We report herein on the study of Li and Mn rich Li-x[MnNiCo]O-2 cathode materials with an emphasis on the effect of AlF3 coating on their electrochemical performance. The initial stoichiometry of these materials was xLi(2)MnO(3)center dot(1-x)LiMnyNizCowO2 where x is in the range 0.4-0.5 and the y:z:w ratio was as we previously reported. Their structure was considered on the basis of two-components model, namely monoclinic Li2MnO3 (C2/m) and rhombohedral LiMO2 (R-3m) (M = Mn, Ni, Co) that are structurally compatible and closely integrated phases. Based on TEM studies we concluded that the coating had a crystalline tetragonal structure t-AlF3 (P4nmm symmetry) and AlF3 nano-crystals were regularly distributed over the particles surface. Amorphous clusters of AlF3 and/or other Al-containing species, like AlFxOy, Al[FOH], etc. may also present, as it follows from solid-state NMR measurements. It was shown that electrodes comprising the AlF3-coated material exhibited higher reversible capacities of similar to 250 mAh/g at a C/5 rate, more stable cycling behavior, higher lithium storage capability at 60 degrees C, and lower impedance measured during Li-deinteraclation comparing to electrodes prepared from the uncoated material. An important finding is that Li-x[MnNiCo]O-2/AlF3 materials revealed much higher thermal stability both in the pristine (lithiated) and cycled (delithiated) states than their uncoated counterparts. (C) 2013 The Electrochemical Society. All rights reserved.