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Nanoscale structural oscillations in perovskite oxides induced by oxygen evolution

Nature Materials volume 16, pages 121–126 (2017)Cite this article

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Abstract

Understanding the interaction between water and oxides is critical for many technological applications, including energy storage, surface wetting/self-cleaning, photocatalysis and sensors. Here, we report observations of strong structural oscillations of Ba0.5Sr0.5Co0.8Fe0.2O3−δ (BSCF) in the presence of both H2O vapour and electron irradiation using environmental transmission electron microscopy. These oscillations are related to the formation and collapse of gaseous bubbles. Electron energy-loss spectroscopy provides direct evidence of O2 formation in these bubbles due to the incorporation of H2O into BSCF. SrCoO3−δ was found to exhibit small oscillations, while none were observed for La0.5Sr0.5CoO3−δ and LaCoO3. The structural oscillations of BSCF can be attributed to the fact that its oxygen 2p-band centre is close to the Fermi level, which leads to a low energy penalty for oxygen vacancy formation, high ion mobility, and high water uptake. This work provides surprising insights into the interaction between water and oxides under electron-beam irradiation.

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Figure 1: TEM images and TED patterns of a BSCF particle.
Figure 2: Oscillation frequency and amplitude when exposed to different water vapour pressures and electron dose rates.
Figure 3: EELS of BSCF.
Figure 4: Structural oscillation mechanism and modelling.
Figure 5: Comparison of structural oscillations in BSCF to the lack thereof for other oxides in H2O and under e-beam irradiation.

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Acknowledgements

This work was supported in part by the MRSEC Program of the National Science Foundation under award number DMR-0819762 and the Skoltech-MIT Center for Electrochemical Energy Storage. The ETEM/EELS experiments were carried out at the Center for Functional Nanomaterials, Brookhaven National Laboratory, which is supported by the US Department of Energy, Office of Basic Energy Sciences, under Contract No. DE-SC0012704, which also supported A.D.G. and E.A.S.

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Authors and Affiliations

  1. Department of Materials Science and Engineering, Cambridge, Massachusetts 02139, USA

    Binghong Han, Kelsey A. Stoerzinger & Yang Shao-Horn

  2. Institute of Materials, École Polytechnique Fédérale de Lausanne, Station 12, CH–1015 Lausanne, Switzerland

    Vasiliki Tileli

  3. Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, New York 11973-5000, USA

    Andrew D. Gamalski & Eric A. Stach

  4. Department of Mechanical Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA

    Yang Shao-Horn

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Contributions

B.H., Y.S.-H. and E.A.S. designed the experiments. B.H. and K.A.S. prepared the materials. A.D.G., E.A.S., B.H. and V.T. carried out the ETEM experiments. B.H. prepared the initial manuscript. All authors contributed to the discussions and revisions of the manuscript.

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Correspondence to Eric A. Stach or Yang Shao-Horn.

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Han, B., Stoerzinger, K., Tileli, V. et al. Nanoscale structural oscillations in perovskite oxides induced by oxygen evolution. Nature Mater 16, 121–126 (2017). https://doi.org/10.1038/nmat4764

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