Nano-composite of polypyrrole/modified mesoporous carbon for electrochemical capacitor application

Nano-thin polypyrrole (PPy) layers were coated on chemically modified ordered mesoporous carbon (m-CMK-3) by an in situ chemical polymerization. Structural and morphological characterizations of m-CMK-3/PPy composites were carried out using field emission scanning electron microscopy. Pseudo-capacitive behavior of the deposited PPy layers on m-CMK-3 was investigated by cyclic voltammetry, galvanostatic charge-discharge and electrochemical impedance spectroscopy. As results of this study, the thin layer of PPy in the composite electrode was effective to obtain fully reversible and very fast Faradaic reaction. A maximum discharge capacity of 427 F g⁻¹ or 487 F g⁻¹ after correcting for weight percent of PPy phase at the current density of 5 mA cm⁻², could be achieved in a half-cell setup configuration for the m-CMK-3/PPy composites electrode, suggesting its potential application in electrode material for electrochemical capacitors.     

Facile synthesis and electrochemical capacitance of composites of polypyrrole/multi-walled carbon nanotubes

Composites of polypyrrole (PPy) and multi-walled carbon nanotubes (MWCNTs) were synthesized by a facile method involving one-step electrochemical deposition from a thin-layer of ionic liquid solution attached on a glassy carbon electrode. The morphology of the composites was characterized by field emission scanning electron microscopy, and the capacitance properties were investigated by cyclic voltammetry (CV). The charge-discharge behavior of the composites prepared in this work was examined by chronopotentiometry at a constant current density for multi-cycle scans. The results show that the PPy/MWCNT composites have a porous 3D nanostructure, with high specific capacitance (SC) of 890 F/g (for the mass of the PPy in the composites) calculated from CV at 2 mV/s in 1.0 M KCl. The stability of the composites in 1.0 M KCl electrolyte was also examined by multi-cycle CV and only 9% decrease of SC value was observed for the 1000 cycles.     

Two-layer materials of polyethylene and a carbon nanotube/cyanate ester composite with high dielectric constant and extremely low dielectric loss

Double-layer materials with one layer being a polyethylene (PE) film and the other layer a multi-wall carbon nanotube (MWCNT)/cyanate ester (CE) resin composite, PE-MWCNT/CE, were prepared. They have high dielectric constant and extremely low dielectric loss. For comparison, MWCNT/CE composites with different contents of MWCNTs were also prepared. Results show that the two kinds of materials have greatly different dielectric properties. With the same content of MWCNTs, the PE-MWCNT/CE material shows a higher dielectric constant and much lower dielectric loss than the MWCNT/CE composite. More specifically, the dielectric constant and loss tangent at 10 Hz of the PE-MWCNT/CE material with 0.5 wt.% MWCNTs are respectively 168 and 0.006, about 1.4 and 2.5 × 10⁻⁵ times the values of the corresponding MWCNT/CE composite. The nature behinds these interesting data was detected from the space charge polarization effect and equivalent circuits. The mechanism for the unique dielectric behavior of the PE-MWCNT/CE materials is that the presence of PE film not only reinforces the space charge polarization, but also subdues the leakage current. On the other hand, based on the discussion on the Cole–Cole plots, an effective method is developed to accurately calculate the relaxation time of space charge polarization in electric conductor/polymer materials.     

Ultrasonic synthesis of highly dispersed Pt nanoparticles supported on MWCNTs and their electrocatalytic activity towards methanol oxidation

A new method of synthesis of highly dispersed Pt nanoparticles with large catalytic surface area on multi-walled carbon nanotubes (MWCNTs) under high-intensity ultrasonic field was developed. The method, with low processing temperature at 25 °C, took only about 5 min. The surface characterization of MWCNTs was carried out by fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy methods. The electrochemical surface area and pore volume of MWCNTs were also examined. The result showed that functional groups of the MWCNTs which favored the high loading and high dispersion of particles and electrochemical surface area of MWCNTs were reinforced in the case of high-intensity ultrasonic field. The Pt/MWCNT catalysts were characterized by energy dispersion X-ray spectra analysis (EDX), transmission electron microscopy (TEM) and X-ray diffraction (XRD) measurements. The prepared Pt nanoparticles were uniformly dispersed on the MWCNT surface. The mean size of Pt particles was 3.4 ± 0.2 nm. The electrocatalytic properties of Pt/MWCNT composites and kinetic characterization for methanol electro-oxidation were investigated by cyclic voltammetry. The Pt/MWCNT catalysts prepared for 5 min in ultrasonic field present excellent electrochemical activities. The schematic of the reaction was also introduced.     

Preparation of high‐k composites with low dielectric loss based on the double‐layer coaxial structure of inorganic/polymer

This study presents a novel and simple modification of cladding multiwalled carbon nanotubes (MWCNTs) using organic polymer and inorganic nanoparticles to synthesize a product, which has a double‐cladding coaxial structure and can be applied as filler in the dielectric field. The first layer of MWCNTs was coated with polyaniline (PANI) through the oxidation–reduction reaction mechanism using Ce(NH₄)₂(NO₃)₆ as oxidizing agent and metal precursor of cerium oxide. Cerium ions on the second cladding layer of MWCNTs were directly deposited from the solution to the surface of the PANI layer forming the double‐cladding hybrid (CeO₂/PANI@MWCNTs). The external inorganic layer provides an insulating shell, which can prevent the contact between the conductive particles and hinder the migration of electrons between the MWCNTs. The intermediate layer of PANI provides the bonding between CeO₂ and the conductive core of MWCNTs, which also shows lower conductivity than carbon nanotubes. The CeO₂/PANI@MWCNTs were compounded with epoxy (EP) resin and formed a dielectric material with the advantage of reducing dielectric loss while ensuring high dielectric constant. The dielectric constant of the coated MWCNTs/EP composites was 194.90 at 10³ Hz with the content of fillers reaching 30 wt %, which is 28 times that of the pure EP. Accordingly, the dielectric loss of 30 wt % coated MWCNTs/EP composites was only 0.09 at 10³ Hz, which is only 2.25 times that of the pure EP. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46299.     

Electrical and dielectric properties of multiwall carbon nanotube/polyaniline composites

In this paper, electrical and dielectric properties of multiwall carbon nanotubes (MWCNTs)/insulating polyaniline (PANI) composites were studied. A mixture of MWCNTs and insulating polyaniline was dispersed in an ethanol solution by ultrasonic process, subsequently dried, and was hot-pressed at 200 °C under 30 MPa. Electrical and dielectric properties of the composites were measured. The experimental results show that the dc conductivities of the composites exhibit a typical percolation behavior with a low percolation threshold of 5.85 wt.% MWCNTs content. The dielectric constant of the composites increases remarkably with the increasing MWCNTs concentration, when the MWCNTs concentration was close to percolation threshold. This may be attributed to the critical behavior of the dielectric constant near the percolation threshold as well as to the polarization effects between the clusters inside the composites.     

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.     

Spray deposited fluoropolymer/multi-walled carbon nanotube composite films with high dielectric permittivity at low percolation threshold

High performance perfluoro alkoxy (PFA) and chemical vapor deposition-grown multi-walled carbon nanotube (MWCNT) composite films with thicknesses of 30 μm were prepared using a scalable spray deposition technique. A homogeneous distribution of MWCNTs within the PFA matrix was confirmed by electron and optical microscopy. Dielectric and AC conductivity measurements showed a significant enhancement of dielectric permittivity for PFA/MWCNT films at low frequencies, and a very weak dependence of dielectric permittivity on temperature in the range 25-230 °C. Very low percolation threshold volume fractions of ca. 0.0043 and 0.0017 were attained for MWCNTs with two different aspect ratios, which have been explained by an inherent feature of spray route, a microcapacitor model and percolation theory. The combination of PFA/MWCNT composites and the spray deposition route provides a promising approach for the fabrication of industrial scale composite films with well-controlled dielectric properties for micro-electronic and high temperature applications.     

Formation of thin boron nitride coating on multiwall carbon nanotube surfaces

Thin boron nitride films were deposited onto outer surfaces of multiwall carbon nanotubes (MWCNTs) by dip coating, which involves infiltration by boric acid solutions and subsequent nitridation of the boron oxide in ammonia flow at 1050 °C. The overall composition of the samples was determined by electron energy loss (EELS) and X-ray photoelectron spectroscopy (XPS), the surface composition and chemical structure of the BN coatings by XPS, the morphology of the BN/MWCNT composites by scanning and transmission electron microscopy (SEM, TEM), and the resistance against oxidation at elevated temperatures by thermal analysis (TGA). It was proved that single and multilayer BN coverage were achieved at the applied experimental conditions, and the coated samples showed significantly increased oxidation resistance compared to the uncoated MWCNTs.     

Amperometric urea biosensors based on the entrapment of urease in polypyrrole films

Urease (Urs) was immobilized in electrochemically prepared polypyrrole (PPy) and the resulting films were characterized by cyclic voltammetry, scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and ultraviolet visible spectroscopy (UV-VIS). The enzymatic activity of Urs entrapped in the PPy matrix was confirmed by the catalytic conversion of urea into carbon dioxide and ammonia, when urea was detected amperometrically at different concentrations in standard samples and commercial fertilizers. The PPy/Urs biosensors exhibited selectivity, a relatively high efficiency at urea concentrations below 3.0 mmol L⁻¹, and a sensitivity to urea of 2.41 μA cm⁻² mmol⁻¹ L.     

Factors influencing MnO2/multi-walled carbon nanotubes composite's electrochemical performance as supercapacitor electrode

Poor crystallined α-MnO₂ grown on multi-walled carbon nanotubes (MWCNTs) by reducing KMnO₄ in ethanol are characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and Brunauer-Emmett-Telle (BET) surface area measurement, which indicate that MWCNTs are wrapped up by poor crystalline MnO₂ and BET areas of the composites maintain the same level of 200 m² g⁻¹ as the content of MWCNTs in the range of 0-30%. The electrochemical performances of the MnO₂/MWCNTs composites as electrode materials for supercapacitor are evaluated by cyclic voltammetry (CV) and galvanostatic charge-discharge measurement in 1 M Na₂SO₄ solution. At a scan rate of 5 mV s⁻¹, rectangular shapes could only be observed for the composites with higher MWCNTs contents. The effect of additional conductive agent KS6 on the electrochemical behavior of the composites is also studied. With a fixed carbon content of 25% (MWCNTs included), MnO₂ with 20% MWCNTs and 5% KS6 has the highest specific capacitance, excellent cyclability and best rate capability, which gives the specific capacitance of 179 F g⁻¹ at a scan rate of 5 mV s⁻¹, and remains 114.6 F g⁻¹ at 100 mV s⁻¹.     

Fast and clean functionalization of carbon nanotubes by dielectric barrier discharge plasma in air compared to acid treatment

Multi-walled carbon nanotubes (MWCNTs) have been functionalized by a dielectric barrier discharge plasma in air and compared to those functionalized in HNO₃. The MWCNTs were prepared by chemical vapor deposition of xylene using ferrocene as a catalyst at 850 °C. Air oxidation followed by acid treatment was used to purify the MWCNTs, which were then annealed in helium. The MWCNTs were functionalized in air in a plasma reactor at room temperature. Quantitative analyses of gases evolved during the temperature programmed desorption of the functionalized nanotubes were carried out using Fourier transform infrared spectroscopy and gas chromatography. The influence of plasma parameters, including power in the range of 8-90 W and treatment time in the range of 1-9 min, on the number of the functional groups was investigated. It is shown that the extent of functionalization increases with increasing discharge power, provided that the exposure time of the MWCNTs in the plasma atmosphere does not exceed a certain period of time. Compared to acid treatment, plasma functionalization offers the advantages of much shorter treatment time, and produces less damage.     

A new high-performance cathode material for rechargeable lithium-ion batteries: Polypyrrole/vanadium oxide nanotubes

Polypyrrole/vanadium oxide nanotubes (PPy/VOx-NTs) as a new high-performance cathode material for rechargeable lithium-ion batteries are synthesized by a combination of hydrothermal treatment and cationic exchange technique. The morphologies and structures of the as-prepared samples are characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared (FTIR) spectroscopy, thermogravimetry and differential scanning calorimeter (TG-DSC) and X-ray powder diffraction (XRD). The results indicate that the organic templates are mainly substituted by the conducting polymer polypyrrole without destroying the previous nanotube structure. Their electrochemical properties are evaluated via galvanostatic charge/discharge cycling, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). It is found that PPy/VOx-NTs exhibit high discharge capacity and excellent cycling performance at different current densities compared to vanadium oxide nanotubes (VOx-NTs). After 20 cycles, the reversible capacity of PPy/VOx-NTs (159.5 mAh g⁻¹) at the current density of 80 mA g⁻¹ is about four times of magnitude higher than that of VOx-NTs (37.5 mAh g⁻¹). The improved electrochemical performance could be attributed to the enhanced electronic conductivity and the improved structural flexibility resulted from the incorporation of the conducting polymer polypyrrole.     

The production of carbon nanotube/epoxy composites with a very high dielectric constant and low dielectric loss by microwave curing

Multiwalled carbon nanotube (MWCNT)/epoxy (EP) composites were developed using microwave curing (m-MWCNT/EP). They have a very high dielectric constant and low dielectric loss. For comparison, composites based on the same components were also prepared by thermal curing (t-MWCNT/EP). Results show that the two types of composites have greatly different dielectric properties. With the same content of MWCNTs, m-MWCNT/EP composites show a much higher dielectric constant and lower dielectric loss than t-MWCNT/EP composites. Specifically, the dielectric constant and loss at 100 Hz of m-MWCNT/EP composite with 0.04 vol% MWCNTs are about 2.5 and 0.05 times the corresponding value of t-MWCNT/EP composites, respectively, because of their different structures. Compared with t-MWCNT/EP composites, the nanotubes in m-MWCNT/EP composites not only have a better dispersion in the matrix, but also align in a direction. An equivalent circuit model was set up to evaluate the influence of dispersion and spatial distribution of MWCNTs on the dielectric properties. It shows that it is possible to control the dispersion and spatial distribution of carbon nanotubes using a different curing technique to obtain high performance composites with unexpected dielectric properties, especially those with very high dielectric constant and low dielectric loss.     

Preparation and characterization of coaxial halloysite/polypyrrole tubular nanocomposites for electrochemical energy storage

Halloysite nanotubes/polypyrrole (HNTs/PPy) nanocomposites with coaxial tubular morphology for use as electrode materials for supercapacitors were synthesized by the in situ chemical oxidative polymerization method based on self-assembled monolayer amine-functionalized HNTs. The HNTs/PPy coaxial tubular nanocomposites were characterized with transmission electron microscope (TEM), X-ray diffraction (XRD), thermogravimetric analysis (TGA), electrical conductivity measurement at different temperatures, cyclic voltammetry (CV), and galvanostatic charge-discharge measurements. The coaxial tubular nanocomposites showed their greatest conductivity at room temperature and a weak temperature dependence of the conductivity from 298 K to 423 K. A maximum discharge capacity of 522 F/g after correcting for the weight percent of the PPy phase at a current density of 5 mA cm⁻² in a 0.5 M Na₂SO₄ electrolyte could be achieved in a half-cell setup configuration for the HNTs/PPy composites electrode, suggesting its potential application in electrode materials for electrochemical capacitors.     

Layer-by-layer assembly of poly(sodium 4-styrenesulfonate) wrapped multiwalled carbon nanotubes with polyaniline nanofibers and its electrochemistry

A simple and versatile method based on noncovalent supramolecular attachment and layer-by-layer (LBL) assembly is proposed to prepare nanostructured hybrid conducting polymer. The negatively charged poly(sodium 4-styrenesulfonate) (PSS) wrapped multiwalled carbon nanotubes (MWCNTs) is doped with cationic polyaniline (PANI) nanofibers via LBL assembly, and a well-defined PANI/MWCNTs composite was obtained. The LBL assembly process is characterized by scanning electron microscopy, energy dispersive spectrometry and electrochemical methods. It was found that PSS wrapped MWCNTs inside the multilayer film can dope nanostructured PANI effectively and shift its electroactivity to a neutral pH environment. Moreover, the conducting composites show amperometric response for hydrogen peroxide with a linear range of 2.0 × 10⁻⁷-1.0 × 10⁻³ mol L⁻¹.     

Multi-walled carbon nanotubes modified by sulfated TiO2 - A promising support for Pt catalyst in a direct ethanol fuel cell

We report the synthesis of multi-walled carbon nanotubes coated with sulfated TiO₂ (S-TiO₂/MWCNTs) as a promising support for Pt catalyst in a direct ethanol fuel cell. Highly dispersed Pt nanoparticles were supported on the S-TiO₂/MWCNT composites by NaBH₄ reduction procedure (Pt-S-TiO₂/MWCNTs). The presence and nature of the catalyst were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, high-resolution transmission electron microscopy. The size of the sulfated TiO₂ product was about 8 nm, and that of the Pt nanoparticle on the S-TiO₂/MWCNT composites was about 5 nm. The Pt-S-TiO₂/MWCNTs were used to study the electrochemical ethanol oxidation reaction using cyclic voltammetry, chronoamperometry and impedance spectroscopy. The results show that Pt-S-TiO₂/MWCNT catalysts show higher catalytic activity for ethanol oxidation compared with Pt supported on non-sulfated TiO₂/MWCNT composites and commercial Pt/C catalysts.     

Polypyrrole/carbon composite electrode for high-power electrochemical capacitors

Nano-thin polypyrrole (PPy) layers with thickness from ∼5 nm to several 10s nm were deposited on vapor grown carbon fibers (VGCF) by an in situ chemical polymerization. Using different concentrations of the pyrrole could control the thicknesses of deposited PPy layers. Surface morphology and thickness of the deposited PPy layers were confirmed by means of scanning electron microscopy and scanning transmission emission microscopy. Pseudo-capacitive behavior of the deposited PPy layers on VGCF investigated by means of cyclic voltammetry. Then, the PPy/VGCF composites were mixed with activated carbons (AC) at various mixing ratios. For the PPy/VGCF/AC composite electrodes, characteristics of specific capacitance and power capability were examined by half-cell tests. As results of this study, it was investigated that nano-thin PPy layer below ∼10 nm deposited on VGCF had high pseudo-capacitance and fast reversibility. Its specific capacitance per averaged weight of active material (PPy) was obtained as ∼588 F g⁻¹ at 30 mV s⁻¹ and maintained as ∼550 F g⁻¹ at 200 mV s⁻¹ of scan rate. Also, from the mixing 60 wt.% of the PPy/VGCF with 25 wt.% of AC, the PPy/VGCF/AC composite electrode exhibited higher power capability maintaining the specific capacitance per active materials of PPy and AC as ∼300 F g⁻¹ at 200 mV s⁻¹ in 6 M KOH.     

Microstructural,wetting, and dielectric properties of plasma polymerized polypyrrole thin films

Polypyrrole (PPy) thin films were synthesized by plasma polymerization technique and investigated the influence of discharge power on microstructural, optical, surface wettability, and dielectric properties of grown films. As deposited PPy films were characterized by X‐ray diffraction (XRD), Fourier transform Infrared spectroscopy (FTIR), Atomic force microscopy, UV‐VIS spectroscopy and dielectric spectroscopy. The broad XRD peak present at 2θ = 23.5° revealed the amorphous nature of grown PPy films. The FTIR spectra displayed characteristic peaks in the wavenumbers regions 3300–3400 cm^?1 and 1635–1700 cm^?1 and respective peaks intensities decreased slightly as a function of discharge powers. Significant modifications in surface morphology of the films were observed as a function of discharge powers and PPy films synthesized at higher discharge power of 50 W demonstrated characteristic surface morphology composed of characteristic vertical cone shaped clusters provided with rms roughness of 3.42 nm. The UV‐VIS absorption spectra evidenced that the optical density values varied as a function of discharge power. The evaluated band gap energies decreased with an increase of discharge power and found to be 2.53 eV for PPy films prepared at higher discharge power of 50 W. The surface wettability studies evidenced that as prepared PPy films were found to be hydrophilic in nature. The dielectric measurements were carried out for “ITO/polymer/ITO” structures in the frequency range 10 mHz to 100 kHz. As evidenced from dielectric spectroscopic measurements, PPy films synthesized at 50 W were demonstrated conductivity value of 6.0 × 10^?12 S/m. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43982.     

Laccase‐catalyzed synthesis of polypyrrole‐multiwalled carbon nanotube composites as energy storage materials for capacitors

Multiwalled carbon nanotubes (MWNTs) were coated with polypyrrole (PPy) using in situ enzymatic polymerization of pyrrole catalyzed by a laccase (benzenediol:oxygen oxidoreductase, EC 1.10.3.2) from Trametes versicolor. Transmission electron microscopy revealed that the MWNTs were uniformly coated with very thin layers of PPy without any indication of globular polymer aggregate formations. The enzymatic synthesis of the MWNTs/PPy composites was quite simple being performed in a one‐pot aqueous solution (pH 4.0) under mild reaction conditions. The potential of the composites with respect to the development of energy storage devices was demonstrated by fabricating a two‐electrode coin cell capacitor (diameter 20 mm, thickness 1.6 mm) utilizing the composites as electrode materials. The capacitance of the cell was 28.0 F g^?1 for the electrode material as measured by a galvanostatic charge–discharge method. The energy density and power density were 2.55 and 805 W kg^?1, respectively, which were close to those of the capacitors classified as ultracapacitors. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43307.