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Oxygen storage capacity and structural flexibility of LuFe2O4+x (0≤x≤0.5)

Nature Materials volume 13, pages 74–80 (2014)Cite this article

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Abstract

Combining functionalities in devices with high performances is a great challenge that rests on the discovery and optimization of materials. In this framework, layered oxides are attractive for numerous purposes, from energy conversion and storage to magnetic and electric properties. We demonstrate here the oxygen storage ability of ferroelectric LuFe2O4+x within a large x range (from 0 to 0.5) and its cycling possibility. The combination of thermogravimetric analyses, X-ray diffraction and transmission electron microscopy evidences a complex oxygen intercalation/de-intercalation process with several intermediate metastable states. This topotactic mechanism is mainly governed by nanoscale structures involving a shift of the cationic layers. The ferrite is highly promising because absorption begins at a low temperature (), occurs in a low oxygen pressure and the uptake of oxygen is reversible without altering the quality of the crystals. The storage/release of oxygen coupled to the transport and magnetic properties of LnFe2O4 opens the door to new tunable multifunctional applications.

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Figure 1: Perspective view of the monoclinic M structure of LuFe2O4 at room temperature, and comparison with the M′ sub-cell of LuFe2O4+x.
Figure 2: Temperature dependence of the weight evolution and of the XRD patterns of LuFe2O4+x from room temperature up to 500 °C (in a dynamic primary vacuum).
Figure 3: EDPs and corresponding schematized crystal cells versus oxygen content (from O4 to O4.5).
Figure 4: Synchrotron XRPD patterns of the M, R13 and M′ phases.
Figure 5: Oxygen storage/release cycle.
Figure 6: Effect of the oxygen content on magnetic properties of LuFe2O4+x.

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Acknowledgements

This work was supported by financial support from the French Agence Nationale de la Recherche (ANR-08-BLAN-0005-01 and JC08-331297). The authors thank M. T. Sougrati (Institut Charles Gerhardt) for Mössbauer experiments.

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Authors and Affiliations

  1. Laboratoire CRISMAT, UMR 6508 CNRS, ENSICAEN, 6 Boulevard du Maréchal Juin, 14050 Caen Cedex, France

    M. Hervieu, A. Guesdon, J. Bourgeois, A. Maignan & C. Martin

  2. Laboratoire Léon Brillouin, UMR 12, CEA-Saclay, CEA-CNRS, 91191 Gif-sur-Yvette Cedex, France

    J. Bourgeois & F. Damay

  3. Synchrotron Soleil, L’Orme des Merisiers, Saint-Aubin BP 48 91192 Gif-sur-Yvette Cedex, France

    E. Elkaïm

  4. Institut Charles Gerhardt UMR CNRS 5253, Université Montpellier II, Place E Bataillon, cc1503, 34095 Montpellier Cedex, France

    M. Poienar & J. Rouquette

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  1. M. Hervieu
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Contributions

The samples were prepared by J.B., magnetic properties were measured by M.P. and A.M., E.E. collected the synchrotron XRD data, A.G. and C.M. analysed TGA data and XRD diffractograms, and M.H. performed the electron microscopy observations and data analysis. The manuscript was written by M.H. and C.M. and revised by F.D., J.R., A.G. and A.M. The project direction was developed by F.D. and C.M.

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Correspondence to C. Martin.

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Hervieu, M., Guesdon, A., Bourgeois, J. et al. Oxygen storage capacity and structural flexibility of LuFe2O4+x (0≤x≤0.5). Nature Mater 13, 74–80 (2014). https://doi.org/10.1038/nmat3809

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