From the vanadates to 3d-metal oxides negative electrodes |
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Authors: | P Poizot S Laruelle S Grugeon L Dupont J -M Tarascon |
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Institution: | (1) Laboratoire de Réactivité et de Chimie des Solides, UPRES A CNRS 6007, 33 rue Saint Leu, 80039 Amiens cedex, France |
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Abstract: | With respect to lithium batteries, vanadate-based electrodes display large electrochemical capacities that rapidly decay during
the cycling. A full study of the 3d-metal(M)-based vanadates performed using in situ DRX, XAS and TEM has enabled to pinpoint
the important role of the 3d-metal cations, and has motivated the study of simple metal oxides MO, (M=Co, Ni, Cu, Fe) in rechargeable
Li cells. We found that these materials could reversibly react with a large amount of lithium leading to capacities as high
as 800 mAh/g. The reactivity mechanism totally differs from the well established one based on Li insertion-deinsertion or
Li alloying reactions but mainly involves the formation of highly reactive metallic nanoparticles that favor Li2O formation-decomposition. Besides, we gave experimental evidence of an electrochemically driven polymerization-dissolution
process at low potential, which is highly reversible, and emphasized the importance of the role of the electrolyte on such
a process. Finally, the universality of this mechanism to account for the large Li reactivity at low voltage in many 3d-metal
(Co, Ni, Fe, Cu, Mn)-based oxides is discusséd together with the urgent issues to be solved for such oxide anodes to stand
as serious alternative candidates for today’s carbon anodes in Li-ion cells.
Paper presented at the 7th Euroconference on Ionics, Calcatoggio, Corsica, France, Oct. 1–7, 2000. |
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