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Reversible redox reactions in an epitaxially stabilized SrCoOx oxygen sponge

Nature Materials volume 12, pages 1057–1063 (2013)Cite this article

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Abstract

Fast, reversible redox reactions in solids at low temperatures without thermomechanical degradation are a promising strategy for enhancing the overall performance and lifetime of many energy materials and devices. However, the robust nature of the cation’s oxidation state and the high thermodynamic barrier have hindered the realization of fast catalysis and bulk diffusion at low temperatures. Here, we report a significant lowering of the redox temperature by epitaxial stabilization of strontium cobaltites (SrCoOx) grown directly as one of two distinct crystalline phases, either the perovskite SrCoO3−δ or the brownmillerite SrCoO2.5. Importantly, these two phases can be reversibly switched at a remarkably reduced temperature (200–300 °C) in a considerably short time (< 1 min) without destroying the parent framework. The fast, low-temperature redox activity in SrCoO3−δ is attributed to a small Gibbs free-energy difference between two topotatic phases. Our findings thus provide useful information for developing highly sensitive electrochemical sensors and low-temperature cathode materials.

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Figure 1: Epitaxial synthesis of two topotatic SrCoOx phases.
Figure 2: Comparison of oxidation states and magnetism.
Figure 3: Magnetic and d.c. transport properties.
Figure 4: Direct probing of reversible redox activity.
Figure 5: Thermodynamic competition.
Figure 6: Gas phase catalysis.

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Acknowledgements

The work was supported by the US Department of Energy, Basic Energy Sciences, Materials Sciences and Engineering Division. The in situ XRD measurement was conducted at the Center for Nanophase Materials Sciences, which is sponsored at Oak Ridge National Laboratory by the Scientific User Facilities Division, Office of Basic Energy Sciences, US Department of Energy. Use of the Advanced Photon Source was supported by the US Department of Energy, Office of Science, under Contract No. DE-AC02-06CH11357. H.O. was supported by MEXT (25246023).

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Authors and Affiliations

  1. Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, USA

    Hyoungjeen Jeen, Woo Seok Choi, Dongwon Shin, Matthew F. Chisholm & Ho Nyung Lee

  2. Center for Nanophase Materials Science, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, USA

    Michael D. Biegalski

  3. Materials Science Division, Argonne National Laboratory, Argonne, Illinois 60439, USA

    Chad M. Folkman & Dillon D. Fong

  4. Advanced Photon Source, Argonne National Laboratory, Argonne, Illinois 60439, USA

    I-Cheng Tung & John W. Freeland

  5. Department of Materials Science and Engineering, Northwestern University, Evanston, Illinois 60208, USA

    I-Cheng Tung

  6. Research Institute for Electronic Science, Hokkaido University, Sapporo 001-0020, Japan

    Hiromichi Ohta

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Contributions

H.J. conducted sample synthesis, XRD, d.c. transport and SQUID measurements with help from W.S.C., and H.J. and M.D.B. performed the high-temperature environmental XRD, under the direction of H.N.L. M.F.C. performed STEM measurements. I-C.T. and J.W.F. measured XAS and XMCD, and H.O. worked on thermopower measurements. D.S. performed the thermodynamic modelling. C.M.F. and D.D.F. worked on the catalysis measurement. H.N.L. initiated the research and supervised the work. All authors participated in writing the manuscript.

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Correspondence to Ho Nyung Lee.

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Jeen, H., Choi, W., Biegalski, M. et al. Reversible redox reactions in an epitaxially stabilized SrCoOx oxygen sponge. Nature Mater 12, 1057–1063 (2013). https://doi.org/10.1038/nmat3736

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