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The paper describes investigation on new types of supercapacitors based on composite polyaniline / reduced graphene oxide with network nanocomposite polymer electrolyte. Its prototypes are all solid state. The new network polymer electrolytes based on polyethylene glycol diacrylate and nanoparticle SiO2 was synthesized by reaction of radical polymerization in the environment of liquid organic electrolyte. The work is aimed to obtain a polymer electrolyte that is compatible with the electrode materials of supercapacitors. For these purposes the method of FTIR spectroscopy, a.c. electrochemical impedance and galvanostatic cycling were used.