aguesse, F., López Del Amo, J. M., Roddatis, V., Aguadero, A. & Kilner, J. A. Enhancement of the grain boundary conductivity in ceramic Li0.34La0.55TiO3 electrolytes in a moisture-free processing environment. Adv. Mater. Interfaces 1, 1300143 (2014).

    Article  Google Scholar 

  26. Mei, A. et al. Role of amorphous boundary layer in enhancing ionic conductivity of lithium–lanthanum–titanate electrolyte. Electrochim. Acta 55, 2958–2963 (2010).

    Article  CAS  Google Scholar 

  27. García-Martín, S., Amador, U., Morata-Orrantia, A., Rodríguez-Carvajal, J. & Alario-Franco, M. Á. Structure, microstructure, composition and properties of lanthanum lithium titanates and some substituted analogues. Z. fur Anorg. und Allg. Chem. 635, 2363–2373 (2009).

    Google Scholar 

  28. Joshi, D. P. & Bhatt, D. P. Theory of grain boundary recombination and carrier transport in polycrystalline silicon under optical illumination. IEEE Trans. Electron Devices 37, 237–249 (1990).

    Article  CAS  Google Scholar 

  29. Fergus, J. W. Electrolytes for solid oxide fuel cells. J. Power Sources 162, 30–40 (2006).

    Article  CAS  Google Scholar 

  30. Schmitt, R. et al. A review of defect structure and chemistry in ceria and its solid solutions. Chem. Soc. Rev. 49, 554–592 (2020).

    Article  CAS  Google Scholar 

  31. Avila-Paredes, H. J., Choi, K., Chen, C. T. & Kim, S. Dopant-concentration dependence of grain-boundary conductivity in ceria: a space-charge analysis. J. Mater. Chem. 19, 4837–4842 (2009).

    Article  CAS  Google Scholar 

  32. Göbel, M. C., Gregori, G., Guo, X. & Maier, J. Boundary effects on the electrical conductivity of pure and doped cerium oxide thin films. Phys. Chem. Chem. Phys. 12, 14351–14361 (2010).

    Article  Google Scholar 

  33. Gerstl, M. et al. The separation of grain and grain boundary impedance in thin yttria stabilized zirconia (YSZ) layers. Solid State Ion. 185, 32–41 (2011).

    Article  CAS  Google Scholar 

  34. Peter, L. M. Dynamic aspects of semiconductor photoelectrochemistry. Chem. Rev. 90, 753–769 (1990).

    Article  CAS  Google Scholar 

  35. Klotz, D., Ellis, D. S., Dotan, H. & Rothschild, A. Empirical in operando analysis of the charge carrier dynamics in hematite photoanodes by PEIS, IMPS and IMVS. Phys. Chem. Chem. Phys. 18, 23438–23457 (2016).

    Article  CAS  Google Scholar 

  36. Harrington, G. F. et al. The interplay and impact of strain and defect association on the conductivity of rare-earth substituted ceria. Acta Mater. 166, 447–458 (2019).

    Article  CAS  Google Scholar 

  37. Seager, C. H. Grain boundary recombination: theory and experiment in silicon. J. Appl. Phys. 52, 3960–3968 (1981).

    Article  CAS  Google Scholar 

  38. De Souza, R. A. Oxygen diffusion in SrTiO3 and related perovskite oxides. Adv. Funct. Mater. 25, 6326–6342 (2015).

    Article  Google Scholar 

  39. Rockenhäuser, C. et al. Microstructure evolution and cation interdiffusion in thin Gd2O3 films on CeO2 substrates. J. Eur. Ceram. Soc. 34, 1235–1242 (2014).

    Article  Google Scholar 

  40. Beschnitt, S., Zacherle, T. & De Souza, R. A. Computational study of cation diffusion in ceria. J. Phys. Chem. C 119, 27307–27315 (2015).

    Article  CAS  Google Scholar 

  41. Jacobsen, T., Chatzichristodoulou, C. & Mogensen, M. B. Fermi potential across working solid oxide cells with zirconia or ceria electrolytes. ECS Trans. 61, 203–214 (2014).

    Article  CAS  Google Scholar 

  42. Gopal, C. B. & Haile, S. M. An electrical conductivity relaxation study of oxygen transport in samarium doped ceria. J. Mater. Chem. A 2, 2405–2417 (2014).

    Article  CAS  Google Scholar 

  43. Dong, Y. & Chen, I. W. Oxygen potential transition in mixed conducting oxide electrolyte. Acta Mater. 156, 399–410 (2018).

    Article  CAS  Google Scholar 

  44. Spiridigliozzi, L. et al. Engineered co-precipitation chemistry with ammonium carbonate for scalable synthesis and sintering of improved Sm0.2Ce0.8O1.90 and Gd0.16Pr0.04Ce0.8O1.90 electrolytes for IT-SOFC. J. Ind. Eng. Chem. 59, 17–27 (2018).

    Article  CAS  Google Scholar 

  45. Sanna, S. et al. Fabrication and electrochemical properties of epitaxial samarium-doped ceria films on SrTiO3-buffered MgO substrates. Adv. Funct. Mater. 19, 1713–1719 (2009).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

We thank G. F. Harrington for the valuable input on sample preparation and characterization and K. May for help with the atomic force microscopy measurements. T.D. and H.L.T. acknowledge support for their research from the US Department of Energy, Basic Energy Sciences under award number DE-SC0002633 (Chemomechanics of Far-From-Equilibrium Interfaces). D.K. acknowledges support by the Japan Society for the Promotion of Science Core-to-Core Program, A. Advanced Research Networks: ‘Solid Oxide Interfaces for Faster Ion Transport’, as well as funding from the Kakenhi Grant-In-Aid for young scientists, grant numbers 18K13993 and 20K15028. D.K. and H.L.T. appreciate preliminary discussions with H. Matsumoto of Kyushu University and T. Lippert and D. Pergolesi of the Paul Scherrer Institute. J.L.M.R., J.C.G.-R. and T.D. acknowledge the Swiss National Science Foundation for grant number BSSGI0_155986/1, and Equinor for grant Agr no. 4502981450. This work made use of the Materials Research Science and Engineering Center Shared Experimental Facilities at the Massachusetts Institute of Technology, supported by the National Science Foundation under award number DMR-14-19807. A portion of this work was performed at the Center for Nanoscale Systems, a member of the National Nanotechnology Coordinated Infrastructure Network, which was supported by the National Science Foundation under National Science Foundation award no. 1541959.

Author information

Author notes

  1. Juan Carlos Gonzalez-Rosillo

    Present address: Catalonia Institute for Energy Research (IREC), Sant Adrià del Besòs (Barcelona), Spain

  2. Jennifer L. M. Rupp

    Present address: Department of Chemistry, Technical University of Munich, München, Germany

  3. These authors contributed equally: Thomas Defferriere, Dino Klotz.

Authors and Affiliations

  1. Department of Material Science and Engineering, MIT, Cambridge, MA, USA

    Thomas Defferriere, Dino Klotz, Juan Carlos Gonzalez-Rosillo, Jennifer L. M. Rupp & Harry L. Tuller

  2. International Institute for Carbon-Neutral Energy Research (I2CNER), Kyushu University, Fukuoka, Japan

    Dino Klotz & Harry L. Tuller

Authors
  1. Thomas Defferriere
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Dino Klotz
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Juan Carlos Gonzalez-Rosillo
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Jennifer L. M. Rupp
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Harry L. Tuller
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

H.L.T. conceived the concept; T.D. and D.K. performed all experiments except the atomic force microscopy and scanning electron microscopy experiments, which were performed by J.C.G.-R.; H.L.T. and J.L.M.R. supervised the work. The manuscript was written by T.D., D.K., J.L.M.R. and H.L.T., and all authors contributed to discussions and editing.

Corresponding authors

Correspondence to Thomas Defferriere, Dino Klotz or Harry L. Tuller.

Ethics declarations

Competing interests

The authors declare no conflict of interest.

Peer review

Peer review information

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

Additional information

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

Extended data

Extended Data Fig. 1 Additional polycrystalline sample measured at low temperatures.

Arrhenius plot of additional sample A1. As guide, the measurements of the epitaxial and polycrystalline samples from the main text are also plotted as full lines in the same color code as in the main text (same Figure appears as Supplementary Fig. S9).

Source data

Supplementary information

Supplementary Information

Supplementary Sections 1–19, Figs. 1–24 and Tables 1–6.

Source data

Source Data Fig. 1

Unprocessed impedance data.

Source Data Fig. 2

Temperature-dependent conductivity (fits of data from Fig. 1).

Source Data Fig. 3

SFITs (unprocessed raw data over time).

Source Data Fig. 4

IMPS (measured raw data and fitted time constant).

Source Data Extended Data Fig. 1

Unprocessed impedance data gathered from additional sample A1.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Defferriere, T., Klotz, D., Gonzalez-Rosillo, J.C. et al. Photo-enhanced ionic conductivity across grain boundaries in polycrystalline ceramics. Nat. Mater. 21, 438–444 (2022). https://doi.org/10.1038/s41563-021-01181-2

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41563-021-01181-2

This article is cited by

Search

Advanced 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