Effects of FeCl3/ammonium persulfate composite oxidant and magnetic field on film growth rate of polyaniline doped with dodecylbenzenesulfonic acid

Polyaniline (PANI) doped with dodecylbenzenesulfonic acid (DBSA) was synthesized by emulsion polymerization using FeCl₃/ammonium persulfate (APS) as composite oxidant. The effects of different magnetic field (MF) intensities, the molar ratios of FeCl₃/APS, and the concentrations of DBSA on the film growth rate of PANI were analyzed by using a quartz crystal microbalance (QCM) technique. The film growth rate of PANI increased with increasing MF intensity and the concentration of DBSA. However, the film growth rate of PANI decreased with increasing molar ratio of FeCl₃/APS. The polymerization conditions were optimized tentatively by cyclic voltammetry (CV) testing. The peak currents and conductivity were the largest for PANI prepared under the following conditions: MF intensity 0.4 T, molar ratio of FeCl₃/APS 2:1, and concentration of DBSA 0.05 mol/L. The UV–Vis spectra of the PANI polymerization showed that the absorption intensity of PANI polymerized in the presence of MF was greater than that of PANI polymerized in the absence of MF, at the same reaction time.     

Effect of dodecyl benzene sulfonic acid on the preparation of polyaniline/activated carbon composites by in situ emulsion polymerization

Polyaniline (PANI)/activated carbon (AC) composites are prepared by in situ emulsion polymerization using dodecyl benzenesulfonic acid (DBSA). DBSA can play a role as both surfactant and dopant in the process of PANI synthesis. The effect of DBSA on the preparation of PANI/AC composites is investigated in this research. For this purpose, the composites are prepared in micellar solutions with various concentrations of DBSA. It is confirmed using X-ray diffraction (XRD) analysis and Fourier-transform IR (FT-IR) spectroscopy that DBSA actually participates in the PANI doping process. The PANI doped with DBSA (DBSA-PANI) covering the AC surfaces is observed with scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The electrochemical properties of the composites are studied by cyclic voltammetry (CV). The composites show different values of specific capacitance, which was found to be a function of DBSA concentration. The composite prepared in 0.045 M DBSA solution shows the highest specific capacitance (115.2 F g^?1) among the prepared composites. The doping level of DBSA-PANI is increased with the concentration of DBSA in solution.     

Conducting composites of poly(N‐vinylcarbazole), polypyrrole,and polyaniline with 13X‐zeolite

N‐vinylcarbazole (NVC) was polymerized by 13X zeolite alone in melt (65°C) or in toluene (110°C) and a poly(N‐vinylcarbazole) (PNVC)‐13X composite was isolated. Composites of polypyrrole (PPY) and polyaniline(PANI) with 13X zeolite were prepared via polymerization of the respective monomers in the presence of dispersion of 13X zeolite in water (CuCl₂ oxidant) and in CHCl₃ (FeCl₃ oxidant) at an ambient temperature. The composites were characterized by Fourier transform infrared analyses. Scanning electron microscopic analyses of various composites indicated the formation of lumpy aggregates of irregular sizes distinct from the morphology of unmodified 13X zeolite. X‐ray diffraction analysis revealed some typical differences between the various composites, depending upon the nature of the polymer incorporated. Thermogravimetric analyses revealed the stability order as: 13X‐zeolite > polymer‐13X‐zeolite > polymer. PNVC‐13X composite was essentially a nonconductor, while PPY‐13X and PANI‐13X composites showed direct current conductivity in the order of 10^?4 S/cm in either system. However, the conductivity of PNVC‐ 13X composite could be improved to 10^?5 and 10^?6 S/cm by loading PPY and PANI, respectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 913–921, 2006     

Fabrication of carbon nanotubes/polypyrrole/carbon nanotubes/melamine foam for supercapacitor

The carbon nanotubes (CNTs) have been loaded on the melamine foam (MF) to form the composite (CNTs/MF) by dip‐dry process, then polypyrrole (PPy) is coated on CNTs/MF (PPy/CNTs/MF) through chemical oxidation polymerization by using FeCl₃·6H₂O adsorbed on CNTs/MF as oxidant to polymerize the pyrrole vapor. Finally, CNTs are coated on the surface of PPy/CNTs/MF to increase the conductivity of the composite (CNTs/PPy/CNTs/MF) by dip‐dry process again. The composites have been characterized by X‐ray diffraction spectroscopy, scanning electron microscopy and electrochemical method. The results show that the structure of the composites has obvious influence on their capacitive properties. According to the galvanostatic charge/discharge test, the specific capacitance of CNTs/PPy/CNTs/MF is about 184 F g^?1 based on the total mass of the composite and 262 F g^?1 based on the mass of PPy (70.2 wt % in the composite) at the current density of 0.4 A g^?1, which is higher than that of PPy/CNTs/MF (120 F g^?1 based on the total mass of the composite and 167 F g^?1 based on the mass of the PPy). Furthermore, the capacitor assembled by CNTs/PPy/CNTs/MF shows excellent cyclic stability. The capacitance of the cell assembled by CNTs/PPy/CNTs/MF retains 96.3% over 450 scan cycles at scan rate of 20 mV s^?1, which is larger than that assembled by CNTs/PPy/MF (72.5%). © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39779.     

DBSA掺杂聚苯胺的制备、表征及其导电性

采用过硫酸铵(APS)为氧化剂在十二烷基苯磺酸(DBSA)微胶束中化学氧化制备纳米棒状聚苯胺;DBSA既起乳化剂也起掺杂剂的作用。制备的掺杂聚苯胺用红外光谱(FTIR)、紫外光谱(UV-vis)、X-射线衍射(XRD)和扫描电镜(SEM)进行了表征;透射电镜(TEM)下首次观察到了聚苯胺的有序排列结构,晶面间距为5.99 Å。考察了掺杂剂/苯胺、氧化剂/苯胺的摩尔比和反应温度、时间等对聚苯胺电导率影响,最高电导率达到了0.72 S/cm。透射电镜怎能看到5.99     

Copper chloride‐doped polyaniline/multiwalled carbon nanotubes nanocomposites: Superior electrode material for supercapacitor applications

In this study, copper chloride (CuCl₂)‐doped polyaniline (PANI)/multiwalled carbon nanotubes (MWCNTs) nanocomposite (PANI C2 CNT), CuCl₂‐doped PANI (PANI C2) and pure PANI was synthesized by in situ oxidative polymerization method, using ammonium peroxodisulfate as oxidant in HCl medium. These composites were investigated as electrode materials for supercapacitors. The interaction of metal cation (Cu²⁺) with PANI was confirmed by Fourier transform infrared spectroscopy. The morphology of the composites was characterized by field‐emission scanning electron microscopy and high‐resolution transmission electron microscopy analysis. Electrochemical characterizations of the materials were carried out by three electrode probe method, where platinum and saturated standard calomel electrode were used as counter and reference electrode, respectively. 1 M KCl solution was used as electrolyte for all the electrochemical characterizations. The transition metal ion doping enhanced the electrochemical properties of the conducting polymer. Among all the composites, CuCl₂‐doped PANI/MWCNT showed highest specific capacitance value of 724 F/g at 10 mV s⁻¹ scan rate. The Nyquist plot of the polymeric materials showed low equivalent series resistance of the electrode materials. Thermal stability of the composites was examined by thermogravimetric analysis.POLYM. COMPOS., 2013. © 2013 Society of Plastics Engineers     

Facile preparation of conductive paint made with polyaniline/dodecylbenzenesulfonic acid dispersion and poly(methyl methacrylate)

We investigated an easy way to prepare industrially a conductive paint made with polyaniline (PANI)/dodecylbenzenesulfonic acid (DBSA) dispersion and poly(methyl methacrylate) (PMMA) in organic media. First, water‐dispersible PANI doped with DBSA was chemically synthesized with aniline sulfate using ammonium persulfate in water, and the resulting PANI/DBSA was readily extracted from the reaction medium with a mixture of toluene and methyl ethyl ketone (MEK) (toluene:MEK = 1:1 (v/v)), which is useful for industrial applications. The obtained PANI/DBSA organic dispersion was mixed with PMMA organic solution to give the corresponding PANI/DBSA conductive paint containing PMMA. A film prepared with the resulting PANI/DBSA conductive paint was found to possess relatively good conductivity and low surface resistivity for a conductive paint utilized for an electrostatic discharge even at low PANI/DBSA content in the PANI/DBSA–PMMA composite film (the conductivity and the surface resistivity were 9.48 × 10^?4 S cm^?1 and 3.14 × 10⁶ Ω cm^?2, respectively, when the feed ratio of PANI/DBSA:PMMA was 1:39 (w/w)). Furthermore, it was found that the conductivity of the film composed of PANI/DBSA–PMMA composite can be readily and widely controlled by the PANI/DBSA content of the composite or by the amount of DBSA used during the PANI/DBSA synthesis. The highest conductivity of PANI/DBSA–PMMA composite film (7.84 × 10^?1 S cm^?1) was obtained when the feed ratio of PANI/DBSA:PMMA was 1:4 (w/w). Copyright © 2007 Society of Chemical Industry     

Preparation and electrochemistry of nanostructured PPy/graphite nanosheets/rare earth ions composites for supercapacitor

Highly conductive PPy/graphite nanosheets/rare earth ions (PPy/nanoG/RE³⁺) composites were prepared via in‐situ polymerization with p‐toluenesulfonic acid as a dopant and FeCl₃ as an oxidant. The microstructures of nanoG and PPy/nanoG/RE³⁺ were characterized by the SEM and TEM examinations. It was found that nanoG and PPy nanospheres formed the uniform composite with the PPy nanospheres embedded on the nanoG surface and/or filled between the nanoG. The effects of nanoG and RE³⁺ on the electrical conductivity and electrochemical performance of the composites were investigated. The results showed that the nanoG and RE³⁺ as the filler had effect on the conductivity and electrochemical performance of PPy/nanoG/RE³⁺ composites, which played an important role in forming a conducting network in PPy matrix. A specific capacitance of as high as 175 F/g at a current density of 1 A/g was achieved over the PPy/nanoG/Gd³⁺ composite. The capacitance of the PPy/nanoG/Gd³⁺ composite decreased only 5.1% after 800 charging/discharging cycles at a current density of 1 A/g. POLYM. ENG. SCI., 54:2731–2738, 2014. © 2013 Society of Plastics Engineers     

聚苯胺/nano-ATO导电复合材料的原位聚合与表征

用原位聚合法,以十二烷基苯磺酸(DBSA)/HC l混酸为掺杂剂,过硫酸胺(APS)为氧化剂,制备了聚苯胺/掺锑二氧化锡(ATO)导电复合材料。探讨了ATO用量对导电复合材料电导率的影响。在n(苯胺)∶n(APS)∶n(DBSA)=1∶1∶0.7,m(ATO)∶m(苯胺)=0.1∶1时,复合材料室温25℃的电导率最高可达8.35 S/cm,比通常方法合成的聚苯胺和nano-ATO的电导率分别提高约1至2个数量级。通过FTIR、XRD、SEM和TEM对目标物进行了表征,结果表明,苯胺优先在ATO纳米粒子表面聚合,形成聚苯胺包覆ATO的导电复合材料。     

Electrically conductive polyaniline/polyimide microfiber membrane prepared via a combination of solution blowing and subsequent in situ polymerization growth

Dodecylbenzene sulfonic acid (DBSA) doped-polyaniline (PANI) coated conductive polyimide (PI) microfiber membrane was prepared by chemical oxidation polymerization. PI nanofiber membrane was prepared by solution blowing. Fourier transform infrared spectra (FTIR), X-ray photoelectron spectroscopy (XPS) and scanning electron microscope (SEM) proved that the successful preparation of composite microfiber membrane with core-shell structures. At the same time, the PANI had an effect of protection on PI nanofiber, which was detected by thermal gravimetric analysis (TGA). The orthogonal experiments were designed to determine the optimal reaction conditions for the conductivity of PANI/PI microfiber membranes as following: ANI concentration (0.15 mol L^?1), APS concentration (0.1 mol L^?1) and DBSA concentration (0.3 mol L^?1). The conductivity of PANI/PI microfiber membranes could arrive to 3.83 × 10^?2 S cm^?1. Moreover, the PANI/PI microfiber membranes had a superior hexavalent chromium (Cr (VI)) adsorption performance. The factors affecting the performance of hexavalent chromium (Cr (VI)) removal from the aqueous solutions were investigated.     

Preparation of the flexible polypyrrole/polypropylene composite fibrous film for electrochemical capacitor

Polypyrrole (PPy)/polypropylene fibrous membrane (PPF) composite materials with different PPy contents are prepared through in situ chemical oxidation polymerization in the pyrrole atmosphere at room temperature by dissolving the FeCl₃·6H₂O in methanol and acetonitrile as oxidant. The morphology of the composite is examined by scanning electron microscope (SEM), the conductivities of the composites are measured by convenient four‐probe method, and the properties of the capacitor cells assembled by the obtained PPy/PPF are investigated by cyclic voltammetry (CV), galvanostatic charge/discharge, and electrochemical impedance spectroscopy (EIS) measurements. The results show that the morphology, conductivity, and the capacitor property of the composite are influenced strongly by the solvent of the oxidant. The capacitor assembled by the PPy/PPF prepared by using acetonitrile as the solvent for FeCl₃^.6H₂O can adapt for quick charge/discharge, and exhibit the highest capacitance of about 72.5 F g^?1 when the PPy content is about 8.0%. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Multiwalled carbon nanotubes/polypyrrole/graphene/nonwoven fabric composites used as electrodes of electrochemical capacitor

The reduced graphene oxide/nonwoven fabric (rGO/NWF) composites have been fabricated through heating the NWF coated with the mixture of GO and HONH₂·HCl at 130°C, during which the GO is chemically reduced to rGO. Then the composites of polypyrrole (PPy)/rGO/NWF have been prepared through chemically polymerizing pyrrole vapor by using the FeCl₃·6H₂O adsorbed on rGO/NWF substrate as oxidant. Finally, multiwalled carbon nanotubes (MWCNTs) are used as conductive enhancer to modify PPy/rGO/NWF through dip‐dry process to obtain MWCNTs/PPy/rGO/NWF. The prepared composites have been characterized and their capacitive properties have been evaluated in 1.0M KCl electrolyte by using two‐electrode symmetric capacitor test. The results reveal that MWCNTs/PPy/rGO/NWF possesses a maximum specific capacitance (C_sc) of about 319 F g^?1 while PPy/rGO/NWF has a C_sc of about 277.8 F g^?1 at the scan rate of 1 mV s^?1 and that optimum MWCNTs/PPy/rGO/NWF retains 94.5% of initial C_sc after 1000 cycles at scan rate of 80 mV s^?1 which is higher than PPy/rGO/NWF (83.4%). Further analysis reveals that the addition of MWCNTs can increase the charger accumulation at the outer and inner of the composites, which is favorable to improve the stability and the rapid charge‐discharge capacity. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41023.     

Ionic conductivity studies and dielectric studies of Poly(styrene sulphonic acid)/starch blend polymer electrolyte containing LiClO4

Proton and lithium-ion conducting biodegradable solid polymer electrolytes were prepared using blends of poly(styrene sulphonic acid) (PSSA) and starch for supercapacitor applications. The ionic conductivities have been calculated using the bulk impedance obtained through impedance spectroscopy with varying blend ratio and plasticizer. Glycerol as plasticizer improved the film formation property, while lithium perchlorate (LiClO₄) as dopant enhanced the conductivity. The maximum conductivity has been found to be 5.7?×?10^?3?Scm^?1 at room temperature for 80/20 (PSSA/starch) blend ratio. The dielectric studies showed relaxation peaks indicating proton and Li⁺ conduction in the plasticized polymer blend matrix and dielectric modulus also exhibited a long tail feature indicating good capacitance. Differential scanning calorimetry thermograms showed two peaks and decreased with varying blend ratio and plasticizer. A carbon?Ccarbon supercapacitor was fabricated using suitable electrolyte, and its electrochemical characteristics using cyclic voltammetry, AC impedance and galvanostatic charge?Cdischarge were studied. Supercapacitor showed a fairly good specific capacitance of 115?Fg^?1 at 10?mV s^?1.     

Preparation of polyaniline/nickel oxide nanocomposites by liquid/liquid interfacial polymerization and evaluation of their electrical,electrochemical and magnetic properties

A novel route has been developed to synthesize polyaniline (PANI)/nickel oxide (NiO) nanocomposites via liquid/liquid interfacial polymerization where NiO and the initiator were dispersed in the aqueous phase and the monomer was dissolved in the organic phase. The synthesized samples were characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, ultraviolet?visible absorption, X‐ray diffraction, and electrochemical, electrical conductivity and magnetic property measurements. NiO was dispersed uniformly within the PANI matrix. The composites exhibited noticeable improvement in thermal stability and electrical conductivity in comparison with pure PANI. The composites showed excellent electrochemical reversibility at a scan rate of 0.1 V s^?1 and good redox stability even up to 100 cycles. The room temperature magnetic hysteresis measurements show a low value of coercivity for the polymer composites in comparison with NiO. The remnant magnetization (M_r) values were found to be increased with increasing concentration of NiO in the composites. © 2013 Society of Chemical Industry     

Thermal and dc Conductivity Behavior of Fly Ash Filled Polyaniline Composites

In this paper temperature dependence of dc conductivity (σ_dc) of emeraldine base form of polyaniline (PANI) and fly ash filled PANI are presented. Samples were prepared by in situ polymerization of aniline using ammonium persulphate as an oxidant and hydrochloric acid as dopant. Fly ash filled PANI composites were prepared by adding 3 gms of fly ash. Thermal characteristics of samples were measured using differential scanning calorimetry. The dc conductivity (σ_dc) of fly ash filled PANI was found to be on the order of 1.63 × 10^?11 s/cm at room temperature, which was lower than that of pure PANI. The activation energies calculated from σ_dc for PANI and the PANI 3 fly ash system were 1.35 and 1.16 eV, respectively. It was found that addition of fly ash to PANI drastically decreased the enthalpy from 2259.2 to 196.6 mJ. the endothermic peak due to the glass transition temperature shifted from 99.8 to 94.6°C. This was attributed to the change in the morphology of the composites on adding fly ash, as observed in the scanning electron micrographs.     

Study on electrochemical performance of porous integrated PANI-Fe in supercapacitors

The iron-coordinated polyaniline (PANI-Fe) integrated nanomaterials was prepared by chemical oxidative and in-situ electrochemical polymerization, which was applied to supercapacitor electrodes. The N–Fe coordination bond is formed between FeCl₃ and the N of quinone diimine to enhance the interaction of the polyaniline molecular chain. The PANI-Fe electrode material forms a crosslinked porous fiber framework through two-step oxidation, which greatly improves the energy storage capacity of PANI-Fe. PANI-Fe achieves higher capacitance of 642 F g⁻¹ at 1 A g⁻¹ than PANI of 310 F g⁻¹, and maintains high capacitance retention of 82.4 % when the current density increases from 1 to 10 A g⁻¹. According to first-principles calculations, the Fermi energy (N(E)) of PANI-Fe drop down to 0.265 eV from 0.901 eV of PANI, which proves that its conductivity is improved. The change of the electrostatic potential of PANI-Fe indicates that the formation of the N–Fe coordination bond can improve the carrier transport behavior. PANI-Fe has a smaller HOMO-LUMO energy gap than PANI, indicating that the formation of N–Fe coordination bonds can increase the electrical activity of PANI.     

Synthesis,characterization and supercapacitors of electrically conductive PPy/graphene/rare earth ions composites

PPy/graphene/rare earth ions (PPy/GR/RE³⁺) were prepared using an in situ chemical polymerization of the monomer in the presence of FeCl₃ oxidant and p-toluenesulfonic acid dopant. The PPy/GR/RE³⁺ composites were characterized by FT-IR spectroscopy, four-point probe conductivity, scanning electron microscopy and transmission electron microscopy. The maximum conductivity of PPy/GR/Gd³⁺ composites is about 9.71 S/cm found with 1 wt% GR and 2 wt% Gd³⁺ at room temperature. The capacitance of the composite electrodes was investigated with cyclic voltammetry. As results of this study, the PPy/GR/Gd³⁺ was effective to obtain fully reversible and very fast faradaic reaction. Hence, the PPy/GR/Gd³⁺ could contribute to the pseudo-capacitive charge storage. The PPy/GR/Gd³⁺ exhibited higher specific capacitance of ~238 F/g at 1 A/g current density. Thermal gravimetric analysis demonstrates an improved thermal stability of PPy in the PPy/GR/Gd³⁺ composites.     

Doping effects of cerium ion on structure and electrochemical properties of polyaniline

Polyaniline (PANI)/Ce³⁺ and PANI/Ce⁴⁺ composites were successfully prepared by in situ polymerization in an aqueous solution of poly(2‐acrylamido‐2‐methylpropane sulfonic acid) and characterized by Fourier transform infrared spectroscopy, ultraviolet–visible spectroscopy, X‐ray photoelectron spectroscopy, SEM, TEM and electrochemical methods. The results showed that the PANI/Ce ion composites had a high degree of sphericity, high electrical conductivity and good electrochemical performance. The conductivity of PANI/Ce(NO₃)₃ reaches a maximum of 46.76 S cm^?1 at 20 wt% of Ce(NO₃)₃. It is increased by 377% by comparison with that of pure PANI. In particular, the polarization results showed that the corrosion current density (0.47 µA cm^?2) and the inhibition efficiency (97%) of PANI/Ce(NO₃)₃ were better than the results for PANI and PANI/Ce(SO₄)₂ composite. This suggested that the PANI/Ce(NO₃)₃ composite has promising applications in conductive materials, anticorrosion coatings and other related fields. © 2017 Society of Chemical Industry     

Facile synthesis of graphene/polyaniline composite hydrogel for high-performance supercapacitor

The graphene/polyaniline (PANI) composite hydrogel was successfully prepared by a one-step hydrothermal method. The morphology and structure of the sample were characterized by digital camera, scanning electron microscopy, and Fourier transform infrared spectroscopy spectra. By combining the advantages of high conductivity of graphene and high pseudocapacitance of PANI, the composite hydrogel was taken as supercapacitor electrode material. Cyclic voltammetry and galvanostatic charge/discharge experimental results show that the composite has excellent electrochemical performance. The specific capacitance value is 258.5 F g^?1 at a scan rate of 2 mV s^?1 and the specific capacitance value is up to 307 F g^?1 at a current density of 0.2 A g^?1. The specific capacitance value can still maintain 90 % of the initial value after repeating the galvanostatic charge–discharge for 1000 cycles at a current density of 1.0 A g^?1 showing good cycle stability.     

Electrically conducting polyaniline‐PBMA composite films obtained by extrusion

Poly(n‐butyl methacrylate) (PBMA)–polyaniline (PANI) composite films were obtained by extrusion by use of two methods: the first method consisted of polymerizing a thin layer of PANI, with Cl^? as dopant, on the extruded film of PBMA; the second method was based on blends of PBMA and PANI produced by the extrusion of the two polymers by using dodecylbenzene sulfonic acid (DBSA) as dopant. The thermal properties, electrical conductivity, and morphology of the composite films obtained were measured. The sensitivity of the composites films as detectors of hydrogen peroxide and ammonia was evaluated. The change in the electrical resistance on exposure to different aqueous solutions of these components shows a linear behavior. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 179–183, 2003