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A reversible copper extrusion–insertion electrode for rechargeable Li batteries


Although widely used, the most promising Li-based technologies still suffer from a lack of suitable electrodes. There is therefore a need to seek new materials concepts to satisfy the increasing demands for energy storage worldwide. Here we report on a new layered electrode material, Cu2.33V4O11, which shows a sustainable reversible capacity of 270 mA h g−1 at a voltage of about 2.7 V, and electrochemically reacts with Li in an unusual and spectacular way. The reaction entails a reversible Li-driven displacement process leading to the growth and disappearance of Cu dendrites with a concomitant reversible decomposition and recrystallization of the initial electrode material. We show from structural considerations that the uniqueness of Cu2.33V4O11 is rooted in the peculiar flexibility of the stacked [V4O11]n layers, which is due to the presence of pivot oxygen atoms. Fully reversible displacement reactions could provide a new direction for developing an alternative class of higher energy density Li storage electrodes.

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Figure 1: Electrochemical test data for Cu2.33V4O11, and its crystal structure.
Figure 2: In situ X-ray diffraction performed on a Cu2.33V4O11/Li cell discharged and charged at a rate of 1 Li in 20 h.
Figure 3: Cycle testing of an in situ X-ray electrochemical cell at C/5 between 1.5 and 3.5 V.
Figure 4: TEM studies of Cu2.33V4O11 electrodes recovered from Cu2.33V4O11/Li cells.
Figure 5: Live SEM observations of a polymeric Cu2.33V4O11/Li cell cross-section during cycling.
Figure 6: Polyhedral representation of the V oxygenated surrounding (blue) and copper ions (green) arrangement in various copper-based vanadate structures.


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We thank M. G. Karkut, D. Larcher, P. Poizot and B. Beaudoin for many useful discussions.

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Correspondence to J.-M. Tarascon.

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Morcrette, M., Rozier, P., Dupont, L. et al. A reversible copper extrusion–insertion electrode for rechargeable Li batteries. Nature Mater 2, 755–761 (2003).

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