Novel preparation of electrically conducting poly (vinyl chloride) by photo-dehydrochlorination from poly (vinyl chloride)/polypyrrole composite film

Polypyrrole (PPy) was deposited electrochemically on a platinum plate from a nitric acid solution of pyrrole. The PVC/PPy composite film was finally obtained by casting poly(vinyl chloride) (PVC) onto the PPy electrode from a tetrahydrofuran solution of PVC. The prepared composite film was irradiated at 90°C with a low-pressure mercury lamp in the stream of hydrogen gas saturated with steam, and the PVC film was dehydrochlorinated, leading to the formation of conjugated polyene. The electrical conductivity (σ) of the PVC film in the irradiated composite film was reveled: σ=2.51 × 10^?5S cm^?1. By iodine doping, σ was further enhanced up to 5.04 X 10^?3 S cm^?1. The tensile strength of the irradiated composite film became larger than that of the original PVC film; i.e., the stress at break was: 461 (composite film); 401 kg cm^?2 (PVC). These results were brought about by the doping of radical species to the conjugated polyene. The anion, NO^?₃, doped during the electrodeposition of PPy was photodecomposed to generate radical NO₂ and this species was doped to the polyene, resulting in the formation of electrically conductive PVC and mechanically improved composite film. © 1994 John Wiley & Sons, Inc.     

Synthesis and electrochemical characterization of LiFePO<Subscript>4</Subscript>/C-polypyrrole composite prepared by a simple chemical vapor deposition method

A LiFePO₄/C-polypyrrole (LiFePO₄/C-PPy) composite as a high-performance cathode material is successfully prepared through a simple chemical vapor deposition (CVD) method. According to the transmission electron microscope (TEM) analysis, the surface of the LiFePO₄/C is surrounded with PPy in the LiFePO₄/C-PPy composite. The as-prepared LiFePO₄/C-PPy material shows outstanding rate capability at 20°C and good cycle performance at 55°C in comparison with those of the bare LiFePO₄/C material against Li anode. After 700 cycles, the discharge capacity of LiFePO₄/C-PPy could still remain 110 mA h g⁻¹ with the retention of 82% at 5 C rate at 55°C. This could be ascribed to the fact that PPy coating on LiFePO₄/C could significantly improve the ionic conductivity of the LiFePO₄/C-PPy composite and could greatly reduce the electrode resistance. Furthermore, the PPy coating on LiFePO₄/C could effectively decrease the dissolution of Fe in the LiPF₆ electrolyte and subsequently suppress the reduction of Fe ions on anode.     

Impact of polypyrrole incorporation on nickel oxide@multi walled carbon nanotube composite for application in supercapacitors

In this article we report the synthesis of polypyrrole incorporated nickel oxide multi walled carbon nanotube (NiO@NMWCNT/PPy) composites by thermal reduction protocol for supercapacitor applications. The structural and morphological properties of the composites were confirmed by the aid of X-ray diffraction (XRD), Field-emission scanning electron microscope (FE-SEM) with energy-dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS) and Field-emission transmission electron microscopy (FE-TEM) analysis indicating the hexagonal crystal structure of NiO decorated on NMWCNT/Ppy. The electrochemical characteristics of the NiO@MWCNT/PPy composite were analyzed in the presence of 2 M KOH as an electrolyte. The NiO@NMWCNT/PPy nanostructured composite produced a plenty of active sites for ion migration reactions that facilitate the energy storage mechanism. As a proof of concept demonstration, the NiO@NMWCNT/PPy composite was explored as an electrode materials in supercapacitor and exhibited specific capacitance of 395 F g⁻¹ and cyclic stability up to 5000 cycles at 0.5 A g⁻¹. Enhanced performance of composite is attributed to the incorporation of polypyrrole in NiO@NMWCNT. The improved capacitance and cyclic stability demonstrated by the composite indicates the NiO@NMWCNT/PPy to be a promising candidate for supercapacitor applications.     

Electropolymerized composite film of polypyrrole and functionalized multi-walled carbon nanotubes: effect of functionalization time on capacitive performance

The composite film of polypyrrole and functionalized multi-walled carbon nanotubes (PPy/F-MWNTs) was prepared by electropolymerization. MWNTs were functionalized by sonicating with a concentrated solution of H₂SO₄/HNO₃ (3/1, volume ratio) in a water bath for different times. The carbon nanotubes (CNTs) are cut into smaller portions with more functional groups introduced on their surface when the sonicating time (nominated as functionalization time hereafter) is increased. However, the specific capacitance of the composite film reaches a maximum of 240 F g⁻¹ at the scanning rate of 10 mV s⁻¹ when MWNTs are functionalized for 24 h, which is about 205 F g⁻¹, 225 F g⁻¹ and 232 F g⁻¹, respectively, when MWNTs are functionalized for 6 h, 12 h and 48 h. At a current load of 1.0 A g⁻¹, PPy/F-MWNT composite film functionalized for 24 h (PPy/F-MWNTs (24 h)) retains 93.49% of its initial capacitance after 1,000 cycles of galvanostatic charge/discharge, and the discharge efficiency is higher than 98.15% during cycling. High specific capacitance, good rate performance, fast charge/discharge ability and long cycling life are ascribed to the synergistic effect of the two components to form a porous composite film as well as the easy accessibility of counter ions into the film. Therefore, PPy/F-MWNT (24 h) composite film is a kind of promising electrode material for supercapacitors. The mechanism of underfunctionalization and overfunctionalization of carbon nanotubes is also discussed.     

Electrochemical properties of LiFePO4/C synthesized using polypyrrole as carbon source

LiFePO₄/C composites were synthesized by pyrolysis of LiFePO₄/polypyrrole (PPy), which was obtained by an in situ chemical polymerization involving pyrrole monomer and hydrothermal synthesis LiFePO₄. All samples were characterized by X-ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy, cyclic voltammetry, and galvanostatic charge–discharge techniques. The results showed the LiFePO₄/C sintered at 800 °C containing 2.8 wt.% carbon exhibited a higher discharge capacity of 49.6 mAh·g⁻¹ at 0.1 C, and bare LiFePO₄ only delivered 11.6 mAh·g⁻¹ in 2 M LiNO₃ aqueous electrolyte. The possible reason for the improvement of electrochemical performance was discussed and could be attributed to the formation of aromatic compounds during the carbonization of PPy.     

Well-dispersed sulfur anchored on interconnected polypyrrole nanofiber network as high performance cathode for lithium-sulfur batteries

Preparation of novel sulfur/polypyrrole (S/PPy) composite consisting well-dispersed sulfur particles anchored on interconnected PPy nanowire network was demonstrated. In such hybrid structure, the as-prepared PPy clearly displays a three-dimensionally cross-linked and hierarchical porous structure, which was utilized in the composite cathode as a conductive network trapping soluble polysulfide intermediates and enhancing the overall electrochemical performance of the system. Benefiting from this unique structure, the S/PPy composite demonstrated excellent cycling stability, resulting in a discharge capacity of 931 mAh g⁻¹ at the second cycle and retained about 54% of this value over 100 cycles at 0.1 C. Furthermore, the S/PPy composite cathode exhibits a good rate capability with a discharge capacity of 584 mAh g⁻¹ at 1  C.     

In Situ Synthesis of Robust Conductive Cellulose/Polypyrrole Composite Aerogels and Their Potential Application in Nerve Regeneration

Nanostructured conductive polymers can offer analogous environments for extracellular matrix and induce cellular responses by electric stimulation, however, such materials often lack mechanical strength and tend to collapse under small stresses. We prepared electrically conductive nanoporous materials by coating nanoporous cellulose gels (NCG) with polypyrrole (PPy) nanoparticles, which were synthesized in situ from pyrrole monomers supplied as vapor. The resulting NCG/PPy composite hydrogels were converted to aerogels by drying with supercritical CO₂, giving a density of 0.41–0.53 g cm^?3, nitrogen adsorption surface areas of 264–303 m² g^?1, and high mechanical strength. The NCG/PPy composite hydrogels exhibited an electrical conductivity of up to 0.08 S cm^?1. In vitro studies showed that the incorporation of PPy into an NCG enhances the adhesion and proliferation of PC12 cells. Electrical stimulation demonstrated that PC12 cells attached and extended longer neurites when cultured on NCG/PPy composite gels with DBSA dopant. These materials are promising candidates for applications in nerve regeneration, carbon capture, catalyst supports, and many others.     

Nano-wire networks of sulfur–polypyrrole composite cathode materials for rechargeable lithium batteries

Polypyrrole (PPy) nanowire was synthesized through a surfactant mediated approach. The sulfur–polypyrrole (S–PPy) composite materials were prepared by heating the mixture of element sulfur and polypyrrole nanowire. The materials were characterized by FTIR, SEM. PPy with special morphology serves as conductive additive, distribution agent and absorbing agents, which effectively enhanced the electrochemical performance of sulfur. The initial discharge capacity of the active materials was 1222 mA h g⁻¹ the remaining capacity is 570 mA h g⁻¹ after 20th cycles.     

γ-Zirconium and γ-Titanium Phosphates Platinum Intercalation Compound Preparation, characterization and thermal behaviour

Inorganic ion-exchangers with a layered structure such as γ-zirconium and γ-titanium phosphates, intercalated with organic diamines, are able to exchange Pt²⁺ ions to give new intercalation compounds that can be utilized in heterogeneous catalysis. The experiments performed at different temperatures (25 and 45°C), show different ion uptakes, greater at 45°C and for the materials derived from γ-zirconium phosphate. After platinum exchange, all the materials show an amorphization in the XRD if compared with their precursors. The thermal behaviour of the platinum materials is specific, depending on the exchanger used and the ligand inside the exchanger. Pt²⁺ ion has a catalytic effect on ligand elimination in the γ-zirconium phosphate platinum compounds, but not in those derived from γ-titanium. All the obtained yellow materials show a small step in the TG curves and simultaneously we have the Pt²⁺→Pt⁰ reduction: this is confirmed by XRD registered at the temperatures of the thermal effect, showing peaks at d_hkl=2.27 and 1.95 Å. This revised version was published online in July 2006 with corrections to the Cover Date.     

Fabrication of gold nanoparticles/polypyrrole composite-modified electrode for sensitive hydroxylamine sensor design

A highly sensitive hydroxylamine (HA) electrochemical sensor is developed based on electrodeposition of gold nanoparticles with diameter of 8 nm on the pre-synthesized polypyrrole matrix and formed gold nanoparticles/polypyrrole (GNPs/PPy) composite on glassy carbon electrode. The electrochemical behavior and electrocatalytic activity of the composite-modified electrode are investigated. The GNPs/PPy composite exhibits a distinctly higher electrocatalytic activity for the oxidation of HA than GNPs with twofold enhancement of peak current. The enhanced electrocatalytic activity is attributed to the synergic effect of the highly dispersed gold metal particles and PPy matrix. The overall numbers of electrons involved in HA oxidation, the electron transfer coefficient, catalytic rate constant, and diffusion coefficient are investigated by chronoamperometry. The sensor presents two wide linear ranges of 4.5 × 10⁻⁷–1.2 × 10⁻³ M and 1.2 × 10⁻³–19 × 10⁻³ M with the detection limit of 4.5 × 10⁻⁸ M (s/n = 3). In addition, the proposed electrode shows excellent sensitivity, selectivity, reproducibility, and stability properties.     

Electrochromic properties of Prussian blue–polypyrrole composite films in dependence on parameters of synthetic procedure

Composite materials of Prussian blue–polypyrrole (PB/PPy) on the surface of indium tin oxide (ITO)-coated glasses were obtained via one-step chemical (redox) and one-stage electrochemical procedures in mixed solution of iron (III), hexacyanoferrate (III), and pyrrole with various concentration ratios of components in nitrate supporting electrolyte. Electrochemical stability of composite films depends on the amount of Py in synthetic solution, whereas color contrast coefficient values depend on the type of synthetic procedure. PB/PPy film electrochromic response (tested by spectroelectrochemical potentiodynamic measurements) was compared with response of both pure PB and pure PPy films. It was shown that degradation of composite films occurs due to PB component instability in Prussian white form. The highest value of color contrast coefficient and great electrochemical stability were revealed for composite films obtained via redox-synthesis procedure from solution with 0.1 mM [Fe³⁺ + Fe(CN)₆ ^3?] and 1.0 mM Ру (PB/PPy-Ch-1:1:10 system).     

Pt and Pt–Ru nanoparticles decorated polypyrrole/multiwalled carbon nanotubes and their catalytic activity towards methanol oxidation

Conducting polymer composite films comprised of polypyrrole (PPy) and multiwalled carbon nanotubes (MWCNTs) [PPy–CNT] were synthesized by in situ polymerization of pyrrole on carbon nanotubes in 0.1 M HCl containing (NH₄)S₂O₈ as oxidizing agent over a temperature range of 0–5 °C. Pt nanoparticles are deposited on PPy–CNT composite films by chemical reduction of H₂PtCl₆ using HCHO as reducing agent at pH = 11 [Pt/PPy–CNT]. The presence of MWCNTs leads to higher activity, which might be due to the increase of electrochemically accessible surface areas, electronic conductivity and easier charge-transfer at polymer/electrolyte interfaces allowing higher dispersion and utilization of the deposited Pt nanoparticles. A comparative investigation was carried out using Pt–Ru nanoparticles decorated PPy–CNT composites. Cyclic voltammetry demonstrated that the synthesized Pt–Ru/PPy–CNT catalysts exhibited higher catalytic activity for methanol oxidation than Pt/PPy–CNT catalyst. Such kinds of Pt and Pt–Ru particles deposited on PPy–CNT composite polymer films exhibit excellent catalytic activity and stability towards methanol oxidation, which indicates that the composite films is more promising support material for fuel cell applications.     

Preparation and characterization of conducting poly(acryloyl chloride)‐g‐ polypyrrole copolymer

The electroactive copolymer of poly(acryloyl chloride) (PAC) and polypyrrole (PPy) can be synthesized by electrochemical polymerization using a polymer precursor which contains a pyrrole moiety in its side chain. Poly(acryloyl pyrrole) (PAP) was synthesized chemically with acryloyl chloride and potassium pyrrole salt and characterized using FT‐IR and ¹H‐NMR spectroscopy. PAP dissolved in dimethyl formamide (DMF), was spin‐coated on a platinum electrode and polymerized electrochemically in the electrolytic mixture solution consisting of acetonitrile, 0.1 M pyrrole, and 0.1 M lithium perchlorate. Constant potential electrolysis showed that pyrrole groups in the precursor were oxidized to form PPy, that is, they acted as grafting centers at which the PPy grew. Scanning electron microscopy (SEM) results and conductivity measurements supported the formation of the graft copolymer. The morphological feature of PAC‐g‐PPy copolymer films showed homogeneous structure, but that of PAC/PPy composite films showed irregular structure. The maximum conductivity of the final products was about 1 S/cm. Copyright © 2002 John Wiley & Sons, Ltd.     

原位包覆导电聚吡咯的Li1.26Fe0.22Mn0.52O2富锂铁锰基正极材料的制备及电化学性能的提高

采用化学氧化聚合的方法成功合成了导电聚吡咯(PPy)包覆的纳米尺寸Li_1.26Fe_0.22Mn_0.52O₂(LFMO)正极材料。通过X射线衍射(XRD)检测样品的晶体结构,并通过扫描电子显微镜(SEM)和透射电子显微镜(TEM)观察材料形态和微观结构。元素映射和傅里叶变换红外光谱结果表明,PPy导电网络存在于复合材料中,并且PPy均匀分布在LFMO颗粒上。通过恒流充放电测试和电化学阻抗谱(EIS)分析研究了所有样品的电化学性能,结果表明表面上的PPy显著降低了LFMO的电荷转移电阻。包覆PPy质量分数为2%的LFMO-2%PPy表现出极好的倍率性能和良好的循环稳定性,其在1C倍率下首次放电容量为206 mAh·g^-1,首圈库仑效率为87%,在1C和2C分别循环50圈后,其容量分别稳定在131和139 mAh·g^-1。     

Dopant effect and characterization of polypyrrole-cellulose composites prepared by in situ polymerization process

Polypyrrole (PPy)-cellulose composites were prepared by in situ polymerization of pyrrole in pulp suspension using ferric chloride as an oxidant. Some sulfonic compounds including p-toluenesulfonic acid and its sodium salt (PTSA and PTSA-Na), benzenesulfonic acid (BSA), dodecylbenzene sulfonic acid and its sodium salt (DBSA and DBSA-Na), 2-naphthalene sulfonic acid (NSA) and 9,10-anthraquinone-2-sulfonic acid sodium salt (AQSA-Na) were used as dopants, and their effect on the conductivity of PPy-cellulose composite was investigated. The results showed that the species and dose of dopants had significant effect on the surface resistivity and environmental stability of PPy-cellulose composite. As the dopant, PTSA and DBSA had a superior doping effect compared to their sodium salts. The doping result of BSA was close to that of PTSA. NSA bearing a naphthalene ring and AQSA-Na bearing an anthraquinone ring gave the best conductivity. Using NSA or AQSA-Na as a dopant, along with suitable polymerization conditions, the PPy-cellulose composite obtained showed a surface resistivity as low as 20 Ω cm⁻². For most dopants, the lowest surface resistivity could be obtained when the molar ratio of dopant to pyrrole was 1:1. Both ATR-FTIR (attenuated total reflection-Fourier transform infrared spectroscopy) and XPS (X-ray photoelectron spectroscopy) analysis confirmed that the PPy on pulp fibers doped with PTSA, PTSA-Na, NSA and AQSA-Na had different doping levels. The higher doping level of the PPy in the composites doped with NAS and AQSA-Na might be related to the stronger interaction of cellulose with PPy chains. Both SEM (scanning electron microscopy) and AFM (atomic force microscopy) observation revealed the fine grain microstructure of the PPy on the composites with average grain sizes in the range of 100–200 nm, and the PPy on the samples doped with NSA and AQSA-Na exhibited quite different morphology as compared to those doped with PTSA and its sodium salt.     

Facile synthesis and performance of polypyrrole-coated sulfur nanocomposite as cathode materials for lithium/sulfur batteries

In situ chemical oxidation polymerization of pyrrole on the surface of sulfur particles was carried out to synthesize a sulfur/polypyrrole （SIPPy） nanocomposite with core-shell structure. The composite was characterized by elemental analysis, X-ray diffraction, scanning/transmission electron microscopy, and electrochemical measurements. XRD and FTIR results showed that sulfur well dispersed in the core-shell structure and PPy structure was successfully obtained via in situ oxidative polymerization of pyrrole on the surface of sulfur particles. TEM observation revealed that PPy was formed and fixed to the surface of sulfur nanoparticle after polymerization, developing a well-defined core-shell structure and the thickness of PPy coating layer was in the range of 20-30 nm. In the composite, PPy worked as a conducting matrix as well as a coating agent, which confined the active materials within the electrode. Consequently, the as prepared SIPPy composite cathode exhibited good cycling and rate performances for rechargeable lithium/sulfur batteries. The resulting cell containing SIPPy composite cathode yields a discharge capacity of 1039 mAh·g^-1 at the initial cycle and retains 59% of this value over 50 cycles at 0.1 C rate. At 1 C rate, the SIPPy composite showed good cycle stability, and the discharge capacity was 475 mAh·g^-1 after 50 cycles.     

Direct evidence of chemical effect of surface-enhanced Raman scattering observed on electrochemically prepared rough gold substrates

In this study, polypyrrole (PPy) films were electrochemically deposited on gold substrates roughened by an electrochemical triangular-wave oxidation-reduction cycles (ORC) in an aqueous solution containing 0.1N KCl. Then the substrates were heated from 25 to 50 °C and the corresponding SERS performances of PPy were observed in situ. The results indicate that the SERS enhancement capabilities of substrates are gradually raised from 25 °C to a maximum at 40 °C and monotonically decreased from 40 to 50 °C. These SERS enhancement capabilities ascribed to the charge transfers from PPy to Au, which are responsible for the chemical effects of SERS mechanisms, are successfully observed via SERS and high resolution X-ray photoelectron spectroscopy (HRXPS) analyses. The variation in content of the oxidized PPy peak of the double peaks in the range of 1000-1150 cm⁻¹ in SERS spectrum obtained on an Au substrate at different temperatures is consistent with its corresponding variation in the SERS intensity of PPy. The variation in content of the oxidized nitrogen of PPy deposited on an Au substrate at different temperatures revealed from an HRXPS analysis also confirms this consistence.     

Capacitive characteristics of nanocomposites of conducting polypyrrole and functionalized carbon nanotubes: effects of in situ dopant and film thickness

The nanocomposites of functionalized single-walled carbon nanotubes (FSWNTs) and conducting polypyrrole (PPy) doped by FSWNTs, Cl⁻, toluenesulfonate (TOS⁻), and dodecylbenzenesulfonate (DBS⁻), respectively, were electrochemically co-deposited to evaluate their applicability in supercapacitors. The effects of the dopants, with focus on their mass, size and surfactivity, and film thickness on the capacitive characteristics were investigated in 3 M KCl aqueous solution. Although the nanostructure of composites can admittedly improve the capacitive properties, dopant anion was demonstrated to be a more essential factor. The specific capacitance of PPy-TOS/FSWNT nanocomposites was greater than that of pristine PPy/FSWNT nanocomposites and PPy-DBS/FSWNT nanocomposites by ten and 100 times, respectively. Furthermore, PPy-TOS/FSWNT nanocomposites exhibited the lowest dependence of capacitance on the charging–discharging rate and composite thickness due to its high electronic and ionic conductivity resulting from the appropriate doping level and size of TOS^- as well as the synergic effect of PPy-TOS and FSWNTs. In addition, PPy-TOS/FSWNT nanocomposites presented a remarkably stable cycling performance.     

Electroconductive Hydrogels: Electrical and Electrochemical Properties of Polypyrrole‐Poly(HEMA) Composites

Composites of inherently conductive polypyrrole (PPy) within highly hydrophilic poly(2‐hydroxyethyl methacrylate)‐based hydrogels (p(HEMA)) have been fabricated and their electrochemical properties investigated. The electrochemical characteristics observed by cyclic voltammetry suggest less facile reduction of PPy within the composite hydrogel compared to electropolymerized PPy, as shown by the shift in the reduction peak potential from ?472 mV for electropolymerized polypyrrole to ?636 mV for the electroconductive composite gel. The network impedance magnitude for the electroconductive hydrogel remains quite low, ca. 100 Ω, even upon approach to DC, over all frequencies and at all offset potentials suggesting retained electronic (bipolaronic) conductivity within the composite. In contrast, sustained application of +0.7 V (vs. Ag/AgCl, 3 M Cl^?) for typically 100 min. (conditioning) to reduce the background amperometric current to <1.0 μA, resulted in complete loss of electroactivity. Nyquist plots suggest that sustained application of such a modest potential to the composite hydrogel results in impedance characteristics that resembles p(HEMA) without evidence of the conducting polymer component. PPy composite gels supported a larger ferrocene monocarboxylate diffusivity (D_appt=7.97×10^?5 cm² s^?1) compared to electropolymerized PPy (D_appt=5.56×10^?5 cm² s^?1), however a marked reduction in diffusivity (D_appt=1.01×10^?5 cm² s^?1) was observed with the conditioned hydrogel composite. Cyclic voltammograms in buffer containing H₂O₂ showed an absence of redox peaks for electrodes coated with PPy‐containing membranes, suggesting possible chemical oxidation of polypyrrole by the oxidant     

Preparation and Properties of Composite Polypyrrole/Pt Catalyst Systems

Three different methods for the preparation and modification of conducting polymer/noble metal catalyst systems consisting of polypyrrole (PPy) and platinum (Pt) are described for the anodic oxidation of methanol. The first method consists of the electrochemical deposition of a thin PPy film on glassy carbon substrate, which is modified with Pt either by electroreduction of hexachloroplatinate, codeposition from a nanodispersed Pt solution, or incorporation of tetrachloroplatinate as counterion followed by cathodic reduction. A second method is based on the preparation of nanoscale PPy(PSS) particles by chemical polymerization with polystyrenesulfonate PSS^– as the counterion. This material is a favorable catalyst support for nanodispersed Pt due to its mixed electronic and cationic conductivity. To study the electrochemical properties, the particulate system PPy(PSS)/Pt is fixed in a carbon fiber electrode. A third method was developed which brings the polypyrrole in close contact to a proton exchanger membrane (Nafion) using a special chemical deposition procedure. This method is useful for preparing a membrane electrode assembly (MEA) consisting of Nafion/PPy/Pt. The structural, morphological, and electrocatalytic properties for methanol oxidation were studied depending on the preparation method applied using surface analytical techniques (TEM, SEM, and EDX) and electrochemical measurements (cyclic voltammetry and transient techniques).