Carbon/carbon supercapacitors

Supercapacitors, or electrochemical capacitors, are a power storage system applied for harvesting energy and delivering pulses during short periods of time. The commercially available technology is based on charging an electrical double-layer (EDL), and using high surface area carbon electrodes in an organic electrolyte. This review first presents the state-of-the-art on EDL capacitors, with the objective to better understand their operating principles and to improve their performance. In particular, it is shown that capacitance might be enhanced for carbons having subnanometric pores where ions of the electrolyte are distorted and partly desolvated. Then, strategies for using environment friendly aqueous electrolytes are presented. In this case, the capacitance can be enhanced through pseudo-faradaic contributions involving i) surface functional groups on carbons, ii) hydrogen electrosorption, and iii) redox reactions at the electrode/electrolyte interface. The most promising system is based on the use of aqueous alkali sulfate as electrolyte allowing voltages as high as 2 V to be reached, due to the high overpotential for di-hydrogen evolution at the negative electrode.     

Flexible conducting polymer transistors with supercapacitor function

Planar organic electrochemical transistors (OECTs) using PEDOT:PSS as the channel material and nanostructured carbon (nsC) as the gate electrode material and poly(sodium 4‐styrenesulfonate (PSSNa) gel as the electrolyte were fabricated on flexible polyethylene terephthalate (Mylar^®) substrates. The nsC was deposited at room‐temperature by supersonic cluster beam deposition (SCBD). Interestingly, the OECT acts as a hybrid supercapacitor (to give a device that we indicate as transcap). The energy storage ability of transcaps has been studied with two cell configurations: one featuring PEDOT:PSS as the positive electrode and nsC as the negative electrode and another configuration with reversed electrode polarity. Potentiostatic charge/discharge studies show that both supercapacitors show good performance in terms of voltage retention, in particular, when PEDOT:PSS is used as the positive electrode. Galvanostatic charge–discharge characteristics show typical symmetric triangular shape, indicating a nearly ideal capacitive behavior with a high columbic efficiency (close to 100%). © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 96–103     

Cellular adhesion, proliferation and viability on conducting polymer substrates

This work reports a comprehensive study about cell adhesion and proliferation on the surface of different electroactive substrates formed by pi-conjugated polymers. Biological assays were performed considering four different cellular lines: two epithelial and two fibroblasts. On the other hand, the electroactivity of the three conducting systems was determined in physiological conditions. Results indicate that the three substrates behave as a cellular matrix, even though compatibility with cells is larger for PPy and the 3-layered system. Furthermore, the three polymeric systems are electro-compatible with the cellular monolayers.     

超级电容器用炭/导电聚合物复合材料*

炭/导电聚合物复合材料是近年来发展起来应用于超级电容器的一种新型电极材料。炭材料与氧化物的复合材料,或者炭材料与导电聚合物的复合材料,能够将双电层电容与法拉第电容结合,既可提高超级电容器的比电容,改变其充放电电压,又可提高其循环性能。本文综述了近年来国内外各种炭材料,如活性炭,碳纳米管等与导电聚合物复合材料的研究进展,认为炭与导电聚合物的复合材料,尤其是性能优良的炭气凝胶,模板法制备的中孔炭,以及由金属或非金属碳化物与氯气等刻蚀剂反应制备的骨架炭与导电聚合物的复合材料是超级电容器电极材料研究的一个重要发展方向。     

Design of free‐standing microstructured conducting polymer films for enhanced particle removal from non‐uniform surfaces

Efficient removal of particles from topologically‐complex surfaces is of significant import for a range of applications (e.g., explosive residue removal in security arenas). Here, we synthesize next‐generation polymeric particle removal swabs with tuned structural features to elucidate the influence of the polymer microstructure on the removal of trace particles from surfaces. Specifically, microstructured free‐standing films of the conducting polymer polypyrrole (PPy) were synthesized through template‐assisted electropolymerization techniques. The removal of polystyrene microspheres from representative aluminum surfaces of varying roughness was evaluated as a function of the PPy microstructure. PPy‐based microstructured swabs displayed increased particle trapping properties relative to non‐textured PPy‐based swabs and current commercial swabs. This increased effectiveness occurred from the more intimate particle‐swab contact, leading to increased van der Waals interactions for the microstructured swabs. Therefore, this effort provides critical design rules for the production of microstructured conducting polymer materials for their application toward advanced particle removal technologies. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1968–1974     

Synthesis and in situ doping of highly conductive polypyrrole nanocomplexes with binary acids

The synthesis of doped polypyrrole (PPy) nanocomplexes and their size, morphology, doping level, and electrical conductivity are discussed. The synthetic route of doped PPy nanocomplexes is presented by means of the chemical oxidative polymerization and in situ doping process in the presence of a binary acid mixture (hydrochloric acid and perchloric acid). The electrical conductivities of the doped PPy nanocomplexes are enhanced from 0.88 to 4.5 S/cm by the optimum molar ratio of HClO₄ and HCl in the binary acid mixture. In addition, the average particle size of the doped PPy nanocomplexes decreases from 280 to 30 nm with a narrow particle size distribution when increasing the proportion of HClO₄ relative to HCl in the binary acid mixture; this result is confirmed by scanning electron microscopy, transmission electron microscopy, and capillary hydrodynamic fractionation instrument analyses. Moreover, at different molar ratios in the binary acid mixture, the zeta‐potential and oxidation level of the doped PPy nanocomplexes have a confirmed association with particle size and electrical properties. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2329–2336     

Electrically conductive sensors for liquids based on ternary immiscible polymer blends containing polyaniline

Electrically conductive blends, containing two immiscible polymers (ethylene vinyl acetate, EVA‐19, and copolyamide 6/6.9, CoPA) and polyaniline (PANI), were produced by melt processing. These blends showed a preferred localization of PANI in the CoPA phase, thus enhancing the formation of continuous conducting networks. Electrically conductive PANI‐containing filaments produced by a capillary rheometer process at various shear rate levels were studied as sensing materials for a homologous series of alcohols (methanol, ethanol and 1‐propanol). All filaments showed a decreasing resistance upon exposure to these solvents. Filaments exposed to methanol, liquid or vapor, exhibited the highest resistance decrease. This behavior was related to the highest polarity of methanol, compared with ethanol and 1‐propanol. The filaments' rate of production significantly affects the relative resistance change upon exposure to the various alcohols and their reproducibility. Copyright © 2004 John Wiley & Sons, Ltd.     

Paper-based supercapacitors for self-powered nanosystems

Energy storage on paper: paper-based, all-solid-state, and flexible supercapacitors were fabricated, which can be charged by a piezoelectric generator or solar cells and then discharged to power a strain sensor or a blue-light-emitting diode, demonstrating its efficient energy management in self-powered nanosystems.     

Conducting graft copolymers of poly(3‐methylthienyl methacrylate) with pyrrole and thiophene

A thiophene‐functionalized methacrylate monomer (3‐methylthienyl methacrylate) was synthesized via the esterification of 3‐thiophene methanol with methacryloyl chloride. The methacrylate monomer was polymerized by free‐radical polymerization in the presence of azobisisobutyronitrile as the initiator. Graft copolymers of poly(3‐methylthienyl methacrylate) (PMTM2) and polypyrrole and of PMTM2 and polythiophene were synthesized by constant‐potential electrolyses. p‐Toluene sulfonic acid, sodium dodecyl sulfate, and tetrabutylammonium tetrafluoroborate were used as the supporting electrolytes. PMTM2‐coated platinum electrodes were used as anodes in the polymerization of pyrrole and thiophene. Moreover, the oxidative polymerization of poly(3‐methylthienyl methacrylate) (PMTM1) was studied with FeCl₃ as the oxidant. The self‐polymerization of PMTM1 was also investigated by galvanostatic electrolysis both in dichloromethane and in propylene carbonate. The structures of PMTM1 and PMTM2 were investigated by several spectroscopic and thermal methods. The grafting process was elucidated with conductivity measurements, Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analysis, and scanning electron microscopy studies. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4131–4140, 2002     

Decorating Polypyrrole Nanotubes with Au Nanoparticles by an In Situ Reduction Process

Au nanoparticle‐decorated polypyrrole nanotubes (defined as PPy/Au nanocomposites) are prepared by an in situ reduction process. Polypyrrole (PPy) nanotubes are prepared by a self‐degraded template method, and Au nanoparticles are deposited in situ by the reduction of HAuCl₄. The size and uniformity of the Au nanoparticles that decorate the PPy nanotubes can be controlled by adjusting the experimental conditions, such as the stabilizers used and the reaction temperature. The morphologies and optical properties of the nanocomposites have been characterized by scanning electron microscopy, transmission electron microscopy, UV‐vis, and FT‐IR spectroscopy. Conductivity measurements show that the conductivities of the nanocomposites decrease with a decrease of temperature, and the conductivity–temperature relationship obeys the quasi‐one dimensional variable range hopping model.

     

Design of New Reaction Fields for Spherical Polypyrrole Particle Synthesis

Summary: Polypyrrole conducting polymers have been investigated widely for various applications because of their thermal and environmental stability and good electrical conductivity. Using chemical oxidative polymerization for the synthesis of polypyrrole particles, the reaction rate is very fast. In this study, we designed two new reaction fields for the synthesis of spherical polypyrrole nanoparticles. In the first system, oxidative polymerization of monomer droplets infused in a water/oil (W/O) emulsion reaction field was investigated. The second system employed dispersed monomer in an aqueous solution with a low concentration of oxidant in which polymerization was augmented by ultrasonic irradiation. Effective control of the reaction rate was important for enabling the synthesis of fine spherical polypyrrole particles.     

Ionic IPNs as novel candidates for highly conductive solid polymer electrolytes

Five ionic imidazolium based monomers, namely 1‐vinyl‐3‐ethylimidazolium bis(trifluoromethylsulfonyl)imide (ILM1), 1‐vinyl‐3‐(diethoxyphosphinyl)‐propylimidazolium bis(trifluoromethylsulfonyl)imide (ILM2), 1‐[2‐(2‐methyl‐acryloyloxy)‐propyl]‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide (ILM3), 1‐[2‐(2‐methyl‐acryloyloxy)‐undecyl]‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide (ILM4), 1‐vinyl‐3‐ethylimidazolium dicyanamide (ILM5) were prepared and used for the synthesis of linear polymeric ionic liquids (PILs), crosslinked networks with polyethyleneglycol dimethacrylate (PEGDM) and interpenetrating polymer networks (IPNs) based on polybutadiene (PB). The ionic conductivities of IPNs prepared using an in situ strategy were found to depend on the ILM nature, T_g and the ratio of the other components. Novel ionic IPNs are characterized by increased flexibility, small swelling ability in ionic liquids (ILs) along with high conductivity and preservation of mechanical stability even in a swollen state. The maximum conductivity for a pure IPN was equal to 3.6 × 10^?5 S/cm at 20 °C while for IPN swollen in [1‐Me‐3‐Etim] (CN)₂N σ reached 8.5 × 10^?3 S/cm at 20 °C or 1.4 × 10^?2 S/cm at 50 °C. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4245–4266, 2009     

Polypyrrole electrodeposition on inorganic semiconductors CuInSe2 and CuInS2 for photovoltaic applications

Thin polypyrrole (PPy) layers with an average thickness of about 0.5 μm were deposited, using potentiostatic and galvanostatic techniques, on CuInSe₂ (CISe) structures prepared electrochemically on glass/ITO substrates and on CuInS₂ (CIS) structures fabricated on Cu tape substrates. The polymer layer of p-type is considered as an alternative to the traditional buffer layer and window layer in the conventional cell structure. The deposition proceeded from an aqueous solution containing sodium naphthalene-2-sulfonate as a dopant. In order to prepare stable PPy films of high quality with a good adherence to the surface of inorganic semiconductors CIS and CISe, the optimal concentrations of reagents, current densities and electrodepositing potentials were selected experimentally. Electrochemical polymerization of pyrrole to PPy on CIS surfaces is faster under white light irradiation and the polymerisation starts at lower potential than in the dark. Significant photovoltage and photocurrent of the fabricated CISe/PPy and CIS/PPy structures have been observed under standard white light illumination.     

Recent progress in conductive polymeric materials for biomedical applications

Advanced polymeric materials undoubtedly constitute one of the most promising classes of new materials due to their intriguing electronic, optical, and redox properties. The incredible progress in this area has been driven by the development of novel synthetic procedures owing to the emergence of nanotechnology and by the large array of applications. In particular, hybridization of polymeric materials with nanomaterials has allowed the production of promising functional materials with tailored properties and functionalities for targeted biomedical applications. Consequently, sufficient researchers have carried out imperative studies on these advanced polymeric materials over the last decade. Beyond scientific and fundamental interest, such advanced materials are conspicuous from technological perspectives as well. In this review, we accentuate the proliferation of advanced polymeric materials in diverse biomedical applications.     

Solution route to inorganic nanobelt‐conducting organic polymer core‐shell nanocomposites

A facile and versatile solution‐based approach was developed to prepare semiconductor metal oxide nanobelt‐conducting organic polymer core‐shell nanocomposites. Well‐defined nanobelts of several types of oxide nanobelts were combined with conducting polymer [polypyrrole (PPy) and polyaniline (PANi)] via in situ polymerization in aqueous solution to obtain a new type of inorganic–organic composite nanostructure. Samples were characterized by using X‐ray diffraction, scanning electron microscopy, transmission electron microscopy, Fourier transform infrared, electron energy loss spectra, high‐resolution transmission electron microscopy, and ultraviolet–visible techniques. Electron energy loss spectra revealed the existence of C?C and C? N bonds in coating layers to prove the encapsulation of PPy or PANi. The red‐shift of absorption band at high‐energy was observed for PPy‐encapsulated composites via ultraviolet–visible spectroscopy, and significant absorption band shifts were also encountered to PANi‐encapsulated composites, which suggest possibilities of band‐gap tuning of such metal oxide‐conducting polymer composites to be applied especially in solar cell devices. However, the sacrifice of nanobelts‐core led to hollow structures of PPy and PANi, which expands the synthetic strategies to prepare conducting polymer nanotubes. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2892–2900, 2005     

In situ polymerization and morphology of polypyrrole obtained in water‐soluble polymer templates

Several water‐soluble polymers were used as templates for the in situ polymerization of pyrrole to determine their effect on the generation of nanosized polypyrrole (PPy) particles. The polymers used include: polyvinyl alcohol (PVA), polyethylene oxide (PEO), poly(vinyl butyral), polystyrene sulfonic acid, poly(ethylene‐alt‐maleic anhydride) (PEMA), poly(octadecene‐alt‐maleic anhydride), poly(N‐vinyl pyrrolidone), poly(vinyl butyral‐co‐vinyl alcohol‐co‐vinyl acetate), poly(N‐isopropyl acrylamide), poly(ethylene oxide‐block‐propylene oxide), hydroxypropyl methyl cellulose, and guar gum. The oxidative polymerization of pyrrole was carried out with FeCl₃ as an oxidant. The morphology of PPy particles obtained after drying the resulting aqueous dispersions was examined by optical microscopy, and selected samples were further analyzed via atomic force microscopy. Among the template polymers, PVA was the most efficient in generating stable dispersions of PPy nanospheres in water, followed by PEO and PEMA. The average size of PPy nanospheres was in the range of 160 nm and found to depend on the molecular weight and concentration of PVA. Model reactions and kinetics of the polymerization reaction of pyrrole in PVA were carried out by hydrogen ¹H NMR spectroscopy using ammonium persulfate as an oxidant. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

钛双极片上网印导电聚合物——碳纳米管复合物及其在水型不对称超级电容器中的电化学性能

用导电聚合物（聚吡硌、聚苯胺）与碳纳米管（经酸处理）复合物（ECP-CNT）以及功能添加剂（表面活性剂：苄索氯铵 benzethonium chloride,粘结剂：聚乙烯醇 polyvinyl alcohol）配成水型印泥（aqueous ink),在钛片（厚度：0.1 mm）上网印（screen printing）成所需载量及面积（例如：75 mg cm^-2,100 cm²）的均匀的ECP-CNT膜. 以该膜为正极,网印活性炭（pigment black）膜为负极,3.0 mol L^-1 KCl 或 1.0 mol L^-1 HCl 为电解质,组装不对称超级电容器. 用循环伏安、恒电流充放电、电化学阻抗、光及电显微等方法研究了ECP-CNT复合物、网印膜、单池以及由双极片（bipolar plate）连接的多池堆（multi-cell stack）. 以两片印刷面积为100 cm² 的钛双极片组装成三池堆,得到较好的技术指标：堆电压3.0 V,电极电容1.29~1.83 F cm^-2,比能量2.30~3.24 Wh kg^-1,最大比功率1.04 kW kg^-1.     

Multilayer films composed of conductive poly(3‐hydroxybutyrate)/carbon nanotubes bionanocomposites and a photoresponsive conducting polymer

In order to develop new electronic devices, it is necessary to find innovative solutions to the eco‐sustainability problem of materials as substrates for circuits. We realized a photoresponsive device consisting of a semiconducting polymer film deposited onto optically semitransparent and conductive biodegradable poly(3‐hydroxybutyrate) (PHB)/carbon nanotube (CNT) substrates. The experiments indicated that the PHB‐CNT bionanocomposite substrate behaves as an optical window trapping electric charges produced by the photoexcitation of the semiconducting polymer. Such PHB‐CNT functional substrates are expected to be attractive for eco‐friendly electronics. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 596–602