In recent years, tremendous research effort has been aimed at increasing the energy density of supercapacitors without sacrificing high power capability so that they reach the levels achieved in batteries and at lowering fabrication costs For this purpose, two important problems have to be solved: first, it is critical to develop ways to design high performance electrode materials for supercapacitors; second, it is necessary to achieve controllably assembled supercapacitor types (such as symmetric capacitors including double-layer and pseudo-capacitors, asymmetric capacitors, and Li-ion capacitors) The explosive growth of research in this field makes this review timely Recent progress in the research and development of high performance electrode materials and high-energy supercapacitors is summarized Several key issues for improving the energy densities of supercapacitors and some mutual relationships among various effecting parameters are reviewed, and challenges and perspectives in this exciting field are also discussed This provides fundamental insight into supercapacitors and offers an important guideline for future design of advanced next-generation supercapacitors for industrial and consumer applications

Recent Advances in Design and Fabrication of Electrochemical Supercapacitors with High Energy Densities

Recent advances in polyaniline research: Polymerization mechanisms, structural aspects, properties and applications

Conducting polymers (CPs) have received much attention in both fundamental and practical studies because they have electrical and electrochemical properties similar to those of both traditional semiconductors and metals. CPs possess excellent characteristics such as mild synthesis and processing conditions, chemical and structural diversity, tunable conductivity, and structural flexibility. Advances in nanotechnology have allowed the fabrication of versatile CP nanomaterials with improved performance for various applications including electronics, optoelectronics, sensors, and energy devices. The aim of this review is to explore the conductivity mechanisms and electrical and electrochemical properties of CPs and to discuss the factors that significantly affect these properties. The size and morphology of the materials are also discussed as key parameters that affect their major properties. Finally, the latest trends in research on electrochemical capacitors and sensors are introduced through an in-depth discussion of the most remarkable studies reported since 2003.

Electrical and Electrochemical Properties of Conducting Polymers.

With developments in technology, tremendous effort has been devoted to produce flexible, scalable, and high-performance supercapacitor electrode materials. This report presents a novel fabrication method of highly flexible and scalable electrode material for high-performance supercapacitors using solution-processed polyaniline (PANI)/reduced graphene oxide (RGO) hybrid film. SEM, TEM, Raman, and XPS analyses show that the PANI/RGO film is successfully synthesized. The percentages of the PANI component in the film are controlled (88, 76, and 60%), and the maximum electrical conductivity (906 S cm−1) is observed at the PANI percentage of 76%. Notably, electrical conductivity of the PANI/RGO film (906 S cm−1) is larger than both PANI (580 S cm−1) and RGO (46.5 S cm−1) components. XRD analysis demonstrates that the strong π–π interaction between the RGO and the PANI cause more compact packing of the PANI chains by inducing more fully expanded conformation of the PANI chains in the solution, leading to increase in the electrical conductivity and crystallinity of the film. The PANI/RGO film also displays diverse advantages as a scalable and flexible electrode material (e.g., controllable size and great flexibility). During the electrochemical tests, the film exhibits high capacitance of 431 F g−1 with enhanced cycling stability.

Fabrication of Highly Flexible, Scalable, and High-Performance Supercapacitors Using Polyaniline/Reduced Graphene Oxide Film with Enhanced Electrical Conductivity and Crystallinity

Developing energy storage devices to be utilized within a rapidly advancing energy market requires a multipronged approach whereby material synthesis and engineering fundamentals combine to enable technological advances. These devices should be able to store a large amount of energy in a small, lightweight package, and should be able to distribute that energy quickly for high rate applications. Pseudocapacitors made from conducting polymers, which store charge via rapid reduction and oxidation reactions, are a particularly promising candidate. This perspective explores conductivity and charge storage mechanisms in conducting polymers and describes how synthetic strategies can affect these properties. We further develop chemical correlations that have been shown to enhance the performance of pseudocapacitive electrochemical capacitors fabricated from conducting polymers. Important device engineering strategies for improving the lifetime and applicability of pseudocapacitors are also discussed.

Conducting Polymers for Pseudocapacitive Energy Storage

Polyaniline (PANI) is one of the most widely investigated conducting polymers and is considered to be of practical use for many future applications. Here, we first demonstrate that the anisotropic growth of PANI at the nanometer scale can be kinetically controlled by employing a polymeric stabilizer, poly(N-vinylpyrrolidone). The polymerization rate became slower in the presence of the stabilizer (the rate constants calculated at the initial stage decreased with increasing concentration of the stabilizer), yielding PANI nanostructures with lower aspect ratios. Therefore, it is believed that the stabilizer sterically restricts the directional fiber growth mechanism governing PANI chain growth in aqueous solution. Three PANI nanostructures, specifically nanospheres, nanorods, and nanofibers, were fabricated and their oxidation/protonation levels were investigated systematically. It was found that the nanofibers had the most outstanding oxidation/protonation level accompanied by structural ordering (note that the only difference between the polymerization conditions in each case was the concentration of the stabilizer). We also examine the electrochemical properties of PANI nanostructure electrodes in three-electrode and two-electrode (actual capacitor cell) configurations. The intrinsic charge-transport ability of individual nanostructures strongly affected the electrochemical properties of the electrodes. Briefly, the nanofiber electrode had faster electrode kinetics and better capacitance than the nanorods and nanospheres. Lastly, an extrinsic factor, the interparticle contact resistance, also turned out to noticeably influence the capacitances of the electrodes.

Anisotropic Growth Control of Polyaniline Nanostructures and Their Morphology-Dependent Electrochemical Characteristics

Polypyrrole (PPy)/cellulose (PPCL) composite papers were fabricated by vapor phase polymerization. Importantly, the vapor-phase deposition of PPy onto cellulose was assisted by employing different co-vapors namely methanol, ethanol, benzene, water, toluene and hexane, in addition to pyrrole. The resulting PPCL papers possessed high mechanical flexibility, large surface-to-volume ratio and good redox properties. Their main properties were highly influenced by the nature of the co-vaporized solvent. The morphology and oxidation level of deposited PPy were tuned by employing co-vapors during the polymerization, which in turn led to change in the electrochemical properties of the PPCL papers. When methanol and ethanol were used as co-vapors, the conductivities of PPCL papers were found to have improved five times, which was likely due to the enhanced orientation of PPy chain by the polar co-vapors with high dipole moment. The specific capacitance of PPCL papers obtained using benzene, toluene, water and hexane co-vapors was higher than those of the others, which is attributed to the enlarged effective surface area of the electrode material. The results indicate that the judicious choice and combination of co-vapors in vapor-deposition polymerization (VDP) offers the possibility of tuning the morphological, electrical and electrochemical properties of deposited conducting polymers.

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Jinyoung Huh

Papers

Anisotropic Growth Control of Polyaniline Nanostructures and Their Morphology-Dependent Electrochemical Characteristics

Role of co-vapors in vapor deposition polymerization.