In this work, layered lithium-excess materials Li1..,Ni0.5Mo0.3C00.202,8 (x = 0, 0.05, 0.10 and 0.15), of spherical morphology with primary nanoparticles assembled in secondary microspheres, were synthesized by a coprecipitation method. The effects of lithium content on the structure and electrochemical performance of these materials were evaluated by employing X-ray diffraction (XRD), inductive coupled plasma (ICP), scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS) and galvanostatic charge/discharge tests. It is found that Li LI 5Ni05Mn5,3Co0.202.6, i.e., Li[(Ni0,5Mn03C00.2)0.951j0.05102 showed the best electrochemical performance due to the highly ordered layered structure, reduced cation mixing and the lowest charge transfer resistance. LiI,I0Ni0.5Mo0.3Co0.202,8 delivered a discharge capacity of 145 mA h g-1 at 125 mA g-1 in the cut-off voltage of 2.5-4.3 V, and had a capacity retention of 100% after 50 cycles at room temperature. 2011 Elsevier Ltd. All rights reserved.