Li-Driven Copper Extrusion/Re-injection in Various Cu-based Oxides and Sulfides

Autor: Mickaël Dollé, Olivier Szajwaj, V. Bodenez, Mathieu Morcrette, Jean-Marie Tarascon, Christine Surcin, Loic Dupont, Patrick Rozier
Rok vydání: 2008
Předmět:
Zdroj: Israel Journal of Chemistry. 48:235-249
ISSN: 1869-5868
0021-2148
DOI: 10.1560/ijc.48.3-4.249
Popis: The present paper is in part a continuation of our recent work dealing with the fully reversible Li-driven Cu extrusion/injection of Cu in Cu2.33V4O11. The peculiar electrochemical property of such a compound was mainly ascribed to both structural considerations (presence of anchoring oxygen, giving flexibility to the [V4O11] layers) and electronic considerations, such as the existence of a delicate balance between the two Cu+/Cu2+ and V4+/V5+ redox centers. To support such suggestions, numerous compounds were revisited for their electrochemical–structural interplay. Network dimensionality, lattice flexibility, and cationic mobility parameters were addressed by exploring in depth the richness of the Cu–V–O system, while the importance of the donor/acceptor energy levels was checked via the choice of compounds having the right energy match between the two redox centers. As an extensive trial-and-error approach was not realistic, we relied on simple considerations based on the ionization energy of the various d-metals to narrow down metal pairs having redox levels occurring within the same range of energies. Bearing this in mind, it was logical to consider compounds still containing Cu ions but with Nb instead of V or compounds having V and Ag instead of Cu. Regardless of our effort, it turned out that the number of potential candidates worth considering for practical applications is still very limited, in spite of the elegance of this new Li reactivity mechanism.
Databáze: OpenAIRE
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