Layered LiNi0.2Mn0.2Co0.6O2 phase, belonging to a solid solution between LiNi1/2Mn1/2O2 and LiCoO2 most commercialized cathodes, was prepared via the combustion method at 900 degrees C for a short time (1 h). Structural and magnetic properties of this material during chemical extraction were investigated. The powders adopted the alpha-NaFeO2 structure with almost none of the well-known Li/Ni cation disorder. The analysis of the magnetic properties in the paramagnetic domain agrees with the combination of Ni2+ (S = 1), Co3+ (S = 0) and Mn4+ (S = 3/2) spin-only values. X-ray analysis of the chemically delithiated LiyNi0.2Mn0.2Co0.6O2 reveals no structural transition. The process of lithium extraction from and insertion into LiNi0.2Mn0.2Co0.6O2 was discussed on the basis of ex situ EPR experiments and magnetic susceptibility. Oxidation of Ni2+ (S = 1) to Ni3+(S = 1/2) and to Ni4+ (S = 0) was observed upon lithium removal. (C) 2012 Elsevier Ltd. All rights reserved.