Spherical Li1.167−xNaxNi0.18Mn0.548Co0.105O2 (0⩽x⩽0.1) particles were prepared by spray pyrolysis, and subjected to electrochemical characterization for lithium battery applications. It was confirmed that Na doping enhances the charge/discharge rate capability. The structure of prepared samples was characterized by XRD: the c-axis lattice parameter increases with increase in the amount of Na ions (parameterized by x, above). The Na-doped sample with x=0.05 shows capacities of 208 and 184mAhg−1 at high current densities of 1.0C and 2.0C, respectively. These values are enhanced, compared to values of 189 and 167mAhg−1 for the bare sample. The ratio of the capacity at 1.0C to that at 0.1C is enhanced from 77% for the bare sample to 84% for the Na-doped sample with x=0.05. The Li diffusion coefficients obtained from the galvanostatic intermittent titration technique (GITT) are higher for Na-doped samples than for the bare sample. In particular, the Na-doped sample (x=0.05), in the potential range around 4V, has a higher DLi+ value of 3.34×10−9cm2s−1, compared with 1.35×10−9cm2s−1 for the bare sample. The Na-doped samples (0<x<0.075) show high capacity retention: the Na-doped sample (x=0.05) shows a capacity retention of 92% compared to 83% for the bare sample.