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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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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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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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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DOI: https://doi.org/10.1038/nmat3736
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