The invention discloses a preparation method of a lithium ion battery composite material with a double-shell structure, which comprises adding cobalt nitrate hexahydrate into N,N-dimethylformamide, and then dissolving by ultrasonic to obtain a solution I, and then adding 2,5-dihydroxyterephthalic acid was added to the absolute ethanol solution, and ultrasonically dissolved to obtain solution II. After the solutions I and II were mixed and stirred, distilled water was added and then moved to a polytetrafluoroethylene reaction kettle. React at ℃ for 24-30 h, and cool to obtain metal-organic framework Co-MOF-74, adding copper nitrate trihydrate to methanol solution, ultrasonically dissolving, adding metal-organic framework Co-MOF-74 in step S1, magnetically at room temperature Stir for 3 to 6 hours, then add citric acid to sonicate, move to a polytetrafluoroethylene reactor, react at 60 to 80 °C for 3 to 5 hours, cool, filter, and dry; place the dried product in a tube furnace, In an air atmosphere, the temperature is raised to 580-520°C at a heating rate of 5-8°C/min, maintained at this temperature for 4-7 hours, and then brought to room temperature at a rate of 0.5-1.2°C/min to obtain the composite material.