Charging and discharging rate studies of polypyrrole films in AlCl3: 1-methyl-(3-ethyl)-imidazolium chloride molten salts and in CH3CN

The chronocoulometric charging and discharging of polypyrrole films in basic AlCl₃/1-methyl-(3-ethyl)-imidazolium chloride molten salts and CH₃CN have been investigated. Both processes follow a t^{$\text{1}\text{2}$} time dependence and are significantly faster in the molten salts. Comparison with redox polymer and porous electrode models shows that neither model is satisfactorily applicable over the entire potential region studied. The charging and discharging rates are limited by ion migration in the polymer and for potential steps in the “double layer charging” region polypyrrole behaves as a porous electrode material. In this region there is a good correlation between the charging/discharging rates and the solvent conductivity.     

Temperature characterization analysis of LiFePO<Subscript>4</Subscript>/C power battery during charging and discharging

In order to study the surface temperature change and distribution during charging and discharging and in the simulation working condition of LiFePO₄/C power battery at normal temperature, the surface temperature is tested by placing the battery in the incubator and fixing 10 temperature probes on the battery surface. Results show that the temperature of the upper part is higher, and the temperature at the bottom is the lowest, while around the positive electrode is the highest during charging and discharging. The maximum temperature rising rate is reached at the moment of constant current charging transforming to the constant voltage charging during charging, and at the end moment during discharging. During charging in a certain range and discharging, the relations between the maximum temperature, the average temperature rising rate, and the maximum temperature difference of all the measurement points at the same time and the current are approximately linear, respectively. In the simulation working condition, the moment of the maximum temperature is consistent with the large current discharging instantaneous in each stage.     

Transition Metal Salt Doping on Polypyrrole/MWCNT Composites for Supercapacitor Applications

Polypyrrole doped by Zn²⁺ ions was synthesized as nanocomposites with MWCNT by in-situ oxidative polymerization and investigated as electrode material for supercapacitors. The uniform coating of polypyrrole on MWCNT was characterized by field emission scanning electron microscopy (FESEM) and high resolution transmission electron microscopy (HRTEM). The effect of Zn²⁺ ions were characterized by Fourier transform infrared (FTIR) spectroscopy. The electrochemical performances were investigated by cyclic voltammetry (CV), constant current charging/discharging cyclic test (CC) and electrochemical impedance spectroscopy (EIS) using a three-electrode system. The doped polypyrrole composites show higher specific capacitance and better cyclic stability.     

The preparation of polyaniline/polypyrrole conductive polymer films on polycarbonate‐coated Pt electrodes

In this study, free‐standing polymer films were obtained first with an electrochemical coating of polyaniline and then with a coating of polypyrrole on an insulating polycarbonate‐coated Pt electrode. The films contained varying amounts of polyaniline and polypyrrole obtained by varying the electrolysis time, and their conductivities were determined. The Raman spectra of the films taken from the electrode side were similar to those of pure polyaniline, whereas the spectra of the solution side were identical to those of pure polypyrrole. The resistance change in the films between −15 and +120°C revealed that the films were sensitive to temperature. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 51–59, 2000     

钛双极片上网印导电聚合物——碳纳米管复合物及其在水型不对称超级电容器中的电化学性能

用导电聚合物（聚吡硌、聚苯胺）与碳纳米管（经酸处理）复合物（ECP-CNT）以及功能添加剂（表面活性剂：苄索氯铵 benzethonium chloride,粘结剂：聚乙烯醇 polyvinyl alcohol）配成水型印泥（aqueous ink),在钛片（厚度：0.1 mm）上网印（screen printing）成所需载量及面积（例如：75 mg cm^-2,100 cm²）的均匀的ECP-CNT膜. 以该膜为正极,网印活性炭（pigment black）膜为负极,3.0 mol L^-1 KCl 或 1.0 mol L^-1 HCl 为电解质,组装不对称超级电容器. 用循环伏安、恒电流充放电、电化学阻抗、光及电显微等方法研究了ECP-CNT复合物、网印膜、单池以及由双极片（bipolar plate）连接的多池堆（multi-cell stack）. 以两片印刷面积为100 cm² 的钛双极片组装成三池堆,得到较好的技术指标：堆电压3.0 V,电极电容1.29~1.83 F cm^-2,比能量2.30~3.24 Wh kg^-1,最大比功率1.04 kW kg^-1.     

Polyaniline–Polypyrrole Composites with Enhanced Hydrogen Storage Capacities

A facile method for the synthesis of polyaniline–polypyrrole composite materials with network morphology is developed based on polyaniline nanofibers covered by a thin layer of polypyrrole via vapor phase polymerization. The hydrogen storage capacity of the composites is evaluated at room temperature exhibits a twofold increase in hydrogen storage capacity. The HCl‐doped polyaniline nanofibers exhibit a storage capacity of 0.46 wt%, whereas the polyaniline–polypyrrole composites could store 0.91 wt% of hydrogen gas. In addition, the effect of the dopant type, counteranion size, and the doping with palladium nanoparticles on the storage properties are also investigated.

     

Self‐assembled anionic micellar template for polypyrrole,polyaniline, and their random copolymer nanomaterials

We report an anionic surfactant approach for size and shape control in polyaniline, polypyrrole, and their polyaniline‐co‐polypyrrole random copolymer nanomaterials. A renewable resource azobenzenesulfonic acid anionic surfactant was developed for template‐assisted synthesis of these classes of nanomaterials. The surfactant exists as 4.3 nm micelle in water and self‐organizes with pyrrole to produce spherical aggregates. The sizes of the spherical aggregates were controlled by water dilution and subsequent oxidation of these templates, produced polypyrrole nanospheres of 0.5 μM to 50 nm dimensions. The anionic surfactant interacts differently with aniline and forms cylindrical aggregates, which exclusively produce nanofibers of ∼180 nm in diameter with length up to 3–5 μM. The template selectivity of surfactant toward aniline and pyrrole was used to tune the nanostructure of the aniline‐pyrrole random copolymers from nanofiber‐to‐nanorod‐to‐nanospheres. Dynamic light scattering technique and electron microscopes were used to study the mechanistic aspects of the template‐assisted polymerization. The four probe conductivity of the copolymers showed a nonlinear trend and the conductivity passes through minimum at 60–80% of pyrrole in the feed. The amphiphilic dopant effectively penetrates into the crystal lattices of the polymer chain and induces high solid state ordering in the homopolymer nanomaterials. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 830–846, 2009     

电活性导电聚合物在生物医学中的应用

以聚吡咯、聚噻吩和聚苯胺为代表的电活性导电聚合物(electroactive conducting polymers,ECP)已成为生物材料、组织工程及临床医学领域关注的焦点.目前研究主要集中在生物相容性、细胞及组织工程、蛋白质分离、DNA吸附修复、可控药物释放、生物传感器、神经探针等方面.ECP在神经细胞、脑细胞、心肌干细胞再生和功能调节,定向诱导组织器官的再生修复方面具有潜在的应用前景.本文主要综述了聚吡咯(PPy)和聚苯胺(PANi)在生物医学领域的研究进展,和电刺激对细胞生长和干细胞分化的影响,并建议了一些前景可观的相关研究方向.     

Effect of polar solvent acetonitrile on the electrochemical behavior of polyaniline in ionic liquid electrolytes

Polyaniline film was electropolymerized in organic acidic media (CF3COOH) and then investigated by cyclic voltammetry, AC impedance, and galvanostatic charging and discharging tests in ionic liquid-1-methyl-3-butylimidazolium hexafluorophosphate (BMIPF6) and the mixture electrolytes of BMIPF6 and acetonitrile (ACN) with different ratios. The results showed that the polymer in mixture of BMIPF6 and ACN have lower solution resistance, higher cycle life, and higher electrochemical capacitance. The relationship of the peak current to the scan rates provides some insight into the nature of the polyaniline film switching reaction in different electrolytes.     

An Aqueous Rechargeable Formate‐Based Hydrogen Battery Driven by Heterogeneous Pd Catalysis

The formate‐based rechargeable hydrogen battery (RHB) promises high reversible capacity to meet the need for safe, reliable, and sustainable H₂ storage used in fuel cell applications. Described herein is an additive‐free RHB which is based on repetitive cycles operated between aqueous formate dehydrogenation (discharging) and bicarbonate hydrogenation (charging). Key to this truly efficient and durable H₂ handling system is the use of highly strained Pd nanoparticles anchored on graphite oxide nanosheets as a robust and efficient solid catalyst, which can facilitate both the discharging and charging processes in a reversible and highly facile manner. Up to six repeated discharging/charging cycles can be performed without noticeable degradation in the storage capacity.     

顺序加料法制备聚苯胺与聚吡咯复合物及其电化学电容性能

以顺序加料原位聚合法化学氧化制备了聚吡咯(PPy)和聚苯胺(PANi)的复合物.采用SEM、红外光谱表征其结构,采用电化学工作站测试其超级电容性能.结果表明:制得的聚苯胺与聚吡咯的复合物,形成了二次结构;复合物的循环伏安特性曲线均接近于理想的矩形,恒流充放电曲线基本为线性,呈现双电层电容;PANi-PPy和PPy-PANi复合物的最高比电容分别达到227.6、195.5 F/g.     

聚苯胺/活性碳复合型超电容器的电化学特性

电化学电容器作为一种新型储能器件具有广泛的应用.采用(NH₄)₂S₂O₈化学氧化聚合苯胺法制备了聚苯胺电极材料，采用化学物理二次催化活化法制备了高比表面积活性碳材料.并用循环伏安、恒流充放电以及交流阻抗等方法对上述电极材料的电化学特性进行了研究.实验结果表明,所制备的聚苯胺电极材料具有高于420 F•g^－1的法拉第赝电容和良好的电化学特性，所制备的活性碳电极材料则具有160 F•g^－1的双电层电容量.分别采用聚苯胺作为正极，活性碳作为负极，38％硫酸作为电解液制备了复合型电化学电容器.复合型电容器工作电压达到1.4 V, 电容器单体比电容达到57 F•g^－1，最大比能量和最大真实比功率分别达到15.5 W•h•kg^－1和2.4 W•g^－1, 峰值比功率达到20.4 W•g^－1,电容器循环工作寿命超过500次. 与活性碳双电层电容器相比，复合型电容器还具有较低的自放电率.     

A High‐Energy‐Density Potassium Battery with a Polymer‐Gel Electrolyte and a Polyaniline Cathode

A safe, rechargeable potassium battery of high energy density and excellent cycling stability has been developed. The anion component of the electrolyte salt is inserted into a polyaniline cathode upon charging and extracted from it during discharging while the K⁺ ion of the KPF₆ salt is plated/stripped on the potassium‐metal anode. The use of a p‐type polymer cathode increases the cell voltage. By replacing the organic‐liquid electrolyte in a glass‐fiber separator with a polymer‐gel electrolyte of cross‐linked poly(methyl methacrylate), a dendrite‐free potassium anode can be plated/stripped, and the electrode/electrolyte interface is stabilized. The potassium anode wets the polymer, and the cross‐linked architecture provides small pores of adjustable sizes to stabilize a solid‐electrolyte interphase formed at the anode/electrolyte interface. This alternative electrolyte/cathode strategy offers a promising new approach to low‐cost potassium batteries for the stationary storage of electric power.     

基于静电吸附作用制备PPy/CNTs复合材料

通过添加十二烷基苯磺酸钠(SDBS), 在碳纳米管(CNTs)表面引入具有静电吸附作用的基团, 使吡咯单体附着于CNTs表面, 然后发生化学原位聚合, 得到了由片状聚吡咯(PPy)包覆CNTs所构成的PPy/CNTs复合材料, 开辟了一条易于工业化生产制备PPy/CNTs复合材料的途径. 所得材料和CNTs借助傅立叶变换红外光谱、扫描电子显微镜、透射电子显微镜等设备进行了成分和形貌的表征; 并将所得材料组装成电化学超级电容器, 进行了电化学性能测试. 研究结果表明, 加入SDBS后, 吡咯单体能很好地吸附于CNTs表面; CNTs的应用细化了PPy的颗粒, 改善了PPy的导电性能和机械性能, 使PPy/CNTs复合材料呈现出多孔状; 其电化学容量达到101.1 F·g-1(有机电解液), 是同样制备条件下所得纯PPy电化学容量(19.0 F·g-1)的5倍多, 约是所用纯CNTs电化学容量(25.0 F·g-1)的4倍.     

On the break-in and passivation phenomena in polypyrrole/sulfate films

The influence of different divalent cations (M²⁺) on the electrochemical charging/discharging process of polypyrrole/sulfate (PPy/SO₄) films has been investigated. In principle, two different types of M²⁺ were found: (a) cations that cause the break-in phenomenon in the PPy film during electrochemical cycling with a gradual increase of film electroactivity and (b) cations in whose solutions the PPy film remains mainly electroinactive. Certain correlations have been drawn between several physico-chemical properties of the investigated cations and the break-in and passivation phenomena. The break-in and passivation phenomena were found to be influenced by the size and deformability of the cation hydration shell, ion covalent index and softness, as well as by the pH value of the test solution.     

Polyaniline‐Stabilized Intertwined Network‐like Ferrocene/Graphene Nanoarchitecture for Supercapacitor Application

The present work highlights the effective H–π interaction between metallocenes (ferrocene; Fc) and graphene and their stabilization in the presence of polyaniline (PANI) through π–π interactions. The PANI‐stabilized Fc@graphene nanocomposite (FcGA) resembled an intertwined network‐like morphology with high surface area and porosity, which could make it a potential candidate for energy‐storage applications. The relative interactions between the components were assessed through theoretical (DFT) calculations. The specific capacitance calculated from galvanostatic charging/discharging indicated that the PANI‐stabilized ternary nanocomposite exhibited a maximum specific capacitance of 960 F g⁻ at an energy density of 85 Wh Kg⁻¹ and a current density of 1 A g⁻. Furthermore, electrochemical impedance spectroscopy (EIS) analysis confirmed the low internal resistance of the as‐prepared nanocomposites, which showed improved charge‐transfer properties of graphene after incorporation of Fc and stabilization with PANI. Additionally, all electrodes were found to be stable up to 5000 cycles with a specific capacitance retention of 86 %, thus demonstrating the good reversibility and durability of the electrode material.     

Electrochemical synthesis and characterization of solid-phase microextraction fibers using conductive polymers: application in extraction of benzaldehyde from aqueous solution

In this work, polyaniline, polypyrrole, and polyaniline/polypyrrole composite fibers were synthesized in the absence and presence of oxidized multiwalled carbon nanotubes using electrochemical cyclic voltammetry with CF₃COOH as dopant. Thermal stability of these fibers was studied by differential scanning calorimetry. Then, headspace solid-phase microextraction process coupled with gas chromatography and flame ionization detector was used for comparing extraction capability of benzaldehyde from aqueous solution. Since polyaniline fiber showed better extraction efficiency than the other fibers, its preparation conditions including acid concentration, aniline concentration, scan rate, and amount of multiwalled carbon nanotubes were studied by means of the “one-factor-at-a-time method”. The analytical performance of polyaniline fibers were investigated to determine benzaldehyde from the aqueous solution. The morphology and texture of polyaniline fibers were examined by field emission scanning electron microscopy and Fourier transform infrared spectroscopy analyses. The attained results revealed that the perfect conditions for acid concentration, aniline concentration, scan rate, and multiwalled carbon nanotubes content were 0.5 M, 0.2 M, 25 mV s^?1, and 0.02 wt%, respectively. The limit of detection for the proposed polyaniline fiber was 15 ng ml^?1.     

Synthesis of Multishell Carbon Nanotube Composites via Template Method

Multishell nanotubes of polyaniline and carbon were synthesized via a template approach. A thin layer of MnO₂ coated on carbon nanotubes acts as a reactive template for the consequent formation of the polyaniline coating. The polyaniline-carbon nanotubes show enhanced dispersibility in water and can be possibly used as a functional material of electrochemical capacitors with improved performance. The general method operates by coating carbon nanotubes on functional materials such as poly (3,4-ethylenedioxythiophene), polypyrrole, silica, and carbon.     

Coaxial conducting polymer nanotubes: polypyrrole nanotubes coated with polyaniline or poly(<Emphasis Type="Italic">p</Emphasis>-phenylenediamine) and products of their carbonisation

Polypyrrole nanotubes were prepared by the oxidation of pyrrole with iron(III) chloride in a reaction mixture containing methyl orange. They were subsequently coated with polyaniline or poly(p-phenylenediamine) in situ during the oxidation of respective monomers in their presence. A part of the coaxial nanotubes was deprotonated using ammonia solution. The conductivity of polypyrrole nanotubes of 60 S cm^?1, was reduced after the coating, and again after the deprotonation, but maintained at a level above 10^?4 S cm^?1. Infrared and Raman spectra reflect the presence of the polymer overlayer deposited on the polypyrrole template. Thermogravimetric analysis was used as a tool for the analytical carbonisation of samples in an inert nitrogen atmosphere. The conversion of conducting polymers to nitrogen-containing carbon nanotubes was confirmed using Raman spectra.     

The Phenomenon of Mutual Media in Polypyrrole with Electroactive Ions

The dependence of the differential capacitance of polypyrrole doped with several typical dopants on potential is presented, which shows that the differential capacitance varies with the potential, the doped polypyrroles with electroactive ions give the largest capacitance near their formal potentials, which is attributed to the mutual media for electron transfer between polypyrrole and electroactive dopants. The existence of two conducting phases was observed in the complex capacitance plots. The electroactive anions act as an intra-conducting-phase medium for electron transfer, the electroactive cations act as an inter-conducting phase medium for electron transfer. The mutual media between polypyrrole and redox dopants lead to the increase of the discharging time.