Highly dispersed hydrous ruthenium oxide in poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonic acid) for supercapacitor electrode

Hydrous RuO₂ particles were electrochemically loaded into poly(3,4-ethylenedioxythiophene) doped poly(styrene sulfonic acid), PEDOT-PSS, matrix by employing various potential cycles in cyclic voltammetry and to fabricate the PEDOT-PSS-RuO₂·xH₂O electrode. The amount of hydrous RuO₂ particles loaded into the PEDOT-PSS matrix was easily controlled by varying the number of potential cycles. Scanning electron microscopy photographs reveal a uniform dispersion of hydrous RuO₂ particles in the porous structure of PEDOT-PSS matrix. Raman spectrum confirms the incorporation of hydrous RuO₂ into PEDOT-PSS matrix. Chronopotentiometry and cyclic voltammetry were employed in 0.5 M H₂SO₄ to evaluate the capacitor properties. Specific capacitance values were determined by chronoamperometry. An increasing trend in specific capacitance with loaded amount of hydrous RuO₂ particles in PEDOT-PSS was noticed. A maximum specific capacitance of 653 F/g was achieved.     

Highly flexible supercapacitors with manganese oxide nanosheet/carbon cloth electrode

We report a simple and cost-effective synthesis of hierarchically porous structure composed of Birnessite-type manganese dioxide (MnO₂) nanosheets on flexible carbon cloth (CC) via anodic electrodeposition technique. Petal-shaped MnO₂, having sheet thickness of a few nm and typical width of 100 nm, with a strong adhesion on CC is observed. This hierarchically porous MnO₂–CC hybrid structure dose exhibit not only excellent capacitance properties, such as up to 425 F g⁻¹ in specific capacitance, but also high crack resistance owing to its efficient release of bending stress, as observed by cyclic voltammetry and galvanostatic charge/discharge measurements under different curvature of bending configurations. Furthermore, flexible supercapacitors based on this kind of MnO₂ nanosheet/CC electrode showed significantly improved stability in capacitive performance over 3000 cycles under the bending test, which is highly promising for future applications in flexible energy storage device.     

Enhanced performance of a dye-sensitized solar cell with a modified poly(3,4-ethylenedioxythiophene)/TiO2/FTO counter electrode

ClO₄⁻-poly(3,4-ethylenedioxythiophene)/TiO₂/FTO (ClO₄⁻-PEDOT/TiO₂/FTO) counter electrode (CE) in dye-sensitized solar cells (DSSCs) is fabricated by using an electrochemical deposition method. Comparing with the DSSCs with ClO₄⁻-PEDOT/FTO counter electrode, the photocurrent-voltage (I-V) measurement reveals that the photocurrent conversion efficiency (η), fill factor (FF) and short-circuit current density (J_SC) of DSSCs with a ClO₄⁻-PEDOT/TiO₂/FTO CE increase. The enhanced performances of the DSSCs are attributed to the higher J_SC arising from the increase of active surface area of ClO₄⁻-PEDOT/TiO₂/FTO CE. Electrochemical impedance spectra (EIS) also indicate that the charge-transfer resistance on the ClO₄⁻-PEDOT/electrolyte interface decreases. Cyclic voltammetry results indicate that the ClO₄⁻-PEDOT/TiO₂/FTO electrode shows higher activity towards I₃⁻/I⁻ redox reaction than that of ClO₄⁻-PEDOT/FTO electrode.     

Electrochemical performances of poly(3,4-ethylenedioxythiophene)-NiFe2O4 nanocomposite as electrode for supercapacitor

Poly 3,4-ethylenedioxythiophene (PEDOT)-based NiFe₂O₄ conducting nanocomposites were synthesized and their electrochemical properties were studied in order to find out their suitability as electrode materials for supercapacitor. Nanocrystalline nickel ferrites (5-20 nm) have been synthesized by sol-gel method. Reverse microemulsion polymerization in n-hexane medium for PEDOT nanotube and aqueous miceller dispersion polymerization for bulk PEDOT formation using different surfactants have been adopted. Structural morphology and characterization were studied using XRD, SEM, TEM and IR spectroscopy. Electrochemical performances of these electrode materials were carried out using cyclic voltammetry at different scan rates (2-20 mV/s) and galvanostatic charge-discharge at different constant current densities (0.5-10 mA/cm²) in acetonitrile solvent containing 1 M LiClO₄ electrolyte. Nanocomposite electrode material shows high specific capacitance (251 F/g) in comparison to its constituents viz NiFe₂O₄ (127 F/g) and PEDOT (156 F/g) where morphology of the pore structure plays a significant role over the total surface area. Contribution of pseudocapacitance (C_FS) arising from the redox reactions over the electrical double layer capacitance (C_DL) in the composite materials have also been investigated through the measurement of AC impedance in the frequency range 10 kHz-10 mHz with a potential amplitude of 5 mV. The small attenuation (∼16%) in capacitance of PEDOT-NiFe₂O₄ composite over 500 continuous charging/discharging cycles suggests its excellent electrochemical stability.     

Manganese oxide embedded polypyrrole nanocomposites for electrochemical supercapacitor

MnO₂ embedded PPy nanocomposite (MnO₂/PPy) thin film electrodes were electrochemically synthesized over polished graphite susbtrates. Growing PPy polymer chains provides large surface area template that enables MnO₂ to form as nanoparticles embeded within polymer matrix. Co-deposition of MnO₂ and PPy has a complimentary action in which porous PPy matrix provides high active surface area for the MnO₂ nanoparticles and, on the other hand, MnO₂ nanoparticles nucleated over polymer chains contribute to enhanced conductivity and stability of the nanocomposite material by interlinking the PPy polymer chains. The MnO₂/PPy nanocomposite thin film electrodes show significant improvement in the redox performance as cyclic voltammetric studies have shown. Specific capacitance of the nanocomposite is remarkably high (∼620 F g⁻¹) in comparision to its constituents MnO₂ (∼225 F g⁻¹) and PPy (∼250 F g⁻¹). Photoelectron spectroscopy studies show that hydrated manganese oxide in the nanocomposite exists in the mixed Mn(II) to Mn(IV) oxidation states. Accordingly, chemical structures of MnO₂ and PPy constituents in the nanocomposite are not influenced by the co-deposition process. The MnO₂/PPy nanocomposite electrode material however shows significantly improved high specific capacitity, charge-discharge stability and the redox performance properties suitable for application in the high energy density supercapcitors.     

Synthesis and electrochemical capacitance of core-shell poly (3,4-ethylenedioxythiophene)/poly (sodium 4-styrenesulfonate)-modified multiwalled carbon nanotube nanocomposites

A noncovalent method was used to functionalize multiwalled carbon nanotubes with poly (sodium 4-styrene sulfonate). And then, the core-shell poly (3,4-ethylenedioxythiophene)/functionalized multiwalled carbon nanotubes (PEDOT/PSS-CNTs) nanocomposite was successfully realized via in situ polymerization under the hydrothermal condition. In the process, PSS served for not only solubilizing and dispersing CNTs well into an aqueous solution, but also tethering EDOT monomer onto the surface of CNTs to facilitate the formation of a uniform PEDOT coating. Fourier transform infrared spectroscopy (FT-IR) and transmission electron microscopy (TEM) were used to characterize the resultant PEDOT/PSS-CNTs. In addition, the PEDOT/PSS-CNTs nanocomposite (50 wt.% PEDOT) had a specific capacitance (SC) of 198.2 F g⁻¹ at a current density of 0.5 A g⁻¹ and a capacitance degradation of 26.9% after 2000 cycles, much better than those of pristine PEDOT and PEDOT/CNTs (50 wt.% PEDOT). The enhanced electrochemical performance of the PEDOT/PSS-CNTs nanocomposite (50 wt.% PEDOT) should be attributed to the high uniform system of the nanocomposite, resulting in the large surface easily contacted by abundant electrolyte ions through the three-dimensional conducting matrix.     

Preparation and characterisation of poly(3,4-ethylenedioxythiophene) and poly(3,4-ethylenedioxythiophene)/poly(neutral red) modified carbon film electrodes, and application as sensors for hydrogen peroxide

Poly(3,4-ethylenedioxythiophene) (PEDOT) films have been prepared for the first time on carbon-film electrodes (CFE) in aqueous solution using electropolymerisation by potential cycling, potentiostatically and galavanostatically. Characterisation of the modified electrodes was done by cyclic voltammetry and electrochemical impedance spectroscopy and the stability of the polymer films was probed. The coated electrodes were tested for application as hydrogen peroxide sensors, by oxidation and reduction. A novel polymer film was also formed by modification of CFE by co-electropolymerisation of EDOT and the phenazine dye neutral red (NR) – (PEDOT/PNR) with a view to enhancing the properties for sensor applications. It was found that hydrogen peroxide reduction at the PEDOT/PNR coated electrodes could be carried out at a less negative potential, the sensor performance comparing very favourably with that of other polymer-modified electrodes reported in the literature.     

Poly(ethylene oxide)/poly(propylene oxide)/poly(ethylene oxide) triblock copolymer as a sustained-release carrier for perfume compounds

The volatility behavior of perfume compounds in poly(ethylene oxide)/poly(propylene oxide)/poly(ethylene oxide) copolymer was investigated by means of dynamic and static headspace analyses. Suppression of the volatility of perfume compounds by EO₁₀₅PO₂₇EO₁₀₅ copolymer was markedly greater than by polyethyleneglycol. This suppressive effect may be due to micelle and gel formation of EO₁₀₅PO₂₇EO₁₀₅ copolymer. EO₁₀₅PO₂₇EO₁₀₅ copolymer is expected to be useful as a novel sustained-release carrier that maintains constant release rates for the volatility of perfume compounds over a wide temperature range.     

Electrochemical properties of microwave irradiated synthesis of poly(3,4-ethylenedioxythiophene)/V2O5 nanocomposites as cathode materials for rechargeable lithium batteries

A series of poly(3,4-ethylenedioxythiophene) (PEDOT)/V₂O₅ nanocomposites are prepared via the redox intercalative polymerization reaction of 3,4-ethylenedioxythiophene (EDOT) monomer and crystalline V₂O₅ within 10 min by using rapid 2.45 GHz microwave irradiation with full power (800 W). The unique properties of the resultant nanocomposites are investigated by various characterization techniques using powder XRD, TGA/DTA and four-point probe conductivity analysis supports the intercalation of polymer nanosheet between V₂O₅ layers leading to enhanced bi-dimensionality. X-ray photoelectron spectroscopy analysis clearly shows the presence of mixed valent V⁴⁺/V⁵⁺ in the V₂O₅ framework after the redox intercalative polymerization which also confirms charge transfer from the polymer to the V₂O₅ framework. The application potential of these composites as cathode materials in rechargeable lithium batteries is also demonstrated by the electrochemical intercalation of lithium into the PEDOT/V₂O₅ nanocomposites, where an enhancement in the discharge capacity (370 mAh/g) is observed compared to that of crystalline V₂O₅.     

Electrosynthesis and properties of poly(3,4-ethylenedioxythiophene) films functionalized with titanocene dichloride complex

Synthesis of a titanocene dichloride derivative functionalized with 3,4-etylenedioxythiophene group, Tc1EDOT (Cl₂TiCpC₅H₄(CH₂) (3,4-ethylenedioxythiophene)) has been described. Redox behavior of the monomer in tetrahydrofuran (THF), dichloromethane (DCM) and acetonitrile (AN) at different scan rates has been discussed in terms of different ability of these solvents to coordination with the reduced titanocene (Tc) complex and the solvation of Cl⁻ anions. Electrooxidation of Tc1EDOT to get a conducting polymer film with immobilized titanocene dichloride centers and electrochemical properties of its polymer matrix in background acetonitrile solution have been compared with those of non-substituted PEDOT and PEDOT-methanol derivative (PEDOTMet), to elucidate the effect of substituents both on polymerization and redox potentials of the matrix. STM and AFM images of p(Tc1EDOT) films obtained with potentiodynamic and potentiostatic regimes are compared to illustrate that the films deposited at constant potential are better ordered and more compact than those obtained by cyclic voltammetry. A comparison of the cyclic voltammograms of p(Tc1EDOT) and poly(titanocene-propyl-pyrrole) (p(Tc3Py)) films in 0.1 TBAPF₆ in THF has shown that the electroactivity of the polymer matrix of p(Tc1EDOT) is extended to more negative potentials in comparison to that of p(Tc3Py). This results in the anodic shift of redox potential of Tc centers immobilized in p(Tc1EDOT) film with respect to that of the centers fixed in p(Tc3Py).     

Synthesis and electrochemical properties of CeO2 nanoparticle modified TiO2 nanotube arrays

In this paper, a cerium dioxide (CeO₂) modified titanium dioxide (TiO₂) nanotube array film was fabricated by electrodeposition of CeO₂ nanoparticles onto an anodized TiO₂ nanotube array. The structural investigation by X-ray diffraction, scanning electron microscopy and transmission electron microscopy indicated that the CeO₂ nanoparticles grew uniformly on the walls of the TiO₂ nanotubes. The composite was composed of cubic-phase CeO₂ crystallites and anatase-phase TiO₂ after annealing at 450 °C. The cyclic voltammetry and chronoamperometric charge/discharge measurement results indicated that the CeO₂ modification obviously increased the charge storage capacity of the TiO₂ nanotubes. The charge transfer process at the surface, that is, the pseudocapacitance, was the dominate mechanism of the charge storage in CeO₂-modified TiO₂ nanotubes. The greater number of surface active sites resulting from uniform application of the CeO₂ nanoparticles to the well-aligned TiO₂ nanotubes contributed to the enhancement of the charge storage density.     

Preparation and electrochemical capacitance of Me double hydroxides (Me = Co and Ni)/TiO2 nanotube composites electrode

In this paper, Me double hydroxides (Me = Co and Ni)/TiO₂ nanotube composites were synthesized by a simple chemical co-precipitation method. Electrochemical properties of the composites were examined by cyclic voltammetry, galvanostatic and impedance measurements. The highest specific capacitance values of 1053 F/g could be achieved with Me double hydroxides loaded on the TiO₂ nanotube, which was comparable to that of hydrated ruthenium oxide.     

One-pot synthesis of poly(3,4-ethylenedioxythiophene)-Pt nanoparticle composite and its application to electrochemical H2O2 sensor

ABSTRACT: Poly(3,4-ethylenedioxythiophene)-Pt nanoparticle composite was synthesized in one-pot fashion using a photo-assisted chemical method, and its electrocatalytic properties toward hydrogen peroxide (H2O2) was investigated. Under UV irradiation, the rates of the oxidative polymerization of EDOT monomer along with the reduction of Pt4+ ions were accelerated. In addition, the morphology of PtNPs was also greatly influenced by the UV irradiation; the size of PtNPs was reduced under UV irradiation, which can be attributed to the faster nucleation rate. The immobilized PtNPs showed excellent electrocatalytic activities towards the electroreduction of hydrogen peroxide. The resultant amperometric sensor showed enhanced sensitivity for the detection of H2O2 as compared to that without PtNPs, i.e., only with a layer of PEDOT. Amperometric determination of H2O2 at 0.55 V gave a limit of detection of 1.6 uM (S N = 3) and a sensitivity of 19.29 mA cm2 M1 up to 6 mM, with a response time (steady state, t95) of 30 to 40 s. Energy dispersive X-ray analysis, transmission electron microscopic image, cyclic voltammetry (CV), and scanning electron microscopic images were utilized to characterize the modified electrode. Sensing properties of the modified electrode were studied both by CV and amperometric analysis.     

Copper oxide catalysts supported on ceria for low-temperature CO oxidation

Copper oxide catalysts supported on ceria were prepared by wet impregnation method using finely CeO₂ nanocrystals, which was derived from alcohothermal synthesis, and copper nitrate dissolved in the distilled water. The catalytic activity of the prepared CeO₂ and CuO/CeO₂ catalysts for low-temperature CO oxidation was investigated by means of a microreactor-GC system. The samples were characterized using BET, XRD, SEM, HRTEM and TPR.     

A novel photoelectrocatalytic system for organic contaminant degradation on a TiO2 nanotube (TNT)/Ti electrode

A novel degradation system, combined with photon-efficient thin-film photocatalysis, conventional bulk-phase photocatalysis and photocarrier-efficient electrocatalysis (TBPE), was developed on a vertically ordered one-dimensional (1D) TiO₂ nanotube (TNT)/Ti electrode for the purification of organics. The TBPE system possessed excellent optical, electrochemical, photoelectrochemical and photoelectrocatalytic properties as well as a high mass-transfer coefficient and interfacial activity. The combined degradation of methyl orange (MO) was optimized by varying the rotation angular velocity, applied bias and substrate concentration, and a photoelectrochemical synergetic effect of 62.2% was observed under the optimized conditions for TBPE compared to the individual electrocatalytic (EC) and photocatalytic (PC) systems. To explore the mechanisms, the combined thin-film degradation system of photon-efficient thin-film photocatalysis with photocarrier-efficient electrocatalysis (TPE), and the combined bulk-phase degradation system of conventional bulk-phase photocatalysis with photocarrier-efficient electrocatalysis (BPE), were comparatively estimated. A dramatic increase of 29.4-74.4% was observed in the MO removal efficiency via the thin-film TPE system compared to the bulk-phase BPE system. The results indicated that in the proposed TBPE system on the 1D TNT electrode, the predominant degradation occurred via the TPE system due to its excellent UV utilization efficiency and resultant interfacial photoactivity.     

AC impedance and state-of-charge analysis of alkaline zinc/manganese dioxide primary cells

Alternating current impedance data of alkaline Zn/MnO₂ cells were analysed in view of identification of suitable parameters, which depend on the state-of-charge (SOC) of the cells. The impedance of a slightly discharged cell was found to possess impedance considerably lesser than that of an undischarged cell. The data in the form of Nyquist plot contained an inductance part at very high frequencies, a capacitive semicircle at high frequencies and a diffusion linear spike at low frequencies. The low frequency linear spike gradually transformed into a capacitive semicircle with the decrease of SOC of the cell, which was attributed to the nature of the reactions at the Zn anode. Of several impedance parameters that were examined, equivalent series capacitance (C_s) was found to have a strong dependence on SOC of the alkaline Zn/MnO₂ cells. There was a continuous change in a partially discharged cell during its ageing, which was reflected by transformation of low frequency data into a clear semicircle.     

Light energy storage and photoelectrochemical behavior of the titanate nanotube array/Ni(OH)2 electrode

A new kind of TiO₂ nanotube array/Ni(OH)₂ (TiO₂/Ni(OH)₂) composite electrode with the storage ability of light energy was prepared by the deposition of Ni(OH)₂ on the TiO₂ nanotube array, which was synthesized by anodizing Ti foils in an HF aqueous solution. SEM and XRD results showed that Ni(OH)₂ particles were well distributed on high density, well-ordered and uniform TiO₂ nanotube arrays. The photoelectrochemical properties of the TiO₂/Ni(OH)₂ electrode were investigated in NaHCO₃/NaOH buffer solution (pH 10) by means of UV-vis absorption spectra, cyclic voltammogram (CV) and photocurrent measurements. It was found that the TiO₂/Ni(OH)₂ electrode was highly sensitive to light and exhibited excellent photoelectrochromic properties. Upon UV irradiation, the photogenerated holes by TiO₂ nanotube arrays can oxidize Ni(OH)₂ to NiOOH, and thus the TiO₂/Ni(OH)₂ electrode can be photo-charged by light.     

Electrochemical preparation and characterization of V2O5/polyaniline composite film cathodes for Li battery

Vanadium pentoxide/polyaniline (V₂O₅/PANi) composite films were prepared by a two-step electrochemical method and evaluated for their application in lithium batteries. As a first step the PANi film was potentiodynamically grown in an acid solution containing aniline monomer, and secondly vanadium oxide was oxidatively deposited on the polyaniline film in a temperature controlled VOSO₄ solution. The increased current efficiency obtained with the larger anodic current in the high temperature solutions results in high contents of V₂O₅ in the composites, even if the oxidative dissolution of PANi also occurs. The large value of the diffusion coefficient estimated from the cyclic voltammograms for the composite film provides evidence for the synergistic effect of the conducting polymer and the inorganic composite. The cell exhibited excellent cycle stability with a high charge storage capacity. The large increase in the specific capacity for the composite film prepared in this work demonstrates that the conducting polymer in the composite acts as a binding and conducting element by contributing its electroactivity. The V₂O₅/PANi composite film cathodes show a large specific capacity (ca. 270 mAh/g) and improved cyclability with an extremely small amount of capacity fading (ca. 3.4%) during repeated charge/discharge cycles.     

Enhanced electrochemical stability and charge storage of MnO2/carbon nanotubes composite modified by polyaniline coating layer in acidic electrolytes

Manganese dioxide/multiwalled carbon nanotubes (MnO₂/MWCNTs) were synthesized by chemically depositing MnO₂ onto the surface of MWCNTs wrapped with poly(sodium-p-styrenesulfonate). Then, polyaniline (PANI) with good supercapacitive performance was further coated onto the MnO₂/MWCNTs composite to form PANI/MnO₂/MWCNTs organic-inorganic hybrid nanoarchitecture. Electrochemical performance of the hybrid in Na₂SO₄-H₂SO₄ mixed acidic electrolytes was evaluated by cyclic voltammetry (CV) and chronopotentiometry (CP) in detail. Comparative electrochemical tests revealed that the hybrid nanoarchitecture could operate in the acidic medium due to the protective modification of PANI coating layer onto the MnO₂/MWCNTs composite, and that its electrochemical behavior was greatly dependent upon the concentration of protons in the acidic electrolytes. Here, PANI not only served as a physical barrier to restrain the underlying MnO₂/MWCNTs composite from reductive-dissolution process so as to make the novel ternary hybrid material work in acidic medium to enhance the utilization of manganese oxide as much as possible, but also was another electroactive material for energy storage in the acidic mixed electrolytes. It was due to the existence of PNAI layer that an even larger specific capacitance (SC) of 384 F g⁻¹ and a much better SC retention of 79.9% over 1000 continuous charge/discharge cycles than those for the MnO₂/MWCNTs nanocomposite were delivered for the hybrid in the optimum 0.5 M Na₂SO₄-0.5 M H₂SO₄ mixed acidic electrolyte.     

Transparent conductive oxide films mixed with gallium oxide nanoparticle/single-walled carbon nanotube layer for deep ultraviolet light-emitting diodes

We propose a transparent conductive oxide electrode scheme of gallium oxide nanoparticle mixed with a single-walled carbon nanotube (Ga₂O₃ NP/SWNT) layer for deep ultraviolet light-emitting diodes using spin and dipping methods. We investigated the electrical, optical and morphological properties of the Ga₂O₃ NP/SWNT layers by increasing the thickness of SWNTs via multiple dipping processes. Compared with the undoped Ga₂O₃ films (current level 9.9 × 10^-9 A @ 1 V, transmittance 68% @ 280 nm), the current level flowing in the Ga₂O₃ NP/SWNT increased by approximately 4 × 10⁵ times and the transmittance improved by 9% after 15 times dip-coating (current level 4 × 10^-4 A at 1 V; transmittance 77.0% at 280 nm). These improvements result from both native high transparency of Ga₂O₃ NPs and high conductivity and effective current spreading of SWNTs.