A prepn. method for protective film of lithium ion cell. At least one organic polymer among phenolic resin, epoxy resin, polyvinyl acetate, polyurethane, polytetrafluoroethylene, chloronorgutta, phenolic chloronorgutta, epoxy polyamide and phenolic polyvinyl acetal is added into particular solvent selected at least one from diionized water, carbinol, benzene, toluene, chloroform dichloroethylene, diethyl ether, acetone, ethyl acetate and normal ethane, they are mixed and stirred to organic solution which is coated on case of lithium ion cell, then the case is static placed to volatilize particular solvent in the organic solution in room temp. to form a layer of uniform and densify protective film on cell case. Said film can prevent corrding of electrolyte and perspiration in prodn process. The invent is also relates to a solvent used for cleaning said proctive film selected from deionized water, alcohol, acetone, oxolane and formyldimethylamine.