三元复合材料PANI／Ag／MWNT的电化学行为和比电容

通过原位聚合的方式在银纳米粒子/多壁碳纳米管（Ag/MWCNT）复合材料的表面成功聚合苯胺单体制备了聚苯胺/银纳米粒子/多壁碳纳米管（PANI/Ag/MWCNT）三元复合材料苯．通过对三元复合材料的结构以及表面形貌进行分析,表明聚苯胺层完全包覆了Ag/MWCNT复合材料,形成了核壳式结构．同时银纳米粒子则以单质晶体的形态存在于多壁碳纳米管与聚苯胺层之间．三元复合材料电极在1 mol/L的KOH溶液中具有极低的阻抗,而与聚苯胺电极相比,这些复合材料电极则表现出更低的电阻、更高的电化学活性和更好的循环稳定性．尤其是当苯胺和Ag：MWCNTs质量比为5：5时,该复合材料电极在0.25 A/g的电流密度下表现出最大的比电容值为160 F/g．     

Influence of silver-decorated multi-walled carbon nanotubes on electrochemical performance of polyaniline-based electrodes

In this work, silver (Ag) nanoparticles were deposited on multi-walled carbon nanotubes (MWNTs) by chemical reduction while Ag-decorated MWNTs (Ag-MWNTs)/polyaniline (PANI) composites were prepared by oxidation polymerization. The effect of the Ag incorporated into the interface of the composites on the electrochemical performance of the MWNTs/PANI was investigated. It was found that highly dispersed Ag nanoparticles were deposited onto the MWNTs, and the Ag-MWNTs were successfully coated by PANI. According to cyclic voltammograms, the Ag-MWNTs/PANI exhibited significantly increased electrochemical performances compared to MWNTs/PANI and the highest specific capacitance obtained of MWNTs/PANI and 0.15 M Ag-MWNTs/PANI was 162 F/g and 205 F/g, respectively. This indicated that Ag nanoparticles that were deposited onto the MWNTs caused an enhanced electrochemical performance of the MWNTs/PANI due to their high electric conductivity, which resulted in an increase of the charge transfer between the MWNTs and PANI by a bridge effect.     

季铵盐掺杂聚苯胺电极的电容性能

采用循环伏安法,在铂电极表面聚合制备了季铵盐[CnH2n+1N(CH3)3]Cl(n=12,14,16,18)掺杂的聚苯胺修饰电极。 利用扫描电子显微镜、红外光谱以及X射线衍射对复合电极的表面形貌和结构进行了表征。 用循环伏安法、交流阻抗和恒电流充放电测试对电极的电化学性质和电容行为进行了系统研究。 结果表明,其中[C18H37N(CH3)3]Cl季铵盐掺杂的聚苯胺复合电极比表面积大,电容性能好,在2×10-3 A的充电电流下,初始比电容高达329.6 F/g,未掺杂电极比电容为199.0 F/g。 而且,复合电极的循环稳定性良好,经30次循环后比电容保持为252.4 F/g。     

Ag+掺杂聚苯胺的制备及其电容特性研究

以苯胺为单体,采用界面聚合法合成了不同浓度的Ag⁺掺杂的聚苯胺(PANI/Ag⁺),使用傅里叶变换红外光谱（FT-IR）、X射线衍射（XRD）和场发射扫描电镜（SEM）等手段对其结构和形貌进行了分析和表征. 在0.5 mol•L^-1 Na₂SO₄电解液中,通过循环伏安（CV）、恒流充放电（CP）以及电化学阻抗（EIS）等技术研究了其电化学性能. 结果表明,当电流密度为5 mA•cm^-2时,PANI/0.12mol•L^-1 Ag⁺的比电容达529 F•g^-1,循环1000次后比电容保持51%,相对于无Ag⁺掺杂的PANI,表现出更优良的电化学电容特性.     

超级电容器用含氮碳与含氮碳/炭气凝胶复合电极材料的制备和性能研究

采用原位聚合法合成聚苯胺(PAIN)及聚苯胺/炭气凝胶(PAIN/CA)复合材料,经过高温裂解制备含氮碳(NC)及含氮碳/炭气凝胶复合材料(NC/CA),再以KOH为活化剂对其进行活化,制备活化含氮碳(ANC)及活化含氮碳/炭气凝胶复合材料(ANC/CA)。采用扫描电镜、循环伏安、恒流充放电以及电化学阻抗等方法进行性能测试,结果表明,由于KOH的活化作用,含氮碳材料的粒径明显变小,其比电容值为138 F/g,高于未活化含氮碳材料(98 F/g),ANC/AC3复合材料电极的比电容值比ACA电极(88 F/g)高,达到127 F/g。     

Synthesis and high electrochemical performance of polyaniline/MnO2-coated multi-walled carbon nanotube-based hybrid electrodes

Multi-layered electrodes which consist of polyaniline (PANI)/manganese dioxide (MnO₂)-multi-walled carbon nanotubes (MWNTs) are prepared as the electrode materials for supercapacitors. MnO₂-MWNTs are made by the in situ direct coating method to deposit MnO₂ onto MWNTs; the core/shell structure of multi-layered fibrous electrodes can also be obtained by PANI coating onto the MnO₂-MWNTs. The effect of PANI coating on the electrochemical performance and cyclic stability of MnO₂-MWNTs is investigated. From the cyclic voltammograms, the PANI/MnO₂-MWNTs show remarkably enhanced specific capacitance and cycle stability compared to MnO₂-MWNTs, where the highest specific capacitance (350 F/g) is obtained at a current density of 0.2 A/g for the PANI/MnO₂-MWNTs as compared to 92 F/g for pristine MWNTs and 306 F/g for MnO₂-MWNTs. This indicates that the improved electrochemical performance of PANI/MnO₂-MWNTs is due to the enhanced electrical properties by nano-scale-coated MnO₂ onto MWNTs and the PANI coating that leads to the increased cycle stability by delaying the dissolution of MnO₂ during charge/discharge tests.     

Antibacterial properties of polyaniline-silver films

In situ polymerised thin polyaniline (PANI) films produced on polystyrene dishes were tested for their antibacterial activity with respect to Escherichia coli and Staphylococcus aureus, representing both gram-positive and gram-negative bacteria. PANI films were subsequently used for the reduction of silver ions to metallic Ag. PANI salt and base in original forms and after the deposition of Ag were studied. PANI salt showed a significant antibacterial effect against both bacteria strains while the efficacy of neat PANI base was only marginal. After the Ag deposition, the PANI base exhibited different levels of antibacterial effect depending on the type of the bacterial strain; the growth of gram-positive Staphylococcus aureus was inhibited depending on the Ag concentration on the film, while Escherichia coli remained uninfluenced. Efficacy of the PANI salt with deposited Ag against both bacteria strains was comparable with that of PANI alone and was not affected by the Ag concentration. The results show that Ag deposition can be a suitable method for the preparation of PANI base films with improved antibacterial properties.     

Electrochemical storage properties of polyaniline-, poly(N-methylaniline)-, and poly(N-ethylaniline)-coated pencil graphite electrodes

Three types of conducting polymers, polyaniline (PANI), poly(N-methylaniline) (PNMA), poly(N-ethylaniline) (PNEA) were electrochemically deposited on pencil graphite electrode (PGE) surfaces characterized as electrode active materials for supercapacitor applications. The obtained films were electrochemically characterized using different electrochemical methods. Redox parameters, electro-active characteristics, and electrostability of the polymer films were investigated via cyclic voltammetry (CV). Doping types of the polymer films were determined by the Mott-Schottky method. Electrochemical capacitance properties of the polymer film coating PGE (PGE/PANI, PGE/PNMA, and PGE/PNEA) were investigated by the CV and potentiostatic electrochemical impedance spectroscopy (EIS) methods in a 0.1 M H₂SO₄ aqueous solution. Thus, capacitance values of the electrodes were calculated. Results show that PGE/PANI, PGE/PNMA, and PGE/PNEA exhibit maximum specific capacitances of 131.78 F g^?1 (≈ 436.50 mF cm^?2), 38.00 F g^?1 (≈ 130.70 mF cm^?2), and 16.50 F g^?1 (≈ 57.83 mF cm^?2), respectively. Moreover, charge-discharge capacities of the electrodes are reported and the specific power (SP) and specific energy (SE) values of the electrodes as supercapacitor materials were calculated using repeating chronopotentiometry.     

聚苯胺纳米刺/掺氮空心碳球复合材料的制备及电容性能

以掺氮空心碳球（N-HCS）为骨架,通过化学氧化聚合法制备了聚苯胺纳米刺/掺氮空心碳球复合材料（PANI/N-HCS）,采用扫描电子显微镜、透射电子显微镜和红外光谱仪等对样品的形貌、结构等进行了表征. 采用循环伏安、计时电位和交流阻抗等方法在1 mol/L H₂SO₄水溶液中考察了材料的电化学性能. 结果表明,PANI/N-HCS具有良好的电化学性能,在0.5 A/g电流密度下,PANI/N-HCS的比电容达346 F/g;当电流密度为20 A/g时,PANI/N-HCS比电容值为228 F/g,电容保持率为66%;在5 A/g电流密度下,经1000次充放电循环后,电容保持率为76%.     

聚苯胺/碳纳米纤维复合材料的制备及电容性能

采用原位聚合法制备了聚苯胺/碳纳米纤维(PANI/CNF)复合材料,用傅里叶变换红外(FT-IR)光谱、热重分析(TGA)、扫描电镜(SEM)和孔分布及比表面积测定仪研究了复合材料的表面官能团、组成、表面形貌及比表面积,并运用循环伏安(CV)法和计时电位法测试了PANI/CNF布作为电极材料的电化学性能.研究结果表明:PANI/CNF复合材料具有粗糙的毛刺结构,PANI沿碳纳米纤维均匀分布;PANI/CNF电极氧化还原反应的可逆性良好;在100mA·g-1电流密度下,当PANI含量为44.4%(w)时,复合材料比电容量高达587.1F·g-1,比能量为66.1Wh·kg-1,电流密度为800mA·g-1时比功率可达1014.2W·kg-1;在5A·g-1的电流密度下,1000次循环充放电后,复合材料的比电容量衰减28%.PANI/CNF复合材料具有良好的导电性和快速充放电能力,是一种优良的超级电容器电极材料.     

The preparation and performance of flocculent polyaniline/carbon nanotubes composite electrode material for supercapacitors

Polyaniline (PANI)/carbon nanotubes (CNTs) composite electrode material was prepared by in situ chemical polymerization. The structure and morphology of PANI/CNTs composite are characterized by Fourier infrared spectroscopy, scanning electron microscope, and transmission electron microscopy. It has been found that a flocculent PANI was uniformly deposited on the surface of CNTs. The supercapacitive behaviors of the PANI/CNTs composite materials are investigated with cyclic voltammetry, galvanostatic charge/discharge, impedance, and cycle life measurements. The results show that the PANI/CNTs composite electrodes have higher specific capacitances than CNT electrodes and better stability than the conducting polymers. The capacitance of PANI/CNTs composite electrode is as high as 837.6 F g⁻¹ measured by cyclic voltammetry at 1 mV s⁻¹. Besides, the capacitance retention of coin supercapacitors remained 68.0% after 3,000 cycles.     

Fabrication of MnS/GO/PANI nanocomposites on a highly conducting graphite electrode for supercapacitor application

We demonstrate a high surface area of manganese sulfide (MnS) nanoparticles via a simple solution method and investigated its morphology, physicochemical, and electrochemical studies. For the first time, we attempted to exploit the polymerization of aniline without adding HCl, as it is corrosive to the metal sulfide. Instead, the acidic group present on the graphene oxide surface plays a significant role to some extent as an acidic dopant in the polymerization process. This in-situ polymerization results in the uniform coverage of granular PANI on the entire MnS/GO nanocomposite, which enhances the interfacial interactions between PANI and MnS/GO nanoparticles. The introduction of graphene oxide (GO) to pristine MnS improved the specific capacitance, surface area, and average pore size. And incorporating PANI to MnS/GO leads to an increase in the interfacial interaction between the different pore sized nanoparticles giving enhanced specific capacitance. The specific capacitance for MnS/GO/PANI nanocomposite as measured by galvanostatic charge-discharge measurements was found to be 773 F/g at 1 A/g current density, and even at higher current density, it showed a specific capacitance of 484 F/g at 3.8 A/g. The specific capacitance obtained for MnS/GO/PANI nanocomposite from CV shows 822 F/g at 10 mV/s and 315 F/g at 200 mV/s. The combinatorial effects without destroying the metal sulfide nanostructure can provide an alternate route to design, promising electroactive nanocomposites is an ideal choice as a cost-effective, next-generation high-performance supercapacitor application.     

Preparation of hierarchical polyaniline nanotubes based on self‐assembly and its electrochemical capacitance

This article reports the preparation and self‐assembly of polyaniline (PANI) nanotubes, which were chemically synthesized by using in situ doping polymerization in the presence of ammonium persulfate (APS; (NH₄)S₂O₈) as the oxidant without the use of an external template. The synthesized hierarchically nanotubes with a shape of a single nanotube with a length of 0.6 to 0.8 µm and an average with of 100 nm assembled from nanoparticles. The effects of the [salicylic acid]/[aniline] ratio on the size and capacitance of PANI nanotubes were studied. The specific capacitance behavior of the PANI nanotubes was also investigated by using cyclic voltammogram and galvanostatic charge–discharge tests. A maximum discharge‐specific capacitance of 422.5 F/g could be achieved, suggesting its potential application in electrode material for electrochemical capacitors. Copyright © 2011 John Wiley & Sons, Ltd.     

不同质子酸掺杂对银/聚苯胺纳米复合材料结构和导电性的影响

利用紫外光作为辅助条件,在反胶束体系中采用一步双原位法合成了硝酸(HNO3)、对甲基苯磺酸(TSA)和5-磺基水杨酸(SSA)掺杂的银/聚苯胺(Ag/PANI)纳米复合材料.通过对复合材料进行红外光谱(FTIR)、紫外光谱(UV-Vis)、扫描电镜(SEM)、X射线衍射(XRD)和导电性能的测试,研究了不同质子酸对Ag/PANI纳米复合材料结构、形貌和导电性能的影响.测试结果表明,3种酸掺杂制备的Ag/PANI纳米复合材料均为聚苯胺包覆银粒子的核-壳结构.不同的质子酸掺杂会对Ag/PANI纳米复合材料的电性能有重要影响.在3种酸掺杂的复合材料中,TSA掺杂的复合材料的电导率最佳,为215.14 S·cm-1.     

The effect of the polyaniline morphology on the performance of polyaniline supercapacitors

The polyaniline (PANI) prepared by the pulse galvanostatic method (PGM) or the galvanostatic method on a stainless steel substrate from an aqueous solution of 0.5 mol/l H₂SO₄ with 0.2 mol/l aniline has been studied as an electroactive material in supercapacitors. The electrochemical performance of the PANI supercapacitor is characterized by cyclic voltammetry, a galvanostatic charge–discharge test and electrochemical impedance spectroscopy in NaClO₄ and HClO₄ mixed electrolyte. The results show that PANI films with different morphology and hence different capacitance are synthesized by controlling the synthesis methods and conditions. Owing to the double-layer capacitance and pseudocapacitance increase with increasing real surface area of PANI, the capacitive performances of PANI were enhanced with increasing real surface area of PANI. The highest capacitance is obtained for the PANI film with nanofibrous morphology. From charge–discharge studies of a nanofibrous PANI capacitor, a specific capacitance of 609 F/g and a specific energy density of 26.8 Wh/kg have been obtained at a discharge current density of 1.5 mA/cm². The PANI capacitor also shows little degradation of capacitance after 1,000 cycles. The effects of discharge current density and deposited charge of PANI on capacitance are investigated. The results indicate that the nanofibrous PANI prepared by the PGM is promising for supercapacitors.     

蒙脱土基氮掺杂多孔碳@聚苯胺复合材料的制备及电化学性能

分别在盐酸和樟脑磺酸-盐酸混酸溶液中,在蒙脱土基新型氮掺杂多孔碳表面原位聚合苯胺,以制备氮掺杂多孔碳@聚苯胺复合电极材料,采用红外光谱(FTIR)、X射线衍射(XRD)和扫描电子显微镜(SEM)表征复合材料的组成和形貌。 盐酸掺杂的复合材料呈短棒状形貌,樟脑磺酸-盐酸掺杂材料形貌呈颗粒状及交联片状,樟脑磺酸-盐酸掺杂的结晶性能优于盐酸掺杂。 电化学测试结果表明,樟脑磺酸-盐酸掺杂的复合材料在0.5 A/g电流密度下的质量比电容为412.5 F/g,比盐酸掺杂的(332.4 F/g)高24.1%,等效串联电阻(R_s)和电荷迁移电阻(R_ct)小;但盐酸掺杂的复合材料在大电流下电容保持率为81.4%,高于混酸掺杂的58.4%。     

纳米纤维聚苯胺在电化学电容器中的应用

采用脉冲电流方法（PGM）合成了具有纳米纤维结构的导电聚苯胺（PANI）.扫描电子显微镜对膜层观察表明, PANI膜是由直径约为100 nm的掺杂态聚苯胺纤维交织而成.以纳米纤维状聚苯胺组成电化学电容器,研究了其电化学电容性能,并与恒电流方法（GM） 制备的颗粒状PANI电容器性能进行了比较.结果表明,在相同的沉积电量下,PGM制备的纳米纤维状PANI电化学电容器比颗粒状PANI电化学电容器具有更大的电容容量,其电化学电容器的比电容可高达699 F•g－1,能量密度为54.6 Wh•kg－1.并且该电化学电容器具有良好的充放电性能和循环寿命.     

Flexible carbon nanotube/polyaniline paper-like films and their enhanced electrochemical properties

The carbon nanotube/polyaniline (CNT/PANI) composites have important potential applications as the electrodes in energy storage devices for their attractive electrochemical properties. In this work, we report a novel method to prepare the interesting paper-like CNT/PANI composites by using the CNT network as the template. Compared with the conventional brittle CNT/PANI composites, these paper-like composites were much thin and flexible. This work demonstrates a new approach, which may transform a brittle polymer into flexible films. Meanwhile, these film electrodes showed much superior electrochemical performance such as higher specific capacitance, lower internal resistivity, and more stability under different current loads. These paper-like composite electrodes have promising applications in new kinds of energy storage devices.     

Electrochemical behavior of nickel–polyaniline electrode in 1 M LiClO<Subscript>4</Subscript>–propylene carbonate electrolyte

Doping of emeraldine-base (EB) with lithium salts involves the addition of lithium cations to nitrogen in imine groups and intercalation of counter ions i.e., proceeds similarly to doping with protonic acids. The results of studies show that doping of polyaniline (PANI) with a lithium salt proceeds relatively difficultly as compared with protonic doping. For a polyaniline electrode, to attain faster the stationary mode by repeated cycling (“electrode training”) in an organic lithium electrolyte and to reach the higher capacitance, the method of preliminary lithiation of the NiO surface layer on the nickel substrate with Li⁺ cations through the EB film is proposed. The studies show that preliminary cycling of the Ni/PANI electrode (7 cycles at 10 mV s^–1) in the region of negative potentials (from 0 to–2.99 V vs. Ag/AgCl) leads to substantial increase in the capacitance characteristics of the PANI film in the region of its intrinsic redox activity from–0.4 to +1.1 V at high charge–discharge currents (2–5 A/g).     

碳纳米管/聚苯胺/石墨烯复合纳米碳纸及其电化学电容行为

通过真空抽滤的方法制备碳纳米管纸,并对其进行循环伏安电化学氧化处理.以该电化学氧化处理的碳纳米管(CV-CNT)纸为基体,采用电化学聚合沉积聚苯胺(PANI),随后吸附石墨烯(GR),制备具有三明治夹心结构的碳纳米管/聚苯胺/石墨烯(CV-CNT/PANI/GR)复合纳米碳纸.该结构外层为GR,内层由PANI包裹的CNT形成网络骨架,充分发挥三者各自优势构建柔性电极材料.用场发射扫描电镜(FE-SEM)、透射电子显微镜(TEM)、拉曼光谱对其形貌与结构进行表征,并测试其电化学性能.研究发现:PANI呈纳米晶须状,并均匀包裹在CV-CNT表面;该复合碳纸具有良好的电容特性、大电流充放电特性以及良好的循环稳定性能.电流密度为0.5A·g-1时,比电容可达415F·g-1;20A·g-1时仍能保持106F·g-1的比电容.由于GR的保护作用,1000次循环之后较CV-CNT/PANI保持更高的有效比电容.该CV-CNT/PANI/GR复合碳纸展现出在高性能超级电容器柔性电极材料的潜在应用价值.