title: First evidence of manganese-nickel segregation and densification upon cycling in Li-rich layered oxides for lithium batteries.
abstract: Lithium-rich manganese-based layered oxides Li[Li(x)Mn(y)TM(1-x-y)]O2 with TM standing for Ni, Co, or Fe are of great interest as cathode materials for lithium ion batteries. Indeed, among all of the materials, they offer the highest rechargeable capacity and energy density. However, when used, they suffer from complex evolutions that need to be understood before their practical use. Here we report on such evolutions studied using advanced transmission electron microscopy. Structural modifications are directly observed at the atomic scale using Cs corrected STEM HAADF imaging technique, and the chemical modifications are probed by the means of STEM EELS experiments. For the first time, segregation between nickel and manganese close the particle surface is pointed out. Finally, observed evolutions are correlated within a proposed mechanism that leads to the densification of the material. Our results allow understanding the link between the decrease of electrochemical performance and these evolutions occurring into the material upon cycling.
authors.affiliation: CEA, LITEN, 17 rue des Martyrs, 38054 Grenoble Cedex 9, France. adrien.boulineau@cea.fr
authors.forename: Adrien
authors.initials: A
authors.lastname: Boulineau
authors.forename: Loïc
authors.initials: L
authors.lastname: Simonin
authors.forename: Jean-François
authors.initials: JF
authors.lastname: Colin
authors.forename: Carole
authors.initials: C
authors.lastname: Bourbon
authors.forename: Sébastien
authors.initials: S
authors.lastname: Patoux