Nanotubes were coated on the surface of active LiCoO2 particles using electrostatic heterocoagulation to enhance the electrochemical properties of a Li-ion battery. Only 0.5wt% of multiwalled carbon nanotubes (MWCNTs) was added as a conducting agent into the LiCoO2 cathode, which had a density of 4.0gcm−3. We found that our electrode that was prepared using heterocoagulation with 0.5wt% of thin MWCNTs maintained a volumetric capacitance of 403mAhcm−1 after 40 cycles from the initial 624mAhcm−1, compared with previous result of 310mAhcm−1 obtained from simple mixing with 3wt% MWCNTs. The high volumetric capacity with smaller swelling using less amount of MWCNTs was attributed to the self-assembled nanotube network formed between active particles during coagulation, which was maintained with volume expansion during cycle testing.