Letter | Published:

Strongly correlated perovskite fuel cells

Nature volume 534, pages 231234 (09 June 2016) | Download Citation


Fuel cells convert chemical energy directly into electrical energy with high efficiencies and environmental benefits, as compared with traditional heat engines1,2,3,4. Yttria-stabilized zirconia is perhaps the material with the most potential as an electrolyte in solid oxide fuel cells (SOFCs), owing to its stability and near-unity ionic transference number5. Although there exist materials with superior ionic conductivity, they are often limited by their ability to suppress electronic leakage when exposed to the reducing environment at the fuel interface. Such electronic leakage reduces fuel cell power output and the associated chemo-mechanical stresses can also lead to catastrophic fracture of electrolyte membranes6. Here we depart from traditional electrolyte design that relies on cation substitution to sustain ionic conduction. Instead, we use a perovskite nickelate as an electrolyte with high initial ionic and electronic conductivity. Since many such oxides are also correlated electron systems, we can suppress the electronic conduction through a filling-controlled Mott transition induced by spontaneous hydrogen incorporation. Using such a nickelate as the electrolyte in free-standing membrane geometry, we demonstrate a low-temperature micro-fabricated SOFC with high performance. The ionic conductivity of the nickelate perovskite is comparable to the best-performing solid electrolytes in the same temperature range, with a very low activation energy. The results present a design strategy for high-performance materials exhibiting emergent properties arising from strong electron correlations.

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  1. 1.

    , , & Fuel Cell Fundamentals (John Wiley & Sons, 2006)

  2. 2.

    Advances in solid oxide fuel cell technology. Solid State Ion. 135, 305–313 (2000)

  3. 3.

    & Lowering the temperature of solid oxide fuel cells. Science 334, 935–939 (2011)

  4. 4.

    et al. A thermally self-sustained micro solid-oxide fuel-cell stack with high power density. Nature 435, 795–798 (2005)

  5. 5.

    Fuel cell materials and components. Acta Mater. 51, 5981–6000 (2003)

  6. 6.

    , & Free standing oxide alloy electrolytes for low temperature thin film solid oxide fuel cells. J. Power Sources 202, 120–125 (2012)

  7. 7.

    Progress in perovskite nickelate research. Phase Transit. 81, 729–749 (2008)

  8. 8.

    Proton conductivity: materials and applications. Chem. Mater. 8, 610–641 (1996)

  9. 9.

    , , & Proton diffusion in perovskites: comparison between BaCeO3, BaZrO3, SrTiO3, and CaTiO3 using quantum molecular dynamics. Solid State Ion. 136/137, 183–189 (2000)

  10. 10.

    , , & A quantum molecular dynamics study of proton conduction phenomena in BaCeO3. Solid State Ion. 86–88, 647–652 (1996)

  11. 11.

    , , & A quantum molecular dynamics study of proton diffusion in SrTiO3 and CaTiO3. Solid State Ion. 125, 39–45 (1999)

  12. 12.

    , & Colossal resistance switching and band gap modulation in a perovskite nickelate by electron doping. Nat. Commun. 5, 4860 (2014)

  13. 13.

    Defect engineering: design tools for solid state electrochemical devices. Electrochim. Acta 48, 2879–2887 (2003)

  14. 14.

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

  15. 15.

    & Effect of interfacial resistance on determination of transport properties of mixed-conducting electrolytes. J. Electrochem. Soc. 143, L109–L112 (1996)

  16. 16.

    , , , & Oxygen ion transference number of doped lanthanum gallate. J. Power Sources 185, 917–921 (2008)

  17. 17.

    & Materials for fuel-cell technologies. Nature 414, 345–352 (2001)

  18. 18.

    , , , & Intermediate temperature solid oxide fuel cells using LaGaO3 electrolyte II. Improvement of oxide ion conductivity and power density by doping Fe for Ga site of LaGaO3. J. Electrochem. Soc. 147, 1332–1337 (2000)

  19. 19.

    & Design of electroceramics for solid oxides fuel cell applications: playing with ceria. J. Am. Ceram. Soc. 91, 1037–1051 (2008)

  20. 20.

    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)

  21. 21.

    , , , & Tailoring the chemical stability of Ba(Ce0.8 − xZrx)Y0.2O3 − δ protonic conductors for intermediate temperature solid oxide fuel cells (IT-SOFCs). Solid State Ion. 179, 558–564 (2008)

  22. 22.

    , , & Solid acids as fuel cell electrolytes. Nature 410, 910–913 (2001)

  23. 23.

    , & Proton conduction in thin film yttrium-doped barium zirconate. Appl. Phys. Lett. 92, 253115 (2008)

  24. 24.

    Structural, magnetic and electronic properties of RNiO3 perovskites (R = rare earth). J. Phys. Condens. Matter 9, 1679 (1997)

  25. 25.

    On the complexity of proton conduction phenomena. Solid State Ion. 136/137, 149–160 (2000)

  26. 26.

    , , & Origins of bad-metal conductivity and the insulator-metal transition in the rare-earth nickelates. Nat. Phys. 10, 304–307 (2014)

  27. 27.

    , , & Analysis of the x-ray-absorption near-edge-structure spectra of La1 − xNdxNiO3 and LaNi1 − xFexO3 perovskites at the nickel K edge. Phys. Rev. B 52, 15823–15828 (1995)

  28. 28.

    et al. Charge disproportionation in RNiO3 perovskites (R = rare earth) from high-resolution x-ray absorption spectroscopy. Phys. Rev. B 80, 245105 (2009)

  29. 29.

    , , , & Nature of hole doping in Nd2NiO4 and La2NiO4: Comparison with La2CuO4. Phys. Rev. B 47, 12365–12368 (1993)

  30. 30.

    , , & In situ x-ray absorption near-edge structure evidence for quadrivalent nickel in nickel battery electrodes. J. Electrochem. Soc. 143, 1613–1617 (1996)

  31. 31.

    & Electronic Properties of Doped Semiconductors Ch. 9/10, 202–250 (Springer, 1984)

  32. 32.

    Electronic and ionic transport properties and other physical aspects of perovskites. Rep. Prog. Phys. 67, 1915 (2004)

  33. 33.

    in EXAFS and Near Edge Structure III Vol. 2 Springer Proceedings in Physics (eds , & ) Ch. 10, 38–42 (Springer, 1984)

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Financial support was provided by the Army Research Office (grants W911NF-14-1-0348 and W911NF-14-1-0669), the Air Force Office of Scientific Research (grant FA9550-12-1-0189), the Advanced Research Projects Agency-Energy (ARPA-E), an IBM PhD Fellowship and the National Academy of Sciences. Part of the work was performed at the Center for Nanoscale Systems at Harvard University. Use of the Advanced Photon Source was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, under contract number DE-AC02-06CH11357. D.D.F. was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Materials Sciences and Engineering Division.

Author information


  1. John A. Paulson School of Engineering and Applied Sciences, Harvard University, Cambridge, Massachusetts 02138, USA

    • You Zhou
    • , Xiaofei Guan
    • , Koushik Ramadoss
    • , Suhare Adam
    • , Jian Shi
    •  & Shriram Ramanathan
  2. X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne, Illinois 60439, USA

    • Hua Zhou
    •  & Sungsik Lee
  3. Materials Science Division, Argonne National Laboratory, Argonne, Illinois 60439, USA

    • Huajun Liu
    •  & Dillon D. Fong
  4. Department of Materials Science and Engineering, Rensselaer Polytechnic Institute, Troy, New York 12180, USA

    • Jian Shi
  5. SiEnergy Systems, Cambridge, Massachusetts 02140, USA

    • Masaru Tsuchiya
  6. School of Materials Engineering, Purdue University, West Lafayette, Indiana 47907, USA

    • Shriram Ramanathan


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Y.Z. and S.R. conceived the study. Y.Z. fabricated the fuel cells and performed the initial tests. X.G. designed and performed the quantitative fuel-cell tests and analysis. Y.Z., H.Z., H.L. and S.L. performed the X-ray absorption spectroscopy measurements. Y.Z. and H.Z. conducted the X-ray diffraction characterizations. K.R. performed the low-temperature electronic transport measurements. S.A. prepared the freestanding Si3N4 membrane. M.T. provided technical advice on the micro-SOFC fabrication and characterization. Y.Z., X.G., J.S. and S.R. wrote the manuscript. All authors discussed the results and commented on the manuscript.

Competing interests

The authors declare no competing financial interests.

Corresponding authors

Correspondence to You Zhou or Shriram Ramanathan.

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