To improve the density and electrochemical performance of LiFePO4, Na-doping modified Li0.95Na0.05FePO4 cathode material was synthesised through co-precipitation method, using a spherical sample prepared by microwave heating as precursor. The morphology, structure, electrochemical performance and the tap density of the materials were characterised by scanning electron microscope, x-ray diffraction, cyclic voltammetry, constant current charge-discharge experiment and the tap density measurement. The results indicated that the samples have rules spherical or similar spherical morphology and simple pure olive-type phase. The Na-doped Li0.95Na0.05FePO4 material showed excellent performance with a tap density of 1.63 g cm(-3). At room temperature, its initial discharge capacities reached 164.2, 151.5 and 130.5 mAh g(-1) at 0.2, 1 and 2 C current rates, respectively.