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Nano carbon film was synthesized on a nickel substrate in molten LiCl-KCl-K2CO3 salt by an electrolytic deposition method. The influence of pulse frequency on the property of the carbon films was studied. Over the carbonate ion concentration range of 0.10–0.20 mol%, the mass of carbon film on unit area increases with increasing pulse frequency over the range of 0.05–33Hz or 33–166Hz, whereas, it decreases with increasing pulse frequency over the range of 33-166Hz. It means that a critical pulse frequency exists, which can be thought to correspond to the natural vibration frequency of the film. When the electrolytic pulse frequency is equal to the natural vibration frequency of film, a resonance maybe happen, and the film exfoliates.