Preparation of porous nanorod polyaniline film and its high electrochemical capacitance performance

Nano-sized polyaniline (PANI) films were electrochemically deposited onto an ITO substrate by a pulse galvanostatic method (PGM) in an aqueous solution. The morphology of the as-prepared PANI film was characterized using a field emission scanning electron microscope (FESEM). It was observed that the as-prepared PANI films were highly porous, and showed a nano-sized rod-like or coralline-like morphology depending on the charge loading performed in the electropolymerization process. Furthermore, the PANI films were electrochemically measured by the galvanostatic charge–discharge (GCD), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) tests in 1 mol L^?1 HClO₄ solution. The results showed that such PANI films had a favorable electrochemical activity and an excellent capacitance. The rod-like PANI film prepared with the charge loading of 1000 mC showed the highest discharge capacitance of 569.1 F g^?1 at a low current density of 1 A g^?1. The discharge capacitance retained 97.7% after 1000 cycles at a large current density of 10 A g^?1.     

Electrosynthesis of polyaniline films on titanium by pulse potentiostatic method

Polyaniline (PANI) was synthesized on titanium electrode from aqueous solution containing 0.3 mol L⁻¹ aniline and 1 mol L⁻¹ HNO₃ by pulse potentiostatic method. The chronoamperogram during polymerization process of aniline was recorded. The effects of the synthesis parameters, such as anodic pulse duration (t_a), cathodic pulse duration (t_c), lower limit potential (E_c) and upper limit potential (E_a), on the morphology and electroactivity of the PANI films were investigated by scanning electron microscopy (SEM) and cyclic voltammetry (CV). SEM results present that flake, mica-like, quasi-fibrous and nano-fibrous PANI film could be synthesized with various polymerization parameters. Under the following conditions, t_a = 0.8 s, t_c = 0.1 s, E_c = 0 V and E_a = 1.0 V, high quality nano-fibrous PANI film with the best electroactivity was obtained. The CV results show that the PANI films with different morphologies, which were prepared under the same anodic polymerization charge, have obvious different characteristics. This means that the PANI films with different morphologies have different electrochemical activity.     

Composite films of nanostructured polyaniline with poly(vinyl alcohol)

The uniform composite films of nanostructured polyaniline (PANI) (e.g. nanotubes or nanorods with 60–80 nm in diameter) were successfully fabricated by blending with water-soluble poly(vinyl alcohol) (PVA) as a matrix. The PANI nanostructures were synthesized by a template-free method in the presence of β-naphthalene sulfonic acid (β-NSA) as a dopant. The molecular structures of PANI–β-NSA and the related composite films were characterized by UV–Vis absorption spectrum, FTIR spectrum and X-ray diffraction. It was found that the electrical, thermal and mechanical properties of the composite films were affected by the content of nanostructured PANI–β-NSA in the PVA matrix. The composite film with 16% PANI–β-NSA showed the following physical properties: room-temperature conductivity is in the range 10⁻² S/cm, tensile strength ∼603 kg/cm², tensile modulus ∼4.36×10⁵ kg/cm² and ultimate elongation ∼80%.     

Preparation and characterization of polyaniline film on stainless steel by electrochemical polymerization as a counter electrode of DSSC

Polyaniline (PANI) films were electrodeposited on stainless steel 304 (SS) from 0.5 M H₂SO₄ solution containing 0.3 M aniline by potentiostatic techniques to prepare a low cost and non-fragile counter electrode in dye-sensitized solar cell (DSSC). The compact layer, micro-particles, nanorods and fibrils were observed on the top of PANI films with different applied potentials (E_appl) by SEM. Then the conductivity and electrochemical test illuminated that a polyaniline film with the highest conductivity and best electrocatalytic activity for I₃^?/I^? reaction was electrodeposited at 1.0 V E_appl. Finally, the photoelectric measurement showed that the energy conversion efficiency of DSSC with the PANI electrode was increased with the E_appl decreasing. And the efficiency of DSSC with PANI counter electrode at 1.0 V was higher than that with Pt electrode, owing to the loosely porous structure, high conductivity and excellent catalytic activity of PANI electrode.     

Kinetic study of the electrochemical degradation of polyaniline

The kinetics of the electrochemical degradation of polyaniline (PANI) layers, deposited by electropolymerization and chemical polymerization onto platinum electrode, was investigated in an acid aqueous solution. The degradation rate was shown to depend greatly on the electrode potential applied. First-order rate constants of degradation, obtained from the kinetic data, were shown to vary between 2.87×10⁻⁵ and 3.11×10⁻³ s⁻¹ for thick PANI films, having the electrochemical charge density of 14 mC/cm², and between 2.0×10⁻⁵ and 3.60×10⁻³ s⁻¹ for thin PANI films, having the charge density of 1.5 mC/cm², within the electrode potential range of 0.3–0.9 V versus Ag/AgCl. Two linear regions were found to present on the dependencies of logarithm of the first-order degradation rate constant on electrode potential, one of them having a slope of 0.44 and 1.34 V⁻¹ within electrode potential limits of 0.3–0.6 V, and another one having a slope of 6.37 and 6.39 V⁻¹ within potential limits of 0.6–0.9 V, for thick and thin polymer films, respectively. The results obtained show that the electrochemical degradation of PANI films proceed at a remarkable rate even at low electrode potential values.     

Electrophoretic deposition of manganese dioxide–carbon nanotube composites

Nanofibers of manganese dioxide have been prepared by a chemical precipitation technique. Electron microscopy studies of the nanofibers showed a large aspect ratio with a length ranged from 0.1 to 1 μm and a diameter of about 2–4 nm. Electrophoretic deposition (EPD) method has been developed for the fabrication of composite films containing manganese dioxide nanofibers and multiwalled carbon nanotubes (MWCNT) for application in electrochemical supercapacitors (ES). Film thickness was varied in the range of 1–20 μm by variation in deposition time and voltage. The method enabled the formation of porous nanostructured composite films with pore size of 10–100 nm. Cyclic voltammetry (CV) data for the films tested in the 0.1 M Na₂SO₄ solutions showed ideal capacitive behavior and high-specific capacitance (SC) in the voltage window of 0–1.0 V versus standard calomel electrode (SCE). Composite films showed higher SC compared to the films without MWCNT. The SC decreased with increasing film thickness and increasing scan rate. Obtained results indicate that EPD is a promising method for the fabrication of manganese dioxide electrodes for ES.     

The manufacture and properties of polyaniline nano-films prepared through vapor-phase polymerization

We succeeded in the chemical preparation of nano-level thick polyaniline (PANI) emeraldine salt films on plastic substrate by an in situ vapor-phase deposition (VDP) polymerization method under ambient conditions, using a self-assembly method which is unprecedented. Homogeneous conductive PANI thin films were uniformly fabricated at nano-level thickness (20–100 nm), but their morphologies could grow as polycrystalline grains of a highly ordered structure, depending on the deposition conditions. The grain size was also controlled between 30 and 100 μm depending on the deposition time/temperature. The surface resistance of PANI films was enhanced up to 10⁴ Ω/square with crystallization and light transmittance was increased up to 90% in the case of a film less than 30 nm thick. A typical spectrum for the oxidized PANI, the emeraldine salts form, showing π–π^* transition and a polaron lattice were observed by UV–visible/IR and infrared /Raman spectroscopy.     

Synthesis and characterization of polyaniline–ZnO composite and its dielectric behavior

Films of polyaniline (PANI) and PANI–zinc oxide (ZnO) composites have been synthesized by solution cast and spin coating technique. The ZnO powder of particle size 100–200 nm was synthesized by sol–gel technique and the polyaniline was synthesized by chemical oxidative polymerization of aniline. The composite films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and Fourier transform infra red (FTIR) and the results were compared with polyaniline films. Dielectric properties of PANI and PANI–ZnO composite films have been investigated between frequency ranges of 8.5 and 13.0 GHz. The ‘a’ lattice parameter of ZnO was found to increase and the ‘c’ lattice parameter was found to decrease after ZnO–PANI composite formed. The characteristic FTIR peaks of PANI were found to shift to higher wave number in ZnO–PANI composite. These observed effects have been attributed to interaction of ZnO particles with PANI molecular chains. Dielectric constant of PANI–ZnO composite film was found to be smaller than the PANI film. The decrease of dielectric constant in PANI–ZnO films as compared to PANI was attributed to the interfaces formed between ZnO particles and PANI.     

Optical evidence of electrochemical modification of polyaniline induced by tetra-fluoro-hydroquinone

We have made an attempt to study electrochemically induced modification of ITO/PANI electrode in tetra-fluoro-hydroquinone (4F-hydroquinone) solution. The conditions at which the host molecule (of 4F-hydroquinone) incorporates into polyaniline were investigated, and the modifications in PANI electrode were monitored by optical absorption spectra measurements.PANI films were exposed to three different modifying conditions: a long-cycle polarization in acid solutions (pH range 0.4–3.2, potential limits between −0.35 and 0.8 V versus SCE) without and with 4F-hydroquinone added and a chemical interaction between PANI and 4F-quinone solution for different times at pH 6. We found that modification is a pH-dependent process and can only occur at pH above 3. Cyclic treatment in electrolyte containing 4F-hydroquinone at pH 3.2 leads to 4F-hydroquinone residue incorporation into the polymer backbone that can be viewed as a new optical absorption band of the polymer (550–600 nm). Other optical transitions of PANI are also changed due to modification. A π–π¹ transition (320–350 nm) is broader and seems to contain two components. A localized polaron absorption (435–450 nm) is several folds more intensive in modified PANI. A conduction band absorption (800–820 nm) shows a blue shift and this band still appears at potentials where the loss of conductivity has occurred for non-modified polymer. We have proposed that modification emerged from interaction of the acid polymer centers and 4F-hydroquinone molecules oxidized during cycling.     

Investigation of polyaniline co-doped with Zn2+ and H+ as the electrode material for electrochemical supercapacitors

Polyaniline co-doped with Zn²⁺ and H⁺ was synthesized in aqueous HCl solution containing ZnCl₂, and tested for its supercapacitive behavior in three-electrode or two-electrode system with 1.0 M H₂SO₄ as electrolyte by cyclic voltammetry, charge–discharge and electrochemical impedance spectroscopy (EIS). Scanning electron microscopy (SEM) and Fourier transform infrared (FTIR) techniques were employed for characterization of polyaniline co-doped with Zn²⁺ and H⁺. Compared with polyaniline doped with H⁺, it shows a larger specific capacitance of 369 F g^?1. Moreover, the specific capacitance remains 90% after 1000 cycles at a current density of 0.5 A g^?1, indicating good cycleability.     

Chemical synthesis of cobalt oxide thin film electrode for supercapacitor application

Cobalt oxide thin film electrode was grown on copper substrate from an aqueous alkaline bath containing cobalt chloride as a cobalt source by adopting simple and inexpensive chemical deposition method and characterized for structural and morphological studies. The supercapacitive properties of cobalt oxide electrode were studied in aqueous KOH electrolyte solution. The effect of electrolyte concentration on specific capacitance and the stability of cobalt oxide electrode were studied. The highest specific capacitance achieved with cobalt oxide films was 118 F g^?1. The specific energy (E), specific power (P) and coulomb efficiency (η%) were 5.8 Wh kg^?1, 0.33 kW kg^?1 and 93.44%, respectively.     

Microwave study of chemically synthesized conducting polyaniline on alumina

Polyaniline (PANI) thin film on alumina was prepared by the chemical oxidation of aniline with ammonium peroxydisulphate in acidic aqueous medium. DC conductivity, microwave transmission and reflection, microwave conductivity, shielding effectiveness and microwave dielectric constant of the conducting PANI films are reported. DC conductivity was between 0.15 × 10^?3 and 3.13 × 10^?3 S/cm. Microwave conductivity was between 0.2 and 10 S/cm. The PANI films coated on alumina gave shielding effectiveness value of ?1 to ?4 db. The ?′ was between 2 and 350 whereas ?″ was between 437 and 60. Measurements have been carried over the frequency range of 8.2–18 GHz.     

RuOx/polypyrrole nanocomposite electrode for electrochemical capacitors

In this study, ruthenium oxide-polypyrrole (RuOx-PPy) composite nanostructures were prepared as electrode materials for electrochemical capacitors. Pyrrole was electrochemically polymerized in the pores of an anodized aluminum oxide (AAO) template. RuOx was further deposited on the surface of the PPy nanorod array by an electrochemical method. The morphology and composition of the RuOx-PPy nanocomposites were observed by SEM and EDX. The capacitive performance of the RuOx-PPy nanocomposites was investigated by the galvanostatic charge/discharge test as a function of the amount of RuOx. The maximum specific capacitance of the RuOx-PPy nanocomposite electrode was 419 mF cm^?2/681 F g^?1.     

Preparation of polyaniline–TiO2 composite and its comparative corrosion protection performance with polyaniline

Due to strict environmental regulations on the usage of chromate in the coating industries, search for effective inhibitive pigment in replacing those chromate pigments has become necessary. In recent years it has been shown that electrically conducting polymers such as polyaniline (PANI) incorporated coatings are able to protect steel due to their passivating ability similar to that of chromates. This work presents the comparative corrosion protection performance of the coatings containing polyaniline and polyaniline–TiO₂ composite (PTC) on steel in acrylic binder. The PANI and PTC were prepared by chemical oxidative method of aniline by ammonium persulfate. The polymers were characterized by FTIR, XRD and SEM. The corrosion protection performance of the coatings containing PANI and PTC on steel was evaluated by immersion test in 3% NaCl for 60 days and salt fog test for 35 days. The performance of the coatings in both the tests was investigated by open circuit potential measurements and EIS technique. It has been found that the open circuit potential values of PTC containing coating are more nobler by 50–200 mV in comparison to that of coatings with PANI. Besides, the resistance values of the coating containing PTC were more than 10⁷ Ω cm² in the 3% NaCl immersion test after 60 days and 10⁹ Ω cm² in the salt fog test of 35 days which were two orders high in comparison to that of PANI containing coatings. The better performance of PTC containing coatings may be due to uniform distribution of polyaniline which can form uniform passive film on the iron surface.     

De-doped polyaniline nanofibres with micropores for high-rate aqueous electrochemical capacitor

Polyaniline nanofibres have been prepared without any template or surfactant. Although the morphology of polyaniline is well kept after dealing with aqueous ammonia, de-doped polyaniline nanofibres with micropores are of better electrochemical capacitor performances in 1 M H₂SO₄ aqueous solution. Its specific capacitance is 593 F g^?1 at a constant current density of 2.5 A g^?1, and can be subjected to charge/discharge over 5000 cycles in the voltage range of 0–0.65 V. Moreover, its capacitance retention ratio reaches circa 87% with the current densities increasing from 2.5 A g^?1 to 15 A g^?1.     

Efficient electrochromic nickel oxide thin films by electrodeposition

Nickel oxide (NiO) thin films were prepared by electrodeposition technique onto the fluorine doped tin oxide (FTO) coated glass substrates in one step deposition at 20, 30, 40 and 50 min deposition times respectively. The effect of film thickness (thereby microstructural changes) on their structural, morphological, optical and electrochromic properties was investigated. The mass change with potential and cyclic voltammogram was recorded in the range from +0.3 to ?0.8 V versus Ag/AgCl. One step deposition of polycrystalline cubic phase NiO was confirmed from X-ray diffraction study. Optical absorption study revealed direct band gap energy of 3.2 eV. The optical transmittance of the film decreased with increase in film thickness. A uniform granular and porous morphology of the films deposited for 20 min was observed. The film becomes more compact and devoid of pores when deposition time was increased to 30 min. Thereafter severe cracks are observed. All the films exhibit anodic electrochromism in OH^? containing electrolyte (0.1 M KOH). The maximum coloration efficiency of 107 cm²/C and electrochemical stability of up to 10⁴ colour/bleach cycles were observed for the films deposited for 20 min (film thickness of 104 nm).     

Analysis of electrochemical impedance of polypyrrole|sulfate and polypyrrole|perchlorate films

PPy|SO₄ and PPy|ClO₄ films have been synthesized and investigated in K₂SO₄, ZnSO₄ and NaClO₄ aqueous solutions by electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV) and electron probe microanalysis (EPMA) methods. On the basis of obtained data and calculated impedance parameters as the potential functions, the role of different processes (diffusion of ions, double-layer charging, adsorption and charge transfer) in oxidized, partially reduced and reduced PPy films is estimated. The lowest pseudocapacitance values (from n × 10⁻⁶ to n × 10⁻⁴ μF cm⁻² for 1 μm film), independent of solution concentration, were established for PPy|SO₄ in ZnSO₄. This phenomenon is related with strongly aggravated film reduction process in the solution of double-charged cations. In the case of PPy|ClO₄ in NaClO₄ and PPy|SO₄ in K₂SO₄,where the mono-charged cations participate in redox process, the capacitance values are in the range from: n × 10⁻³ to n × 10⁻² μF cm⁻² and even somewhat higher for PPy|ClO₄ system at oxidized state. The calculated effective diffusion coefficients of ions D remain inside the range from n × 10⁻¹² to n × 10⁻¹⁴ cm² s⁻¹ for PPy|SO₄ in 0.1 M K₂SO₄ and PPy|ClO₄ in 0.1 M NaClO₄ aqueous solution. In the case of PPy|SO₄ film in ZnSO₄ solution the D values are essentially lower.     

Large-area network of polyaniline nanowires supported platinum nanocatalysts for methanol oxidation

Nanocomposites comprised of Pt nanoparticles and electrically conducting polymers were prepared and tested for the electrocatalytic performance towards oxidation of methanol. Films of polyaniline (PANI) synthesized independently by potentiostatic and galvanostatic method, PANI(V) and PANI(I), respectively, were used as the supporting matrix for loading Pt nanoparticles. PANI(V), PANI(I), PANI(V)/Pt, and PANI(I)/Pt films were characterized for structure and morphology using scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). SEM image of PANI(I) reveals that the particles are highly porous and interconnected nanowires, whilst PANI(V) particles are granular. The large surface area in the nanofibrillar PANI(I) makes the dispersion of Pt particle with a lesser time for the deposition of Pt particles. The porous network structure of PANI(I) helps in effective dispersion of Pt particles (about 10–20 nm) and facilitates easy access of methanol to the catalytic sites. The electrocatalytic activity of PANI(I)/Pt is much higher (current density (24.7 mA/cm² mg) at 0.68 V) in comparison to PANI(V)/Pt and bulk Pt electrodes (the current density values of 5.5 and 7.5 mA/cm² mg).     

A comparative study on polyaniline degradation by an electrochemical quartz crystal impedance system: electrode and solution effects

By combining the piezoelectric quartz crystal impedance (PQCI) and electrochemical impedance spectroscopy (EIS) measurements, we conducted a comparative study on polyaniline (PANI) degradation in different media, HClO₄ and H₂SO₄, and on different piezoelectric quartz crystal (PQC) electrodes, Pt and Au. It is concluded that (1) the PANI film grown on an Au electrode is more stable than that on a Pt electrode; (2) the PANI degradation reaction abides by the zero-order kinetic law in HClO₄ with rate constants from 0.17 to 2.25 Hz s⁻¹ on Pt and 0.16 to 0.83 Hz s⁻¹ on Au, but the first-order kinetic law in H₂SO₄ with rate constants from 2.61×10⁻³ to 7.00×10⁻³ s⁻¹ on Pt and 1.00×10⁻³ to 5.00×10⁻³ s⁻¹ on Au at different ion concentrations. The contrary effects of ClO₄⁻ and SO₄²⁻ on PANI degradation may be understood from the Hofmeister series of anions; (3) the dissolution of the PANI film bulk, the increase of film porosity and the film attenuation occurred simultaneously during degradation via systematic analyses of the motional resistance (R₁)and electrochemical impedance spectra responses, etc.     

Effect of boron doped fullerene C60 film coating on the electrochemical characteristics of silicon thin film anodes for lithium secondary batteries

In this work, boron doped fullerene (B:C₆₀) films were prepared by the radio frequency plasma assisted thermal evaporation technique for use as a coating material for the silicon thin film anode in lithium secondary batteries. Raman and XPS analyses revealed that the boron atoms were well inserted into the fullerene film lattices. The effect of the B:C₆₀ film on the electrochemical characteristics of the silicon thin film was studied by charge–discharge tests, electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The B:C₆₀ coated silicon film exhibited a high reversible capacity of more than 1200 mAh g^?1 when cycled 50 times between 0 and 2 V at a current density of 1200 μA cm^?2 (1.5 C). The film also showed good rate capacity at different current densities and a more improved coulombic efficiency of 87.7% in the first cycle in comparison with that of the C₆₀ coated film electrode.