The layered structure LiNi1/3Co1/3Mn1/3O2 cathode material was successfully prepared via a carbonate co-precipitation method, followed by a calcination process at high temperature. The effects of precipitant agent on the crystal structure and morphology of the prepared materials have been studied by XRD, SEM, and the electrochemical performance was investigated by galvanostatic charge–discharge test, cyclic voltammetry and electrochemical impedance spectroscopy. The carbonate precursors (Ni1/3Co1/3Mn1/3)CO3 synthesized by different precipitant agent show a single phase of hexagonal carbonate but a great difference in morphology. The well-crystallized product LiNi1/3Co1/3Mn1/3O2 with homogeneous mixing of transition metal ions were obtained via different precipitants. The material made form Na2CO3 +NH4HCO3 precipitant shows the smallest particles size without agglomeration, the lowest polarization and the lowest interfacial resistance, which leads to excellent comprehensive electrochemical performance.