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SYNTHESE ET ETUDE ELECTROCHIMIQUE DE NITRURES MIXTES DE LITHIUM ET DE METAL DE TYPE Li3-xMxN (M = Co, Cu, Ni) UTILISABLES COMME ELECTRODE NEGATIVE DANS LES ACCUMULATEURS LI-ION.

Abstract : In this study, we focus on the synthesis of ternary nitrides with the general formulation Li3-nxMx[]nx-xN (Mn+ = Co2+, Cu+ and Ni2+, [] represents vacancies) by a solid state route, under a controlled atmosphere, for a large composition range (0 < x = 0.6). The lattice parameters evolution obtained for these nitrides and a detailed analysis of X-ray diffraction data show the presence of Co2+ and Ni2+ in the interlayer spacing and the simultaneous presence of vacancies in the nitride layer. In the case of copper materials, Cu+ ions are present in the interlayer site, without any vacancies in the nitride layer. Once we master all parameters of the synthesis, we study the structural characterization and the electrochemical properties of each compound in terms of specific capacity, rechargeability, cycle life and kinetics. In all cases, we demonstrate that the redox systems involve several metal oxidation states, but also oxidation of nitrogen through (metal-N) entities. Galvanostatic performances are largely dependent on the metal and the potential range. Intercalation compounds are concerned in the potential range [0.02 – 1.0] V vs. Li+/Li because they involve the electrochemical systems CoII/CoI and NiII/NiI, with reversible Li insertion in vacancies and stable but low capacities (180 mAh.g-1). An optimisation of the electrochemical performances is possible when the potential range is extended up to 1.1 V. Thus, a stable specific capacity of about 320 mAh.g-1 is recovered after hundred of cycles, for the material Li2.23Co0.39N.
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https://tel.archives-ouvertes.fr/tel-00194996
Contributor : Jean-Baptiste Ducros <>
Submitted on : Saturday, December 8, 2007 - 10:15:38 AM
Last modification on : Wednesday, September 4, 2019 - 1:52:04 PM
Long-term archiving on: : Thursday, September 27, 2012 - 11:00:09 AM

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Jean-Baptiste Ducros. SYNTHESE ET ETUDE ELECTROCHIMIQUE DE NITRURES MIXTES DE LITHIUM ET DE METAL DE TYPE Li3-xMxN (M = Co, Cu, Ni) UTILISABLES COMME ELECTRODE NEGATIVE DANS LES ACCUMULATEURS LI-ION.. Matériaux. Université Paris XII Val de Marne, 2006. Français. ⟨tel-00194996⟩

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