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Article Dans Une Revue Journal of The Electrochemical Society Année : 2013

Reversible oxygen participation to the redox processes revealed for Li1.20Mn0.54Co0.13Ni0.13O2

Résumé

Materials prepared by chemical Li deintercalation with NO2BF4 from Li1.20Mn0.54Co0.13Ni0.13O2 and chemical Li reinsertion with LiI show very similar chemical composition, oxidation state of each transition metal ion, structural properties and electrochemical performance to those of the material recovered after the 1st electrochemical cycle. Investigations combining redox titration, magnetic measurement, neutron diffraction and chemical analyzes reveal that uncommon redox processes are involved during the first charge at high voltage and explain the charge overcapacity and large reversible discharge capacity obtained for this material. This further assesses our proposal that oxygen, in addition to nickel and cobalt, participates to the redox processes in charge: within the bulk oxygen is oxidized without oxygen loss, whereas at the surface oxygen is oxidized to O2 and irreversibly lost from the structure. During the subsequent discharge, in addition to nickel, cobalt and oxygen, manganese is also slightly involved in the redox processes (reduction) to compensate for the initial surface oxygen loss.

Domaines

Matériaux
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Dates et versions

hal-00807341 , version 1 (03-04-2013)

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Hideyuki Koga, Laurence Croguennec, Michel Ménétrier, Kaïs Douhil, Stéphanie Belin, et al.. Reversible oxygen participation to the redox processes revealed for Li1.20Mn0.54Co0.13Ni0.13O2. Journal of The Electrochemical Society, 2013, 160 (6), pp.A786-A792. ⟨10.1149/2.038306jes⟩. ⟨hal-00807341⟩
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