For conductive polymers to be competitive with carbon-based electrode materials, it is critical to increase their surface area and electroactivity. In this work, a thick nanofibrous polypyrrole (PPy) membrane with communicating interfiber spaces was prepared through one-pot interfacial polymerization for the first time. The electrochemical properties and conductivity of the membrane were studied with cyclic voltammetry, electrochemical impedance spectroscopy, and a four-point probe. Its morphology, chemistry, and thermostability were evaluated by scanning electron microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, and thermogravimetric analysis. The areal specific capacitances measured between 0.0 and 0.8 V at 1 mA/cm2 were 19179, 13264, 7238, and 4458 mF/cm2 for the membranes doped with docusate sodium (AOT), camphor-10-sulfonic acid (β) (CSA), Cl-, and poly(sodium 4-styrenesulfonate) (PSS), respectively. The capacity retentions after 1000 cycles were 83, 74, 67, and 61% for the AOT-, CSA-, PSS-, and Cl--doped membranes, respectively. The Coulombic efficiency was above 99% for all of the membranes. They showed energy densities of 1.7, 1.2, 0.7, and 0.4 mWh/cm2 and power densities of 0.61, 0.75, 0.66, and 0.62 mW/cm2 for the AOT-, CSA-, Cl--, and PSS-doped membranes, respectively. The ultrahigh areal specific capacitance of PPy-AOT is due to its nanofibrous structure. A mechanism has been proposed to explain how this structure is formed based on the role of AOT as the surfactant. This nanofibrous PPy membrane is easy to prepare and metal-free and offers a very high areal specific capacitance, making it an excellent candidate to construct electrodes in pseudosupercapacitors.
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