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Electrochemical investigation of the P2–NaxCoO2 phase diagram

Nature Materials volume 10, pages 74–80 (2011)Cite this article

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Abstract

Sodium layered oxides NaxCoO2 form one of the most fascinating low-dimensional and strongly correlated systems; in particular P2–NaxCoO2 exhibits various single-phase domains with different Na+/vacancy patterns depending on the sodium concentration. Here we used sodium batteries to clearly depict the P2–NaxCoO2 phase diagram for x≥0.50. By coupling the electrochemical process with an in situ X-ray diffraction experiment, we identified the succession of single-phase or two-phase domains appearing on sodium intercalation with a rather good accuracy compared with previous studies. We reported new single-phase domains and we underlined the thermal instability of some ordered phases from an electrochemical study at various temperatures. As each phase is characterized by the position of its Fermi level versus the Na+/Na couple, we showed that the synthesis of each material, even in large amounts, can be carried out electrochemically. The physical properties of the as-prepared Na1/2CoO2 and Na2/3CoO2 ordered phases were characterized and compared. Electrochemical processes are confirmed to be an accurate route to precisely investigate in a continuous way such a complex system and provide a new way to synthesize materials with a very narrow existence range.

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Figure 1: Galvanostatic cycling curve of a Na//P2–NaxCoO2 battery giving an overview of the phase diagram.
Figure 2: Synergy between electrochemistry and in situ XRD through sodium ion intercalation in P2–NaxCoO2.
Figure 3: Evolution of the chex. parameter as a function of the sodium content.
Figure 4: Overview of single-phase domain thermal stability.
Figure 5: Potentiostatic route to obtain P2–NaxCoO2 material with a given composition.

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Acknowledgements

The authors thank S. Pechev for XRD measurement technical expertise, M. Pollet for fruitful discussions and S. Meng, M-H. Julien and B. J. Hwang for scientific exchanges. Financial support was provided by CNRS, ANR through the OCTE programme and Région Aquitaine. CEA is thanked for the scholarship to R.B.

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Authors and Affiliations

  1. CNRS, Université de Bordeaux, ICMCB, 87 avenue du Dr. A. Schweitzer, 33608 F-Pessac, France

    R. Berthelot, D. Carlier & C. Delmas

  2. CEA-Grenoble, DRT-LITEN, 17, rue des Martyrs, 38054 Grenoble, France

    R. Berthelot

  3. CNRS, ENSCBP, ICMCB, 87 avenue du Dr. A. Schweitzer, 33608 F-Pessac Cedex, France

    D. Carlier & C. Delmas

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  1. R. Berthelot
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D.C. and C.D. planned the research. R.B. and D.C. carried out the experimental work. R.B., D.C. and C.D. analysed the data, and wrote and revised the manuscript.

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Correspondence to D. Carlier.

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Berthelot, R., Carlier, D. & Delmas, C. Electrochemical investigation of the P2–NaxCoO2 phase diagram. Nature Mater 10, 74–80 (2011). https://doi.org/10.1038/nmat2920

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