Résumé
Since their commercialization Li-ion batteries have relied on the use of layered oxides (LiMO2) as positive electrodes. Over the years, via skilful chemical substitution their performances have drastically improved in terms of safety and capacity, which has nearly doubled (280 mAh/g) with the recent arrival of Li-rich NMC, i.e. layered LiCoO2 in which Co has been simultaneously replaced by Mn, Ni and Li. This review will aim to describe the chemical rationale which has led to this material evolution prior to focus on Li-rich NMC phases which are sources of excitement but challenges as well. The benefits of going back to fundamentals to rationalize and understand the new science at work with these Li-rich NMC phases will be stressed and illustrated by the discovery of a new reversible anionic redox process. Issues regarding voltage fade and limited rate capability which are plaguing their present utilization in commercial Li-ion cells will be addressed as well and solutions proposed. Owing to such advances, layered oxides which are over performing spinel or polyanionic-based compounds have a bright future.