Highly efficient reversible protonic ceramic electrochemical cells for power generation and fuel production

Abstract

Reversible fuel cells based on both proton exchange membrane fuel cell and solid oxide fuel cell technologies have been proposed to address energy storage and conversion challenges and to provide versatile pathways for renewable fuels production. Both technologies suffer challenges associated with cost, durability, low round-trip efficiency and the need to separate H2O from the product fuel. Here, we present a reversible protonic ceramic electrochemical cell based on an yttrium and ytterbium co-doped barium cerate–zirconate electrolyte and a triple-conducting oxide air/steam (reversible) electrode that addresses many of these issues. Our reversible protonic ceramic electrochemical cell achieves a high Faradaic efficiency (90–98%) and can operate endothermically with a >97% overall electric-to-hydrogen energy conversion efficiency (based on the lower heating value of H2) at a current density of −1,000 mA cm−2. Even higher efficiencies are obtained for H2O electrolysis with co-fed CO2 to produce CO and CH4. We demonstrate a repeatable round-trip (electricity-to-hydrogen-to-electricity) efficiency of >75% and stable operation, with a degradation rate of <30 mV over 1,000 h.

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Fig. 1: Schematic of RePCECs and comparison with low-temperature proton exchange membrane electrolysis cells, intermediate-temperature solid oxide electrolysis cells and high-temperature solid oxide electrolysis cells.
Fig. 2: Model prediction of BZY20- and BCZYYb-based RePCEC performance.
Fig. 3: Experimental evaluation of BZY20- and BCZYYb-based RePCECs.
Fig. 4: Performance of a BCZYYb-based electrolyser (cell no. 14) under various steam concentrations at 600 °C.
Fig. 5: Electrochemical conversion of both CO2 and H2O in PCEC.
Fig. 6: Long-term stability testing of BCZYYb-based RePCECs in PCEC mode and under reversible cyclic operation.
Fig. 7: SEM images of cell no. 7 after 600 h operation.
Fig. 8: Long-term stability testing of BCZYYb-based RePCECs under reversible cyclic operation.

Data availability

The data that support the findings of this study are available from the corresponding authors on reasonable request. See Author contributions for specific datasets.

Change history

  • 22 July 2020

    An amendment to this paper has been published and can be accessed via a link at the top of the paper.

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Acknowledgements

This work was supported by the Advanced Research Projects Agency–Energy (ARPA-E) through the REFUEL (award DE-AR0000808) and REBELS programmes (award DE-AR0000493). Additional support was provided by the Army Research Office under grant number W911NF-17-1-0051, the Office of Naval Research via grant N00014-16-1-2780, the National Science Foundation via grant DMR156375, the Colorado School of Mines Foundation via the Angel Research Fund and the Colorado Office of Economic Development and International Trade (COEDIT) under their Advanced Industries Proof-of-Concept Grant programme. The views and conclusions contained in this document are those of the authors and should not be interpreted as representing the official policies, either expressed or implied, of ARPA-E, the Department of Energy, the Army Research Office or the US Government.

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C.D. and R.O. developed the intellectual concept, designed the experiments, analysed the data and led the manuscript writing. H.Z. and R.K. developed the PCFC and PCEC model comparisons and contributed to the discussion and analysis. D.J. performed the transmission electron microscopy. N.S., L.Z. and L.B. provided suggestions on the experiments, data interpretation and manuscript refinement.

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Correspondence to Chuancheng Duan or Ryan O’Hayre.

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Supplementary Figures 1–16, Supplementary Note 1, Supplementary Tables 1–5, Supplementary references.

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Duan, C., Kee, R., Zhu, H. et al. Highly efficient reversible protonic ceramic electrochemical cells for power generation and fuel production. Nat Energy 4, 230–240 (2019). https://doi.org/10.1038/s41560-019-0333-2

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