Electrochemical capacitance of well-coated single-walled carbon nanotube with polyaniline composites

Well-coated single-walled carbon nanotube (SWNT) with polyaniline (PANI) composite electrodes with good uniformity for electrochemical capacitors are prepared by the polymerization of aniline containing well-dissolved SWNTs. The capacitance properties are investigated with cyclic voltammetry, charge-discharge tests and ac impedance spectroscopy. The composite electrode shows much higher specific capacitance, better power characteristics and is more promising for application in capacitor than pure PANI electrode. The effect and role of SWNT in the composite electrode are also discussed in detail.     

Potentiodynamic and potentiostatic deposition of polyaniline on stainless steel: Electrochemical and structural studies for a potential application to corrosion control

Polyaniline (PAn) films were electrodeposited on stainless steel 304 (SS) from 0.5 M H₂SO₄ solution containing 0.1 M aniline (An) by using potentiodynamic and potentiostatic techniques. In particular, PAn films were prepared as follows: (i) by cyclic potential sweep (CPS) deposition upon varying the upper potential limit (E_l) of the polymerization potential region between 0.8 and 1.1 V, while the lower potential limit was equal to −0.2 V; (ii) by potentiostatic deposition upon varying the applied potential (E_appl) between 0.8 and 1.1 V. The potential sweep rate (dE/dt) was also varied for the An polymerization during the CPS deposition. Variation of the E_l, dE/dt and E_appl affects the PAn growth leading to films of different electrochemical and structural properties. The electrochemical properties of the PAn were examined by using cyclic voltammetry. Scanning electron microscopy was used to reveal the structure and morphology of the PAn films. Monitoring the open circuit potential (E_OC) of the PAn-coated SS electrode in 0.5 M H₂SO₄ shows that the SS remains in the passive state. PAn films can also provide protection to SS in chloride-containing 0.5 M H₂SO₄ for the studied period of time, although pits were detected during prolonged immersion. The protection efficiency seems to be related with the parameters E_l, dE/dt and E_appl varied during polymerization. The mechanism of the SS protection provided by the PAn coatings is discussed in terms of the active role of PAn in corrosive environments.     

Improvement of electrochemical performance of titania nanowires for supercapacitor electrodes by in-situ growth of polyaniline nanoparticles

Supercapacitors with excellent electrochemical performance are considered the most promising candidates to meet the increasing energy demand. Herein, we developed a novel electrode material for supercapacitors, polyaniline (PANI)-3-aminopropyl triethoxysilane (APTEs)-titania nanowires (TNW), which was synthesized on potassium doped titanium foil via a simple two-step procedure. In the composite, the nano-mesh structure formed by APTEs-coated TNW serves as the framework for the growth of PANI nanoparticles, and PANI nanoparticles act as the electrochemically active part. The specific capacitance of PANI-APTEs-TNW of up to 315.16 mF cm^?2 at 0.2 mA cm^?2 in 1.0 M H₂SO₄ solution is achieved, while that of PANI-TNW is 271.67 mF cm^?2. Meanwhile, the capacitance retention rate of PANI-APTEs-TNW is 86.8% after 1000 cycles under 1.5 mA cm^?2. Compared to PANI-TNW, the better capacitive behavior of PANI-APTEs-TNW is attributed to the anchoring effect of APTEs, which is highly interactive and exhibits compact structures between the TNW and PANI nanoparticles, resulting in a stable structure during the rapid charge-discharge process. This strategy is characterized by its good electrochemical properties, simple equipment, low cost of raw materials, and large-area preparation. Thus, our findings provide an effective method for the design of high-performance supercapacitors and promote their practical applications.     

Fabrication and electrochemical capacitance of hierarchical graphene/polyaniline/carbon nanotube ternary composite film

A film composed of graphene (GN) sheets, polyaniline (PANI) and carbon nanotubes (CNTs) has been fabricated by reducing a graphite oxide (GO)/PANI/CNT precursor prepared by flow-directed assembly from a complex dispersion of GO and PANI/CNT, followed by reoxidation and redoping of the reduced PANI in the composite to restore the conducting PANI structure. Scanning electron microscope images indicate that the ternary composite film is a layered structure with coaxial PANI/CNT nanocables uniformly sandwiched between the GN sheets. Such novel hierarchical structure with high electrical conductivity perfectly facilitates contact between electrolyte ions and PANI for faradaic energy storage and efficiently utilizes the double-layer capacitance at the electrode–electrolyte interfaces. The specific capacitance of the GN/PANI/CNT estimated by galvanostatic charge/discharge measurement is 569 F g⁻¹ (or 188 F cm⁻³ for volumetric capacitance) at a current density of 0.1 A g⁻¹. In addition, the GN/PANI/CNT exhibits good rate capability (60% capacity retention at 10 A g⁻¹) and superior cycling stability (4% fade after 5000 continuous charge/discharge cycles).     

The electrochemical deposition of polyaniline at pure aluminium: electrochemical activity and corrosion protection properties

Polyaniline films were electrodeposited at pure aluminium from a tosylic acid solution containing aniline. These polymer films exhibited similar characteristics as pure polyaniline electrosynthesized at an inert platinum electrode, when removed from their respective substrates and dissolved in NMP. Both polymers had similar molecular weights and similar UV-visible absorption spectra. However, the aluminium substrate had a considerable effect on the electrochemical activity of the films. The polyaniline films deposited at aluminium appeared to lose electroactivity and the electrochemical impedance data were governed by the oxidized aluminium substrate. This is consistent with a galvanic interaction between the polymer and the aluminium substrate, giving rise to oxidation of the aluminium and reduction of the polymer. The polyaniline deposits appeared to offer only a slight increase in the corrosion resistance of aluminium. Surface potential measurements, using a scanning vibrating probe, showed that attack initiated underneath the polymer under anodic polarization conditions, indicating that chloride anions diffuse across the polymer to react at the underlying aluminium substrate.     

pH-controlled morphological structure of polyaniline during electrochemical deposition

Electrodeposition of polyaniline (PAni) was performed across a broad pH range from pH 0.0 to 14.0. PAni films were found to grow from strong acidic environments at much faster rate and appeared to adopt different growth patterns from those grown from higher pH media, thus producing PAni films with very different morphologies ranging from nanofibres to microsized tubules to flakes like structures. The various morphologies of the PAni films were results of homogeneous and heterogeneous nucleation during electrochemical polymerization. These phenomena occurred under specific conditions which could be induced by varying the pH of the reaction media. Characteristic IR absorptions of the films deposited from increasing pH environment indicated little differences in chemical structure of the polymers except for the film grown from pH 14.0. Cyclic voltammetry data also indicated different electron transfer efficiency as a result of different morphology adopted. All except for PAni films obtained from pH 2.0 to 4.0 gave high specific capacitance at around 450 F g⁻¹ in 0.5 M H₂SO₄ and in 1.0 M NaNO₃ (pH 1.0) solution using 1.0 mA cm⁻² charging and discharging current density.     

Preparation and electrochemical investigation of the polyaniline/activated carbon nanocomposite for supercapacitor applications

The polyaniline (PANI)/activated carbon (AC) nanocomposite electrodes were prepared by electropolymerization of aniline monomers on the surface of AC/polyvinyl alcohol (PVA) electrodes for supercapacitor studies. Fourier transforms infrared spectroscopy (FT-IR), X-ray diffraction (XRD), and scanning electron microscopy (SEM) analyses were performed to characterize the structure and morphology of the nanocomposite electrodes. The electrochemical properties of the prepared nanocomposite electrodes and the supercapacitive behavior of the PANI, AC, and AC/PANI/PVA electrodes were investigated using cyclic voltammetry (CV) and galvanostatic charge/discharge measurements, respectively. Morphological studies showed that a thin film of PANI has been uniformly deposited on the porous surface of AC electrode, and an ordered arrangement of nanostructures with interlinked porous network has been made. Electrochemical measurements showed that AC particles prevent the degradation of PANI chains during charge/discharge cycles. The specific capacitance of the AC/PANI/PVA nanocomposite electrode was 338.15 F/g which is higher than that of the pristine AC electrode (0.08 F/g). This is due to the contribution of PANI chains by their pseudocapacitance (redox reaction) properties. Although the specific capacitance of PANI electrode (378.57 F/g) was greater than that of the nanocomposite electrode, the cyclic stability of the PANI electrode was lower than that of the AC/PANI/PVA nanocomposite electrode.     

Use of facile mechanochemical method to functionalize carbon nanofibers with nanostructured polyaniline and their electrochemical capacitance

A facile approach to functionalize carbon nanofibers [CNFs] with nanostructured polyaniline was developed via in situ mechanochemical polymerization of polyaniline in the presence of chemically treated CNFs. The nanostructured polyaniline grafting on the CNF was mainly in a form of branched nanofibers as well as rough nanolayers. The good dispersibility and processability of the hybrid nanocomposite could be attributed to its overall nanostructure which enhanced its accessibility to the electrolyte. The mechanochemical oxidation polymerization was believed to be related to the strong Lewis acid characteristic of FeCl₃ and the Lewis base characteristic of aniline. The growth mechanism of the hierarchical structured nanofibers was also discussed. After functionalization with the nanostructured polyaniline, the hybrid polyaniline/CNF composite showed an enhanced specific capacitance, which might be related to its hierarchical nanostructure and the interaction between the aromatic polyaniline molecules and the CNFs.     

One-dimensional growth and electrochemical properties of polyaniline deposited by a pulse potentiostatic method

One-dimensional growth of polyaniline (PANI) was conducted on carbon cloth through a pulse potentiostatic method. Hydrolysis of PANI was depressed, and the generated PANI film (PPM) displayed improved electroactivities. The specific capacitance of PPM was increased by 39% when compared to that of PANI film made by the conventional potentiostatic method (PM). The influences of the upper limit potential of the pulse potentiometry and the acidity of the polymerization solution on surface morphologies, electroactivities and conformation of the PANI films were studied by SEM, cyclic voltammetry, chronopotentiometry and UV-Vis spectrometry.     

Preparation and electrochemical properties of pitch-based activated carbon aerogels

The porous structure of pitch-based carbon aerogels (P-CAs) can be modified by KOH activation. It is found that decreasing the carbonization temperature of precursor CAs and increasing the mass ratio of KOH to CAs help to the formation of 0.7 nm-sized micropores and 2.7 nm-sized mesopores, respectively. The origin and the pore size of micropores play an important role in controlling electrochemical properties. The carbonization-forming micropores have stronger energy storage efficiency than activation-forming micropores, and only those with diameter below 1 nm (Microp < 1 nm) are the crucial place to storage energy. Due to the substantive increase of the number of the Microp < 1 nm, the highest specific capacitance of the as-prepared activated samples can reach 187.2 F g⁻¹ at 5 mA cm⁻², 1.8 times as large as that of their precursor CAs. Furthermore, this capacitance is still up to 173.3 F g⁻¹ when increasing the current density to 50 mA cm⁻², indicating that the activated samples have a high-rate charge–discharge performance.     

Film mechanical resonance phenomenon during electrochemical deposition of polyaniline

Crystal admittance measurements during potentiodynamic electrodeposition from aqueous HCl of polyaniline films on a thickness shear mode resonator show the phenomenon of film resonance. This special situation arises when the combination of materials properties (film shear modulus and density) and sample nature (film thickness) is such that the acoustic phase shift across the film, φ = π/2 radians. Admittance spectra in the acoustically thick (but pre-film resonance) region were fitted to a standard Butterworth van Dyke (BvD) electrical equivalent circuit (with series L, C, and R elements) to yield film storage and loss shear moduli. From these values, it was possible to calculate φ of the growing film and thereby track the onset of film resonance. As φ approached π/2 radians, the admittance peak rapidly shifted to higher frequencies and changed dramatically in amplitude. An electrical equivalent circuit with parallel L, C, and R elements was used to model film resonance data; this simplified model ignores the contribution of the bathing electrolyte. Agreement of film shear moduli from both models, and of resonant film thickness from the parallel element equivalent circuit model and coulometric extrapolation of pre-resonant responses, supports the basic tenets of the film resonance model. At film resonance, the cyclic voltammetric response changed dramatically; it is speculated that this is a consequence of the unusual polymer dynamics at film resonance.     

A novel method for carbon modification with minute polyaniline deposition to enhance the capacitance of porous carbon electrodes

A novel method was developed for minute deposition of polyaniline onto microporous activated carbon fabric to enhance the capacitance of the carbon serving as electrodes for electrochemical capacitors. The deposition consisted of pre-adsorption of monomer into carbon micropores followed by electrochemical polymerization of the adsorbed monomer in a monomer-free H₂SO₄ solution at 0.85 V vs. Ag/AgCl. In comparison with the conventional polymerization in a monomer solution, the developed deposition resulted in a polymer framework distributed over the vast surface in carbon micropores, thus leading to a lower resistance for ion binding with the polymer in H₂SO₄ during charge-discharge. The lower resistance gave rise to a higher specific capacitance for the deposited polymer. In the assembled two-electrode capacitors, the usage of polyaniline redox reactions to store charges was more prominent for polymer-carbon composite electrodes from the developed method because of the higher electrode open circuit potentials. The present work has demonstrated that a capacitance enhancement of >50% in comparison with bare carbon can be achieved with minute polyaniline deposition (<5 wt.%) using the developed method, while only 22% was reached using the conventional method.     

Effects of the electrical conductivity and orientation of silicon substrate on the synthesis of multi-walled carbon nanotubes by thermal chemical vapor deposition

We studied the effects of the electrical conductivity and orientation of silicon substrate on both catalytic Fe thin film and the structure and morphology of multi-walled carbon nanotube (MWNT) grown by low-pressure chemical vapor deposition. Both p-type Si(100) and Si(111) substrates with three different doping concentrations (high, low, undoped) were used to evaluate the formation of catalytic nanoparticles and the growth of MWNTs. The morphology of catalytic nanoparticles such as size and density was characterized by field-emission scanning electron microscopy, Cs-corrected energy-filtered transmission electron microscopy, and X-ray photoelectron spectroscopy. Structural characteristics of MWNTs grown on different combinations of silicon substrate orientation and electrical conductivities (σ) were also systematically analyzed. Based on the experimental results, growth modes of MWNTs could be controlled by choosing an appropriate combination of σ and orientation of Si substrates.     

Effect of secondary dopants on electrochemical and spectroelectrochemical properties of polyaniline

Polyaniline (PANI) was doped with poly(styrene sulfonic acid) (PSS) via doping-dedoping-redoping procedure. Incorporation of PSS in PANI resulted modifications in electrochemical and electrochromic properties, morphology and polymer structure of the polymer film as evidenced by the results of cyclic voltammetry, in situ UV-vis spectroscopy, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), thermogravimetric analysis and conductivity measurements. PANI doped with PSS was found to have a cross-link/branched structure with a minimum degradation product. The absence of degradation products improves the electrochemical, electrochromic properties and thermal stability of the PANI layer for electrochromic applications.     

Fabrication and characterization of polyaniline coated carbon nanofiber for supercapacitor

Polyaniline coated carbon nanofiber was fabricated using one-step vapor deposition polymerization technique. Fourier transform infrared (FT-IR) spectra and transmission electron microscope (TEM) images indicated that uniform and ultrathin conducting polymer layers were formed on the carbon nanofiber surfaces regardless of the coating thickness. It was also confirmed that the thickness of polyaniline layer could be conveniently tuned by the feeding amount of monomer. The coating thickness was dependent on initiator/monomer ratio, the vacuum pressure of reaction chamber and polymerization temperature. Among them, the vacuum pressure was a major factor to control the coating thickness of polyaniline onto the carbon nanofiber surface. In addition, the electrochemical analysis demonstrated that polyaniline coated carbon nanofiber showed an improved performance as supercapacitor. The specific capacitance of polyaniline coated carbon nanofiber exhibited a maximum value of 264 F/g when the thickness of polyaniline layer was ca. 20 nm.     

Preparation and electrochemical properties of polyaniline doped with benzenesulfonic functionalized multi-walled carbon nanotubes

Nanocomposite of benzenesulfonic functionalized multi-walled carbon nanotubes doped polyaniline (PANi/f-MWCNTs) was synthesized via a low-temperature in situ polymerization method. The PANi/f-MWCNTs composite has a thin film of PANi coating uniformly on the surface of the f-MWCNTs. The electrochemical results show that PANi/f-MWCNTs nanocomposite possesses good rate response, which could ascribe to the uniform structure and the better conductivity of composite as well as the in situ doping/de-doping process between the benzenesulfonic acid groups of f-MWCNTs and PANi chain. In addition, the composite also has better capacity and cyclability than PANi/p-MWCNTs composite. It could attribute to the presence of f-MWCNTs, which makes more electrolyte contact with PANi to participate in faradaic redox reactions and dopes with the PANi polymer chain through the benzenesulfonic acid groups to form stable polyemeraldine salts.     

Improving the electrochemical properties of polyaniline by co-doping with titanium ions and protonic acid

Polyaniline co-doped with titanium ions and protonic acid was synthesized in aqueous H₂SO₄ solution containing Ti(SO₄)₂ (pH 2), and was characterized via Fourier-transform infrared spectra, UV–vis spectroscopy, X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy and cyclic voltammetry. Its conductivity was 2.8 S cm⁻¹ at room temperature (25 °C), which is the same order of magnitude as polyaniline doped with protonic acid (5 S cm⁻¹). Compared with polyaniline doped with protonic acid, it showed a better redox reversibility and cycling stability in aqueous pH 4.0 media, even in an acetate electrolyte (pH 4.0). It could be a promising material for several applications due the increase of the operating pH window of polyaniline in an aqueous environment.     

On the electrochemical and spectroscopic properties of a soluble polyaniline parent copolymer

Copolymers of aniline and 2-ethylaniline can be easily formed by electrochemical or chemical oxidation in acidic medium, but the composition of the polymeric chain differs from the composition of the synthesis solution. Copolymers formed from precursor solutions containing less than 30% (in moles) of 2-ethylaniline show intermediate properties between those of the homopolymers, and these properties vary gradually with the amount of 2-ethylaniline units in the copolymeric chain. The properties of those copolymers have been studied by UV-Vis and resonance Raman spectroscopies, cyclic voltammetry, two-probe conductivity and solubility measurements. Results obtained by these techniques corroborate the formation of a block copolymeric material.     

The effect of anion identity on the viscoelastic properties of polyaniline films during electrochemical film deposition and redox cycling

Acoustic admittance measurements at thickness shear mode resonators were used to determine shear moduli for polyaniline films during their potentiodynamic electrodeposition and subsequent redox cycling in aqueous background electrolyte. Data were acquired for films doped with perchlorate, sulphate or chloride anion. For all media, film shear moduli increased progressively with film thickness, from values consistent with a diffuse fluid-like layer to values typical of a viscoelastic material. At any given thickness, both the storage and loss moduli were largest in perchlorate medium; values in chloride and sulphate media were similar to each other, but smaller than in perchlorate. These measures of polymer dynamics are consistent with a previous classification of polyaniline film behaviour, in which perchlorate-doped films are viewed as compact while chloride- and sulphate-doped films are viewed as more open. In monomer-free background electrolyte solution, both film shear modulus components for all anions increased modestly upon film oxidation. Despite some hysteresis on the timescale of slow scan voltammetry, these variations were chemically reversible. Based on measurements involving deposition from chloride medium and transfer to sulphate medium, film shear moduli respond promptly to changes in dopant identity; this is consistent with rapid redox-driven exchange of anions with the bathing electrolyte.     

Chemical synthesis of cross-linked polyaniline by a novel solvothermal metathesis reaction of p-dichlorobenzene with sodium amide

We reported the chemical synthesis of cross-linked polyaniline (PANI) by a novel solvothermal metathesis reaction of p-dichlorobenzene (C₆H₄Cl₂) with sodium amide (NaNH₂) in benzene at 220 °C. In this method, the aniline monomer and complicated treatment were needless and the yield of final products was over 50%. The as-synthesized brown samples were NMP-soluble but water-insoluble; and they were characterized by XRD, FT-IR, UV-vis absorption, XPS, elemental analysis, TGA, and TEM. It was found that solvents have significant influence on the final product. The predominant mechanism of chain growth in PANI polymerizations was proposed as the ionic S_NAr process; however, further theoretical and experimental investigations are needed to obtain the undoubted evidences. We believe that this novel solvothermal metathesis reaction will give us a new guideline for the synthesis of some polymers.