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P2-NaxVO2 system as electrodes for batteries and electron-correlated materials

Nature Materials volume 12, pages 74–80 (2013)Cite this article

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Abstract

Layered oxides are the subject of intense studies either for their properties as electrode materials for high-energy batteries or for their original physical properties due to the strong electronic correlations resulting from their unique structure. Here we present the detailed phase diagram of the layered P2-NaxVO2 system determined from electrochemical intercalation/deintercalation in sodium batteries and in situ X-ray diffraction experiments. It shows that four main single-phase domains exist within the 0.5≤x≤0.9 range. During the sodium deintercalation (intercalation), they differ from one another in the sodium/vacancy ordering between the VO2 slabs, which leads to commensurable or incommensurable superstructures. The electrochemical curve reveals that three peculiar compositions exhibit special structures for x = 1/2, 5/8 and 2/3. The detailed structural characterization of the P2-Na1/2VO2 phase shows that the Na+ ions are perfectly ordered to minimize Na+/Na+ electrostatic repulsions. Within the VO2 layers, the vanadium ions form pseudo-trimers with very short V–V distances (two at 2.581 Å and one at 2.687 Å). This original distribution leads to a peculiar magnetic behaviour with a low magnetic susceptibility and an unexpected low Curie constant. This phase also presents a first-order structural transition above room temperature accompanied by magnetic and electronic transitions. This work opens up a new research domain in the field of strongly electron-correlated materials. From the electrochemical point of view this system may be at the origin of an entire material family optimized by cationic substitutions.

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Figure 1: X-ray diffraction pattern of the P2-Na0.71VO2 composition obtained by solid-state synthesis.
Figure 2: Evolution of the electrochemical behaviour of the P2-NaxVO2 system.
Figure 3: Synchrotron diffraction pattern of P2-Na1/2VO2 and Rietveld refinement of its structure.
Figure 4: Three-dimensional overview of the structure of P2-Na1/2VO2.
Figure 5: Projection of the structure of P2-Na1/2VO2 along the c axis.
Figure 6: Physical properties of P2-Na1/2VO2.

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Acknowledgements

The authors thank R. Decourt for transport measurements and C. Denage for technical assistance. Financial support was provided by CNRS and Région Aquitaine.

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Authors and Affiliations

  1. CNRS, Université de Bordeaux, ICMCB site de l’ENSCBP-IPB, 87 avenue du Dr. A. Schweitzer, 33608 Pessac Cedex, France

    Marie Guignard, Christophe Didier, Jacques Darriet & Claude Delmas

  2. CNRS, UJF, Institut NEEL, 38042 Grenoble Cedex 9, France

    Pierre Bordet

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

    Erik Elkaïm

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  1. Marie Guignard
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Contributions

M.G., J.D. and C. Delmas planned the research. M.G., C. Didier, P.B. and E.E. carried out the experimental work. M.G., C. Didier, J.D. P.B., E.E. and C. Delmas analysed the data, and wrote and revised the manuscript.

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Correspondence to Claude Delmas.

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Guignard, M., Didier, C., Darriet, J. et al. P2-NaxVO2 system as electrodes for batteries and electron-correlated materials. Nature Mater 12, 74–80 (2013). https://doi.org/10.1038/nmat3478

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