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A 5 × 5 cm2 protonic ceramic fuel cell with a power density of 1.3 W cm–2 at 600 °C

Nature Energy volume 3, pages 870–875 (2018)Cite this article

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Abstract

In spite of various advantages of protonic ceramic fuel cells over conventional fuel cells, distinct scepticism currently remains about their applicability because of lower-than-predicted performance and difficulty with scale-up. These challenges mainly stem from the refractory nature of proton-conducting ceramic electrolytes and the low chemical stability of these materials during the sintering process. Here, we present the fabrication of a physically thin, structurally dense and chemically homogeneous electrolyte, BaCe0.55Zr0.3Y0.15O3-δ (BCZY3), through a facile anode-assisted densification of the electrolyte on a structurally and compositionally uniform anode support, which resulted in breakthroughs in performance and scalability. A BCZY3-based protonic ceramic fuel cell with a size of 5 × 5 cm2 exhibits an area-specific ohmic resistance of 0.09 Ω cm2 and delivers a power as high as 20.8 W per single cell at 600 °C.

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Fig. 1: Anode-assisted densification of electrolyte.
Fig. 2: Fabrication of flat PCFC cell with a dense electrolyte 5 μm thick.
Fig. 3: Electrochemical properties of PCFC cells with a size of 5 × 5 cm2 at various temperatures.
Fig. 4: Results of TEM and EDS analyses.

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References

  1. Steele, B. C. & Heinzel, A. Materials for fuel-cell technologies. Nature 414, 345–352 (2001).

    Google Scholar 

  2. Iwahara, H. Proton conducting ceramics and their applications. Solid State Ionics 86–88, 9–15 (1996).

    Article  Google Scholar 

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

    Article  Google Scholar 

  4. Medvedev, D. A., Lyagaeva, J. G., Gorbova, E. V., Demin, A. K. & Tsiakaras, P. Advanced materials for SOFC application: strategies for the development of highly conductive and stable solid oxide proton electrolytes. Prog. Mater. Sci. 75, 38–79 (2016).

    Article  Google Scholar 

  5. Medvedev, D., Brouzgou, A., Demin, A., Tsiakaras, P. in Advances in Medium and High Temperature Solid Oxide Fuel Cell Technology (eds Boaro, M. & Aricò, A. S.) 77–118 (Springer, Berlin, 2016).

  6. Duan, C. et al. Readily processed protonic ceramic fuel cells with high performance at low temperatures. Science 349, 1321–1326 (2015).

    Article  Google Scholar 

  7. Contini, V. et al. Stationary and Emerging Market Fuel Cell System Cost Assessment DOE Hydrogen and Fuel Cells Program (Battelle Memorial Institute, 2017).

  8. Dubois, A., Ricote, S. & Braun, R. J. Benchmarking the expected stack manufacturing cost of next generation, intermediate-temperature protonic ceramic fuel cells with solid oxide fuel cell technology. J. Power Sources 369, 65–77 (2017).

    Article  Google Scholar 

  9. Coors, W. G. Protonic ceramic fuel cells for high-efficiency operation with methane. J. Power Sources 118, 150–156 (2003).

    Article  Google Scholar 

  10. Kim, J. et al. Triple‐conducting layered perovskites as cathode materials for proton‐conducting solid oxide fuel cells. ChemSusChem 7, 2811–2815 (2014).

    Article  Google Scholar 

  11. Ling, Y., Yu, J., Zhang, X., Zhao, L. & Liu, X. A cobalt-free Sm0.5Sr0.5Fe0.8Cu 0.2O3-δ–Ce0.8Sm0.2O2-δ composite cathode for proton-conducting solid oxide fuel cells. J. Power Sources 196, 2631–2634 (2011).

    Article  Google Scholar 

  12. Bi, L., Fabbri, E., Sun, Z. & Traversa, E. A novel ionic diffusion strategy to fabricate high-performance anode-supported solid oxide fuel cells (SOFCs) with proton-conducting Y-doped BaZrO3 films. Energ. Env. Sci. 4, 409–412 (2011).

    Article  Google Scholar 

  13. Guo, Y., Lin, Y., Ran, R. & Shao, Z. Zirconium doping effect on the performance of proton-conducting BaZryCe0.8−yY0.2O3-δ (0.0 ≤ y ≤ 0.8) for fuel cell applications. J. Power Sources 193, 400–407 (2009).

    Article  Google Scholar 

  14. Nguyen, N. T. Q. & Yoon, H. H. Preparation and evaluation of BaZr0.1Ce0.7Y0.1Yb0.1O3-δ (BZCYYb) electrolyte and BZCYYb-based solid oxide fuel cells. J. Power Sources 231, 213–218 (2013).

    Article  Google Scholar 

  15. Nien, S., Hsu, C., Chang, C. & Hwang, B. Preparation of BaZr0.1Ce0.7Y0.2O3-δ based solid oxide fuel cells with anode functional layers by tape casting. Fuel Cells 11, 178–183 (2011).

    Article  Google Scholar 

  16. Shi, Z., Sun, W. & Liu, W. Synthesis and characterization of BaZr0.3Ce0.5Y0.2−xYbxO3-δ proton conductor for solid oxide fuel cells. J. Power Sources 245, 953–957 (2014).

    Article  Google Scholar 

  17. Liu, M., Gao, J., Liu, X. & Meng, G. High performance of anode supported BaZr0.1Ce0.7Y0.2O3-δ (BZCY) electrolyte cell for IT-SOFC. Int. J. Hydrogen Energ. 36, 13741–13745 (2011).

    Article  Google Scholar 

  18. Yang, L. et al. Enhanced sulfur and coking tolerance of a mixed ion conductor for SOFCs: BaZr0.1Ce0.7Y0.2–xYbxO3-δ. Science 326, 126–129 (2009).

    Article  Google Scholar 

  19. Sun, W., Shi, Z., Liu, M., Bi, L. & Liu, W. An easily sintered, chemically stable, barium zirconate‐based proton conductor for high‐performance proton‐conducting solid oxide fuel cells. Adv. Funct. Mater. 24, 5695–5702 (2014).

    Article  Google Scholar 

  20. Gorte, R. J. Cooling down ceramic fuel cells. Science 349, 6254 (2015).

    Article  Google Scholar 

  21. Katahira, K., Kohchi, Y., Shimura, T. & Iwahara, H. Protonic conduction in Zr-substituted BaCeO3. Solid State Ionics 138, 91–98 (2000).

    Article  Google Scholar 

  22. Guo, Y., Ran, R., Shao, Z. & Liu, S. Effect of Ba nonstoichiometry on the phase structure, sintering, electrical conductivity and phase stability of Ba1±xCe0.4Zr0.4Y0.2O3-δ (0 ≤ x ≤ 0.20) proton conductors. Int. J. Hydrogen Energ. 36, 8450–8460 (2011).

    Article  Google Scholar 

  23. Wang, H., Peng, R. R., Wu, X. F., Hu, J. L. & Xia, C. R. Sintering behavior and conductivity study of yttrium-doped BaCeO3–BaZrO3 solid solutions using ZnO additives. J. Am. Ceram. Soc. 92, 2623–2629 (2009).

    Article  Google Scholar 

  24. Han, D. et al. Origins of structural and electrochemical influence on Y-doped BaZrO3 heat-treated with NiO additive. J. Mater. Chem. A 2, 12552–12560 (2014).

    Article  Google Scholar 

  25. German, R., Suri, P. & Park, S. Review: liquid phase sintering. J. Mater. Sci. 44, 1–39 (2009).

    Article  Google Scholar 

  26. Guo, Y. M., Ran, R. & Shao, Z. P. A novel way to improve performance of proton-conducting solid-oxide fuel cells through enhanced chemical interaction of anode components. Int. J. Hydrogen Energ. 36, 1683–1691 (2011).

    Article  Google Scholar 

  27. Yoo, Y. & Lim, N. Performance and stability of proton conducting solid oxide fuel cells based on yttrium-doped barium cerate–zirconate thin-film electrolyte. J. Power Sources 229, 48–57 (2013).

    Article  Google Scholar 

  28. Ricote, S., Bonanos, N., Manerbino, A. & Coors, W. Conductivity study of dense BaCexZr(0.9−x)Y0.1O(3-δ) prepared by solid state reactive sintering at 1500 ℃. Int. J. Hydrogen Energ. 37, 7954–7961 (2012).

    Article  Google Scholar 

  29. Liu, Y., Yang, L., Liu, M., Tang, Z. & Liu, M. Enhanced sinterability of BaZr0.1Ce0.7Y0.1Yb0.1O3-δ by addition of nickel oxide. J. Power Sources 196, 9980–9984 (2011).

    Article  Google Scholar 

  30. Tong, J. H., Clark, D., Bernau, L., Sanders, M. & O’Hayre, R. Solid-state reactive sintering mechanism for large-grained yttrium-doped barium zirconate proton conducting ceramics. J. Mater. Chem. 20, 6333–6341 (2010).

    Article  Google Scholar 

  31. Von Dollen, P. & Barnett, S. A study of screen printed yttria-stabilized zirconia layers for solid oxide fuel cells. J. Am. Ceram. Soc. 88, 3361–3368 (2005).

    Article  Google Scholar 

  32. Reed, J. S. Principles of Ceramics Processing (Wiley-Interscience, Hoboken, 1995).

  33. Shao, Z. & Haile, S. M. A high-performance cathode for the next generation of solid-oxide fuel cells. Nature 431, 170–173 (2004).

    Article  Google Scholar 

  34. Grimaud, A. et al. Hydration properties and rate determining steps of the oxygen reduction reaction of perovskite-related oxides as H+-SOFC cathodes. J. Electrochem. Soc. 159, B683–B694 (2012).

    Article  Google Scholar 

  35. Lin, Y. et al. Evaluation of Ba0.5Sr0.5Co0.8Fe0.2O3-δ as a potential cathode for an anode-supported proton-conducting solid-oxide fuel cell. J. Power Sources 180, 15–22 (2008).

    Article  Google Scholar 

  36. Marrony, M. & Dailly, J. Advanced proton conducting ceramic cell as energy storage device. J. Electrochem. Soc. 164, F988–F994 (2017).

    Article  Google Scholar 

  37. Hilpert, K., Das, D., Miller, M., Peck, D. H. & Weiβ, R. Chromium vapor species over solid oxide fuel cell interconnect materials and their potential for degradation processes. J. Electrochem. Soc. 143, 3642–3647 (1996).

    Article  Google Scholar 

  38. Kim, Y., Chen, X., Jiang, S. P. & Bae, J. Effect of strontium content on chromium deposition and poisoning in Ba1–xSrxCo0.8Fe0.2O3-δ (0.3 ≤ x ≤ 0.7) cathodes of solid oxide fuel cells. J. Electrochem. Soc. 159, B185–B194 (2012).

    Article  Google Scholar 

  39. Yan, A. et al. A temperature programmed desorption investigation on the interaction of Ba0.5Sr0.5Co0.8Fe0.2O3-δ perovskite oxides with CO2 in the absence and presence of H2O and O2. Appl. Catal. B 80, 24–31 (2008).

    Article  Google Scholar 

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Acknowledgements

This work was supported by Technology Development Program to Solve Climate Changes through the National Research Foundation of Korea funded by the Ministry of Science, ICT & Future Planning (2017M1A2A2044982). H.A. thanks the Manpower Development Program for Energy supported by the Ministry of Knowledge and Economy.

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Authors and Affiliations

  1. High-temperature Energy Materials Research Center, Korea Institute of Science and Technology, Seoul, Republic of Korea

    Hyegsoon An, Hae-Weon Lee, Byung-Kook Kim, Ji-Won Son, Kyung Joong Yoon, Hyoungchul Kim, Ho-Il Ji & Jong-Ho Lee

  2. Department of Fuel Cells and Hydrogen Technology, Hanyang University, Seoul, Republic of Korea

    Hyegsoon An & Dongwook Shin

  3. Nanomaterials Science and Engineering, Korea University of Science and Technology (UST), KIST Campus, Seoul, Republic of Korea

    Ji-Won Son & Jong-Ho Lee

  4. Division of Materials Science and Engineering, Hanyang University, Seoul, Republic of Korea

    Dongwook Shin

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Contributions

H.A. conceived the experiments and analyses. H.-W.L. developed the bilayer fabrication process. B.-K.K. provided suggestions for the cathode preparation. J.-W.S. and K.J.Y. analysed the electrochemical data. H.K. built the test stations. D.S., H.-I.J. and J.-H.L. supervised the research. H.A., H.-I.J. and J.-H.L. prepared and edited the manuscript with input from all the authors.

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Correspondence to Dongwook Shin, Ho-Il Ji or Jong-Ho Lee.

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Supplementary Tables 1–2, Supplementary Figures 1–19

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An, H., Lee, HW., Kim, BK. et al. A 5 × 5 cm2 protonic ceramic fuel cell with a power density of 1.3 W cm–2 at 600 °C. Nat Energy 3, 870–875 (2018). https://doi.org/10.1038/s41560-018-0230-0

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