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Etude par RMN de matériaux d'électrode pour batteries lithium-ion

Abstract : This work is devoted to the study of LiMO2 et LiM2O4 (M: transition metal) intercalation compounds used as electrode material for lithium-ion batteries. Solid state NMR allows one to characterise the local environment of the lithium ions present in these phases by the use of the hyperfine interactions due to the presence of some electron spin density coming from localised electrons (Fermi-contact shift) or itinerant electrons (Knight shift) on the lithium nucleus.
By following the transformation of the LiNiO2 layered phase into the LiNi2O4 spinel material using lithium NMR, we studied the nature of the asymmetric signal observed for LiNiO2, and the influence of the departure from the ideal stoichiometry; we showed a coupled ion/electron hopping in LixNiO2 phases linked to Li/vacancy and Ni3+/Ni4+ ordering, and finally showed the existence of structural defects within the LiNi2O4 spinel phase obtained by thermal treatment of Li0.5NiO2.
Lithium NMR of the intercalated materials obtained from the LiTi2O4 and Li4Ti5O12 spinels showed a metallic behaviour for Li2Ti2O4 with a Knight shift of the NMR signal similar to that of LiTi2O4, and signals intermediate in nature between Knight and Fermi-contact shifts for Li7Ti5O12.
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Submitted on : Friday, September 8, 2006 - 6:17:25 PM
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Cédric Chazel. Etude par RMN de matériaux d'électrode pour batteries lithium-ion. Matériaux. Université Sciences et Technologies - Bordeaux I, 2006. Français. ⟨tel-00092375⟩

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