The sol-gel process, using aqueous solutions, is used for dip coating onto substrates of 316L stainless steel. A suitable coating of LiCoO2 is achieved by varying the thickness and heat treating at 650 ℃ for 3 h. Thermal analysis, X-ray diffraction analysis and SEM are carried out to characterize the microstructure of the coatings. The results show that the coating transforms from an amorphous gel to crystalline phases above 350 ℃, and show a porous structure. The phase transition mechanism is discussed.