Lithium and thin-film lithium cobalt(III) oxide (LiCoO2) were employed in a 2/3 A-size rechargeable battery as negative and positive electrodes. The cell capacity can reach 0.16 Ah/g. The lithium cobalt(III) oxide films were prepared by a spray-coating process. A series of sols were used as precursor for preparing the films. It was shown that different reaction conditions and precursors change the microstructure of the films and affect the electrochemical performance of the cells.