Electrospinning can regulate fiber and membrane structures at the nanoscale, and doping graphene futher enhances the electrochemical function of nanofilms. Starting from the structure of graphene, we optimize the relationship between graphene doping ratio and nanofiber size and study the effects of electrospinning voltage, feed rate, spinning distance and time on membrane structure and electrochemical performance. Research has shown that when the graphene doping mass fraction in the nanofilm is 7%, the voltage is 24 kV, the spinning distance is 15 cm, the feed rate is 0.01 mL/min, and the time is 2 h, the diameter of the fibers in the nanofilm structure is 0.162 μm, and the impedance is 220.8 Ω. Under electrospinning conditions, the doping of graphene can control the preparation of nano films and optimize their electrochemical properties in multiple ways.