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A new synthetic route of Li[NiMnCo]O2 was contrived and its electrochemical characteristics were enhanced by doping small amount of Si. The newly synthesized Li[NiMnCo]O2 showed the capacity of 175 mAh/g and good cycle life at as high cut-off voltage as 4.5V. Si-doped material showed improved rate capability, specific capacity, and cycle life. It seems that the increased lattice parameters and lowered electrochemical impedance are the main causes for the improvement.