▎ 摘　　要

NOVELTY - Preparing graphene composite film comprises e.g. (i) adding ferric chloride into graphene oxide aqueous dispersion, oscillating, applying resulting graphene oxide hydrogel with doctor blade on hydrophilic treated glass plate substrate to scrape out, placing into mixture of hydroiodic acid and acetic acid (HAc), detaching film from glass substrate, and (ii) dissolving 3,4-ethylenedioxythiophene, pyrrole-3-carboxylic acid, lithium perchlorate and titanium oxygen cluster in acetonitrile, ultrasonically mixing as electrolyte and taking porous graphene film material as working electrode. USE - The method is useful for preparing graphene composite film (claimed). ADVANTAGE - The method has high toughness, better hole distribution condition, exhibits excellent electrochemical performance and is suitable as flexible super capacitor electrode material. DETAILED DESCRIPTION - Preparing graphene composite film comprises (i) adding ferric chloride into graphene oxide aqueous dispersion having concentration of 3-10 mg/ml and oscillating to obtain graphene oxide hydrogel, applying resulting graphene oxide hydrogel with doctor blade on hydrophilic treated glass plate substrate to scrape out thickness of 0.1-100 mu m film, allowing to stand at room temperature for 1-30 minutes, placing into mixture of hydroiodic acid and acetic acid (HAc) at room temperature, soaking for 0.1-48 hours, then heating at 50-100 degrees C for 1-24 hours, detaching film from glass substrate, removing film, washing with water and freeze-drying to obtain porous graphene film material, where mass of ferric chloride is 1-15 mg/ml based on the volume of graphene oxide aqueous dispersion; mixed solution of hydroiodic acid and HAc is prepared by mixing hydroiodic acid and HAc in a volume ratio of 1:1.5-2.5, and the amount of hydroiodic acid is 45-60 wt.% of HI aqueous solution, and (ii) dissolving 3,4-ethylenedioxythiophene, pyrrole-3-carboxylic acid, lithium perchlorate and titanium oxygen cluster in acetonitrile, ultrasonically mixing as electrolyte, taking porous graphene film material prepared in step (i) as working electrode, platinum wire as counter electrode, silver/silver chloride electrode as reference electrode, voltage window is -0.8 to 1.5 V, scanning at a rate of 0.001-0.5 V/s lower for 1-100 cycles of cyclic voltammetry electrochemical polymerization, removing film and cleaning to obtain graphene composite film, where the amount of 0.1-100 mmol/100 ml 3,4-ethylenedioxythiophene, 0.1-100 mmol/100 ml pyrrole-3-carboxylic acid and 0.1-100 mmol/100 ml lithium perchlorate is based on the volume of acetonitrile and used amount of titanyl cluster is 0.1-100 mg/100 ml based on the volume of acetonitrile.