New materials and the interactions between them are the basis of novel energy storage devices such as supercapacitors and batteries. In recent years, because of the increasing demand for electricity as an energy source, the development of new energy storage materials is among the most actively studied topics. Conductive polymers (CPs), because of their intrinsic electrochemical activity and electrical conductivity, have also been intensively explored. While most of the high capacitance reported in the literature comes from hybrid materials, for example, conductive polymers composed of metal oxides and carbon materials, such as graphene and carbon nanotubes, new chemistry and the 3D structure of conductive polymers remain critical. This comprehensive review focuses on the basic properties of three popular conductive polymers and their composites with carbon materials and metal oxides that have been actively explored as energy storage materials, i.e., polypyrrole (PPy), polyaniline (PANi), and polythiophene (PTh), and various types of electrolytes, including aqueous, organic, quasi-solid, and self-healing electrolytes. Important experimental parameters affecting material property and morphology are also discussed. Electrochemical and analytical techniques frequently employed in material and supercapacitor research are presented. In particular, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) are discussed in detail, including how to extract data from spectra to calculate key parameters. Pros and cons of CP-based supercapacitors are discussed together with their potential applications.

Polypyrrole (PPy) is one of the attractive conducting polymers that have been investigated as energy storage materials in devices like supercapacitors. Previously, we have reported a free-standing soft PPy membrane synthesized through interfacial polymerization in which methyl orange (MO) and ferric chloride were used as nano template and oxidant. In this work, we report that the presence of MO and the treatment of the PPy–MO membrane with sulfuric acid can dramatically increase the specific capacitance of the membrane. The properties of the membranes were evaluated using scanning electron microscope (SEM) for morphology, Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) for chemistry, thermogravimetric analysis (TGA) for thermal stability, and cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS) for electrochemical activity. It was found that the areal specific capacitance of the PPy membrane increased from 2226 mF/cm² to 6417 mF/cm² and the charge transfer resistivity decreased from about 17 Ω to 3 Ω between 10,000 and 0.1 Hz due to the presence of MO and the acid treatment. It is likely that the superposition effect of MO and acid treatment helped the charge transfer process and consequently enhanced the charge storage performance and specific capacitance of the PPy membrane.