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Positron annihilation spectroscopy using lifetime and Doppler broadening allows the characterization of the lithiation state in LiCoO₂ thin film used in cathode of lithium-ion batteries. The lifetime results reflect positron spillover because of the presence of graphite in between the oxide grains in real cathode Li-ion batteries. This spillover produces an effect in the measured positron parameters which are sensitive to delocalized electrons from lithium atoms as in Compton scattering results. The first component of the positron lifetime corresponds to a bulk-like state and can be used to characterize the state of charge of the cathode while the second component represents a surface state at the grain-graphite interface.