Local Interactions Governing the Performances of Lithium- and Manganese-Rich Cathodes.

The local structural and electronical transformations occurring along the first charge and discharge cycle of Li- and Mn-rich Li[Li _0.2 Ni _0.16 Mn _0.56 Co _0.08 ]O ₂ cathode material have been characterized by X-ray absorption spectroscopy at several complementary edges. The irreversible spinel formation, occurring at the expenses of the cycling layered phase during the first charge, is quantified (about 10%) and spatially localized. The local strains induced by the Ni oxidation have been evaluated. They induce the formation of a low spin Mn ³⁺ in the layered structure in parallel to the irreversible formation of the spinel phase in the particles bulk. The charge balance has been quantified for all the elements along the first charging cycle, confirming a reversible oxygen oxidation along the charge. Overall, these quantitative results provide an experimental basis for modeling aimed to control the structure and its evolution, for instance, hindering the spinel formation for the benefit of the material cycle life.