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.     

可快速充放电聚吡咯/碳纳米管复合材料电化学聚合与表征

采用恒电流法制备了具有可快速充放电性能的对甲基苯磺酸根(TOS-)掺杂聚吡咯/功能化单壁碳纳米管(PPy-TOS/F-SWNTs)复合材料,扫描电镜(SEM)结果表明该复合材料呈纳米棒状构成的多孔结构,棒径约为70nm;比表面积(BET)测试分析表明该复合材料有着较高的比表面积(12.64m2.g-1)和大的介孔孔隙率(20-40nm).循环伏安(CV)、电化学阻抗谱(EIS)和恒电流充放电(GC)电化学分析表明该材料具有优异的快速充放电性能,在800mV的电位窗和2.5A.g-1(功率密度为2kW.kg-1)的电流密度下该材料具有211F.g-1的比容量(能量密度为18.7Wh.kg-1),而当充放电电流高达80A.g-1(功率密度为60kW.kg-1)时比容量仍可达141.8F.g-1(能量密度为12.6Wh.kg-1),同时该材料还表现出优异的稳定性,在10A.g-1大电流下经历10000圈循环后容量仍保持95.2%.     

MoO3基纳米复合材料的制备及其电化学性能研究

以MoO3为基体,分别用超声分散法与碳纳米管(CNTs),化学原位聚合法与聚吡咯(PPy)复合,制备了MoO3/CNTs,MoO3/PPy和MoO3/CNTs/PPy纳米复合材料。利用XRD、SEM、TEM对复合材料进行物性表征,在1 mol·dm-3的HCl溶液中对MoO3,MoO3/CNTs,MoO3/PPy和MoO3/CNTs/PPy四个样品进行电化学测试。结果表明,复合材料的比容量均高于MoO3,其中,由于MoO3/PPy特殊的一维核壳结构使其具有较高的比表面积,相比较其他复合材料而言,有更好的电化学活性。该材料的最大比电容为450.8F·g-1。     

多次聚合法制备多孔聚吡咯厚膜及其电化学容量性能

为了得到高面积比容量的聚吡咯(PPy)膜超级电容器电极材料, 用多次聚合法合成了PPy厚膜, 聚合电量分别为8、10和12 mAh·cm-2, 掺杂离子分别为氯离子和对甲基苯磺酸根离子(TOS-). PPy膜的电化学性能采用恒电流充放电、循环伏安(CV)和电化学阻抗谱(EIS)等方法测试. 研究表明, 多次聚合法可以制备表面平整且内部均匀多孔的PPy厚膜. 在聚合电量为12 mAh·cm-2时, 用Cl-、TOS-两种离子掺杂的PPy厚膜的面积比容量高达5 F·cm-2, 并表现出理想的电化学容量性能. 同时PPy-Cl厚膜的质量比容量达到330 F·g-1, PPy-TOS厚膜的质量比容量略低(191 F·g-1), 但具有更快的充放电速率. 与一次聚合法合成的PPy 薄膜相比, 多次聚合法合成的PPy厚膜的质量比容量没有降低. 通过场发射扫描电镜(SEM)观察了一次聚合法和多次聚合法制备的PPy厚膜的截面形貌, 并讨论了多次聚合法的合成机理.     

聚吡咯/海藻酸钠纳米球的制备及其应用于高性能超级电容器

用海藻酸钠作为结构导向剂,通过原位氧化聚合吡咯法制备了聚吡咯/海藻酸钠(PPy/SA)纳米球.聚吡咯/海藻酸钠纳米球的形貌和结构通过扫描电镜(SEM)、X射线衍射(XRD)和傅里叶变换红外(FTIR)光谱进行表征.材料的电化学性能通过循环伏安法和恒电流充放电方法进行测试.电化学测试表明,聚吡咯/海藻酸钠纳米球在1 mol L-1KCl电解液中,电流密度为1 A g-1时其比电容高达347 F g-1.与纯聚吡咯相比较,聚吡咯/海藻酸钠纳米球具有更优异的循环稳定性能.     

不同状态下聚吡咯膜的电化学阻抗

用恒电流法分别聚合了掺杂对甲苯磺酸根(pTS-)和十二烷基磺酸根(DS-)的聚吡咯膜(PPy/pTS和PPy/DS),通过循环伏安法(CV)和电化学阻抗法(EIS)测试了聚吡咯膜在NaCl溶液中‘过电位’电化学过程前后及不同电位下聚吡咯膜的电化学性能.同时,通过嵌入和脱出Na+和Cl-离子的聚吡咯膜在特定溶液中电化学阻抗图谱,研究了离子的嵌入对聚吡咯膜电化学性能的影响.结果表明‘过电位’现象可以提高聚吡咯膜的离子电导率和膜电容,Cl-离子的嵌入能提高PPy/pTS的电导率,而Na+离子的嵌入对聚吡咯膜的电导率影响不大.另外,嵌入离子对聚吡咯膜形貌的改变会对聚吡咯膜的离子传导率有一定影响,从而导致膜的电化学阻抗的变化.     

ZnO/PPy异质纳米复合材料的制备、表征及其气敏特性

室温下, 采用原位聚合法, 以吡咯(PY)为单体, 氯化铁(FeCl₃·6H₂O)为氧化剂, 在塑料基片上聚合生长了聚吡咯(PPy)纳米微球. 然后在聚吡咯基片上生长ZnO种子, 将表面种有ZnO种子的PPy元件置于六次甲基四胺与硝酸锌的混合溶液中, 90 ℃水浴中, 在PPy微球上生长了ZnO纳米棒, 合成了PPy/ZnO异质纳米复合材料. 分别通过X射线衍射仪(XRD)和场发射扫描电镜(FESEM)对PPy/ZnO异质纳米复合材料的结构和形貌进行了表征. 制备了塑料基的PPy/ZnO异质纳米复合材料气体传感器, 在室温下, 对10×10^-6-150×10^-6 (体积分数)浓度范围的氨气进行了气敏测试, PPy/ZnO气敏元件对氨气响应的灵敏度基本呈线性关系, 且对甲醇、丙酮、甲苯等有机气体表现出很好的选择性. 最后, 对PPy/ZnO异质纳米复合材料的形成机理进行了简要分析.     

掺杂离子对聚吡咯膜的电化学容量性能的影响

用电化学方法制备了分别以对甲基苯磺酸根(TOS-), 高氯酸根(ClO-4)和氯离子(Cl-)掺杂的聚吡咯(PPy)膜. 用循环伏安(CV)、恒电流充放电和电化学阻抗谱(EIS)等测试了它们的电化学容量性能. 用扫描电镜(SEM)和X射线衍射(XRD)分别研究了这三种PPy膜的形貌和结构. 研究发现, 由于具有疏松多孔的形貌和更有序的分子链结构, PPy-TOS和 PPy-Cl膜具有较好的充放电能力, 在深度充放电时仍具有很小的电化学电阻, 其离子扩散接近理想电容器的离子扩散机理. PPy-Cl(聚合电量2 mAh·cm-2)的比容量在扫描速率为5 mV·s-1时高达270 F·g-1, 扫描速率200 mV·s-1时仍高达175 F·g-1, 特别是, 其比能量高达35.3 mWh·g-1. PPy-TOS由于有质量较大的掺杂离子(TOS-)因而比容量略低(146 F·g-1, 扫描速率5 mV·s-1), 但具有超快速充放电能力, 在扫描速率为200 mV·s-1时, 比容量为123.6 F·g-1, 其比功率高达10 W·g-1. 并且, 两种电极材料均具有稳定的电化学循环性能.     

电化学沉积制备氧化石墨烯/聚吡咯复合材料及其用于超级电容器的研究

本文采用改进的Hummers法制备氧化石墨烯(GO),利用电化学沉积法制备聚吡咯(PPy)和GO/PPy复合材料并对其作为超级电容器电极材料进行了探究。通过XRD、FT-IR、AFM和SEM对其结构和形貌进行了表征,研究表明:PPy成功在GO片层上生长,并改变了原来PPy类逗号形的形貌,形成了无定形结构的GO/PPy复合材料。循环伏安法(CV)对不同电沉积时间的PPy和GO/PPy电容量进行了测试,发现电沉积时间为17min的PPy和GO/PPy均表现出较优的电容性能。在1A/g电流密度下进行恒流充放电(CP)测试,通过比较发现GO/PPy比PPy的比电容量提高了82. 3%,达到332. 37F/g。     

9,10-蒽醌-2-磺酸钠盐掺杂对导电聚吡咯电容性能的促进作用

用恒电位法制成以9,10-蒽醌-2-磺酸钠盐(AQS)为掺杂阴离子的导电聚吡咯(PPy)电化学电容器电极材料,并采用循环伏安(CV)、充放电测试、电化学阻抗(EIS)等方法表征电容性质.结果表明,与高氯酸阴离子(ClO4-)掺杂的PPy相比,PPy/AQS电极材料不仅单位质量电容和电极稳定性得到提高,工作电压范围也得以扩大.在1mol·L-1的氯化钾中,工作电压为-0.6至0.6V,扫描速率为50mV·s-1时其单位质量电容达到491F·g-1,比PPy/ClO4-电极材料提高1.5倍.这是由于AQS自身良好的氧化还原活性和AQS掺杂有利于聚吡咯膜形成疏松多孔的纳米及亚微米颗粒结构而导致的.     

Synthesis and characterization of carbon nanotube/polypyrrole core–shell nanocomposites via in situ inverse microemulsion

We demonstrate here a feasible approach to the preparation of multiwalled carbon nanotube (MWNT)/polypyrrole (PPy) core–shell nanowires by in situ inverse microemulsion. Transmission electron microscopy and scanning electron microscopy showed that the carbon nanotubes were uniformly coated with a PPy layer with a thickness of several to several tens of nanometers, depending on the MWNT content. Fourier transform infrared spectra suggested that there was strong interaction between the π‐bonded surface of the carbon nanotubes and the conjugated structure of the PPy shell layer. The thermal stability and electrical conductivity of the MWNT/PPy composites were examined with thermogravimetric analysis and a conventional four‐probe method. In comparison with pure PPy, the decomposition temperature of the MWNT/PPy (1 wt % MWNT) composites increased from 305 to 335 °C, and the electrical conductivity of the MWNT/PPy (1 wt % MWNT) composites increased by 1 order of magnitude. The current–voltage curves of the MWNT/PPy nanocomposites followed Ohm's law, reflecting the metallic character of the MWNT/PPy nanocomposites. The cyclic voltammetry measurements revealed that PPy/MWNT composites showed an enhancement in the specific charge capacity with respect to that of pure PPy. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 6105–6115, 2005     

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.     

Electrochemically Controlled Ion‐exchange Property of Carbon Nanotubes/Polypyrrole Nanocomposite in Various Electrolyte Solutions

The electrochemically controlled ion‐exchange properties of multi‐wall carbon nanotube (MWNT)/electronically conductive polypyrrole (PPy) polymer composite in the various electrolyte solutions have been investigated. The ion‐exchange behavior, rate and capacity of the electrochemically deposited polypyrrole with and without carbon nanotube (CNT) were compared and characterized using cyclic voltammetry (CV), chronoamperometry (CA), electrochemical quartz crystal microbalance (EQCM), X‐ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). It has been found that the presence of carbon nanotube backbone resulted in improvement in ion‐exchange rate, stability of polypyrrole, and higher anion loading capacity per PPy due to higher surface area, electronic conductivity, porous structure of thin film, and thinner film thickness providing shorter diffusion path. Chronoamperometric studies show that electrically switched anion exchange could be completed more than 10 times faster than pure PPy thin film. The anion selectivity of CNT/PPy film is demonstrated using X‐ray photoelectron spectroscopy (XPS).     

Characterization and electrical properties of polypyrrole/multiwalled carbon nanotube composites synthesized by in situ chemical oxidative polymerization

This study describes the preparation of polypyrrole (PPy)/multiwalled carbon nanotube (MWNT) composites by in situ chemical oxidative polymerization. Various ratios of MWNTs, which served as hard templates, were first dispersed in aqueous solutions with the surfactant cetyltrimethylammonium bromide to form micelle/MWNT templates and overcome the difficulty of MWNTs dispersing into insoluble solutions of pyrrole monomer, and PPy was then synthesized via in situ chemical oxidative polymerization on the surface of the templates. Raman spectroscopy, Fourier transform infrared (FTIR), field‐emission scanning electron microscopy (FESEM), and high‐resolution transmission electron microscopy (HRTEM) were used to characterize the structure and morphology of the fabricated composites. Structural analysis using FESEM and HRTEM showed that the PPy/MWNT composites were core (MWNT)–shell (PPy) tubular structures. Raman and FTIR spectra of the composites were almost identical to those of PPy, supporting the idea that MWNTs served as the core in the formation of a coaxial nanostructure for the composites. The conductivities of these PPy/MWNT composites were about 150% higher than those of PPy without MWNTs. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1413–1418, 2006     

Controlled preparation of carbon nanotube-conducting polymer composites at the polarisable organic/water interface

The electro-polymerisation of polypyrrole (PPy) at the interface between two immiscible electrolyte solutions (ITIES) is reported. The approach is used to demonstrate the formation of a carbon nanotube (SWCNT)-conducting polymer composite, by performing polymerisation in the presence of an assembly of SWCNT films. The morphology of the SWCNT/PPy nanocomposites was determined using probe and electron microscopy and complementary spectroscopic techniques (EDAX, Raman).     

Design and synthesis of the polyaniline interface for polyamide 66/multi-walled carbon nanotube electrically conductive composites

A polyaniline interface had been designed and built between multi-walled carbon nanotubes (MWCNTs) and polyamide 66 (PA66) in order to help in the dispersion of MWCNTs in PA66 and improve the interfacial combination between them. Transmission electron microscopy characterizations indicated that functionalized MWCNTs (f-MWCNTs) could be well-distributed in PA66 matrix and the interfacial boundary between them was indiscernible. The mixing conditions, such as f-MWCNT content, temperature, and mixing speed, played important roles in determining the formation of the conductive network and the electrical conductivities of PA66/f-MWCNT composites synthesized. A continuous conductive network was formed at 10 wt% f-MWCNT content, and the corresponding PA66/f-MWCNT composite exhibited an electrical conductivity of 8 orders of magnitude higher than pure PA66. The conducting mechanism agreed well with a thermal fluctuation-induced tunneling model.     

Fabrication and Properties of Conducting Polypyrrole/SWNT‐PABS Composite Films and Nanotubes

We report the electropolymerization and characterization of polypyrrole films doped with poly(m‐aminobenzene sulfonic acid (PABS) functionalized single‐walled nanotubes (SWNT) (PPy/SWNT‐PABS). The negatively charged water‐soluble SWNT‐PABS served as anionic dopant during the electropolymerization to synthesize PPy/SWNT‐PABS composite films. The synthetic, morphological and electrical properties of PPy/SWNT‐PABS films and chloride doped polypyrrole (PPy/Cl) films were compared. Characterization was performed by cyclic voltammetry, atomic force microscopy (AFM), scanning electron microscopy (SEM) and Raman spectroscopy. SEM and AFM images revealed that the incorporation of SWNT‐PABS significantly altered the morphology of the PPy. Cyclic voltammetry showed improved electrochemical properties of PPy/SWNT‐PABS films as compared to PPy/Cl films. Raman Spectroscopy confirmed the presence of SWNT‐PABS within composite films. Field effect transistor (FET) and electrical characterization studies show that the incorporation of the SWNT‐PABS increased the electronic performance of PPy/SWNT‐PABS films when compared to PPy/Cl films. Finally, we fabricated PPy/SWNT‐PABS nanotubes which may lead to potential applications to sensors and other electronic devices.     

Preparation of submicron polypyrrole/poly(methyl methacrylate) coaxial fibers and conversion to polypyrrole tubes and carbon tubes

In an effort to prepare electrically conductive nanofiber and nanotube materials, polypyrrole/poly(methyl methacrylate) coaxial fibers have been prepared using polymer fibers produced from an electrospinning process. Poly(methyl methacrylate) (PMMA) fibers with an average diameter of 230 nm were initially fabricated by electrospinning as core materials. The PMMA fibers were subsequently coated as templates with a thin layer of polypyrrole (PPy) by in-situ deposition of the conducting polymer from aqueous solution. Hollow PPy tubes were produced by dissolution of the PMMA core from PPy/PMMA coaxial fibers. High-temperature (1000 degrees C) treatment under inert atmosphere converted PPy/PMMA coaxial fibers into carbon tubes by complete decomposition of PMMA fiber core and carbonization of the PPy wall. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), and FT-IR spectroscopy confirmed the formation of the PPy/PMMA coaxial fibers, PPy tubes, and carbon tubes.