论文中英文摘要

论文 政研论文下载论文大学下载论文大学下载关于长拳的论文浙大论文封面下载 中英文摘要 附件2 论文中英文摘要 作者姓名:王杰 论文题目:电化学合成聚吡咯膜的电学性能与应用 作者简介:王杰，男，1978年3月出生，2004年3月师从于西安交通大学徐友龙教授，于2008年3月获博士学位。 中 文 摘 要 电子导电高分子(Electronically Conductive Polymer, ECP)是在掺杂状态具有半导体(甚至是金属导体)的电子电导率，并可以在掺杂态和脱掺杂态间快速转换的一种高分子材料。由于ECP兼备导体的电性能和高分子的机械性能，作为一种廉价的、轻型的和不会发生腐蚀的材料，在过去的三十年里得到了广泛的研究，并应用于(或潜在运用于)电子与光子器件、电化学储能、抗静电以及金属防腐等领域。其中，聚吡咯(polypyrrole, PPy)不仅具有优异的电性能和电化学性能，而且具有合成容易、价格低廉和环境友好(environmental firendly)等优势，被认为是一种具有广阔应用前景的ECP材料。大量研究 表 关于同志近三年现实表现材料材料类招标技术评分表图表与交易pdf视力表打印pdf用图表说话 pdf 明，PPy性能容易通过制备条件进行“剪裁”，在各种制备方法中，电化学法兼具原位成膜的便利和膜厚易控制的优势。本文在多种电极(钽、铜和铝阳极体)表面原位电合成PPy膜，着重研究聚合条件对PPy的结构和电化学性能的影响，探索其在超级电容器、防腐和聚合物铝电解电容器中的应用。 首先，在钽电极上实现了0?下高密度PPy(High Density PPy，HD-PPy)的大电流(10 -2-3mA•cm)制备，获得的PPy膜的密度为1.42 g•cm。该密度值和目前报道的在-40?用低电 -2流密度(0.02,0.05 mA•cm)时得到的值相当，而本文的制备方法具有容易实现、周期短和成本低的优势，因此更具有应用价值。X-射线光电子能谱(XPS) 分析 定性数据统计分析pdf销售业绩分析模板建筑结构震害分析销售进度分析表京东商城竞争战略分析 表明，HD-PPy的形成机理是高电流密度导致了平面型二维分子链结构的形成。用四探针法测得HD-PPy的室温电导 -1率高达200 S•cm。通过热失重分析发现，HD-PPy比通常的PPy膜具有更高的脱掺杂温度和降解温度。因其高电导率、高热稳定性，HD-PPy将是一种优异的电极材料。另外，电化学阻抗谱(EIS)和循环伏安(CV)分析表明HD-PPy能显著地阻碍离子传输，因此也将是优异金属防腐材料。 微/纳结构的PPy具有奇异的性能和广泛的潜在应用，得到了大量的关注，但是目前制备微/纳结构的PPy常用的方法为模板法。此外，由于普遍认为碱性溶液中的氢氧根会通过去质子化作用，对吡咯聚合的碳正离子基团耦合过程产生阻碍，因此在碱性溶液中合成聚吡咯的报道较少，一般都在pH为1,5的环境中聚合。一些研究者的尝试也表明了即使在碱性溶液中得到聚吡咯，其电导率也很低，甚至不导电。本文突破性地发现了在碱性溶液中采用较大的电流密度可以制得具有羊角状的聚吡咯(h-PPy)，实现了用无模板法制备微/纳结构的PPy。为了实现无模板法合成特殊微/纳结构的PPy，首先研究了溶液pH值和电流密度对PPy结构 --2和形貌的影响，并在pH,9的对甲基苯磺酸根(TOS)溶液中采用大电流密度(>3mA•cm)首次合成了h-PPy，鉴于在pH,9的LiClO溶液中也制备出了h-PPy，排除了h-PPy是由表面4 -活性剂分子TOS作为分子模板所致。XPS分析表明，其形成机理可能是在高电流密度下形成了一种非平面型的二维分子链结构。h-PPy不仅具有高比表面积和高结晶度，并且室温电导 -1率可达到90 S•cm，与之相比在该pH下用小电流密度合成的常见椰菜花形状PPy的室温电 -1导率<10 S•cm。h-PPy独特的微纳米结构、高比表面积和高电导率必将为之带来广泛的应用。 由于石化资源逐渐枯竭和环境日益恶化，急需开发环保、高效的能源利用方式。超级电容器是兼具传统电容器的高功率密度和电池的高能量密度特性的储能器件，并具有环境友好、寿命长等优点，可以潜在运用于电动车和太阳能/风能绿色能源领域，成为研究热点。超级电容器研究的关键技术之一在于开发出具有高比容量、宽电位窗、快速充放电能力、长期稳定地循环充放电能力并且环境友好的电极材料。目前广泛使用的是基于碳材料的电极材料，但其只能用表面电双层储存电量，难以满足高比容量的要求。基于PPy的电极材料可以通过法拉第反应利用所有活性物质来储存能量，具有高比容量特性，但是目前由于受到离子在聚合物体相中扩散速率的限制，充放电速率还比较低，且充放电过程中如果发生显著的体积变化会致使循环稳定性差。为了提高PPy电极材料的充放电速率和循环稳定性，首先采用了聚(3,4-乙撑二氧噻吩)(PEDOT)表面修饰PPy。由于协同效应，PEDOT/PPy复合物具有比单一材料更高的比容量和充放电速率，并具有PEDOT的高电位窗(1V)。特别是在h-PPy表面获得的多孔PEDOT/h-PPy双层复合物，由于多孔结构有利于电解液的扩散，其比容量达到290 F•-1g并具有快速的充放电性能和稳定性的循环性能。其次，在浓硫酸/浓硝酸中超声振荡单壁碳纳米管(SWNTs)，获取长度小于100 nm并高度离子化的功能化单壁碳纳米管(F-SWNTs)，进 -1一步电化学制备了颗粒尺寸约为100 nm的PPy/F-SWNTs复合物。其比容量达到230 F•g，电荷转移电阻极低(小于0.05 Ω)，且在电位窗0.8 V下具有稳定的循环性能。最后，通过正交实验优化制备条件，获得了多孔的PPy膜，其电化学性能进一步通过掺杂离子剪裁: -1PPy-Cl具有高比容量,可达到270 F•g， PPy-TOS(对甲基苯磺酸根)具有快速充放电能力，并都具有稳定的循环性能。为了提高基于PPy的多孔电极的面积比容量，提出了用多次聚合 -2法制备多孔PPy-Cl和PPy-TOS厚膜，其面积比容量高达5 F•cm，且质量比容量未随膜厚增加而明显降低。因此这四种基于PPy的材料都将是优异的超级电容器电极材料。 据报道，全世界因金属腐蚀造成的经济损失超过7000亿美元，而我国腐蚀造成的年损失超过达5000亿元以上，金属腐蚀问题已经成为影响国民经济和社会可持续发展的重大障碍之一。金属铜广泛使用于电子、 工程 路基工程安全技术交底工程项目施工成本控制工程量增项单年度零星工程技术标正投影法基本原理 等诸多领域，为了延长其使用寿命和扩展应用领域，必须提高其腐蚀电阻，因此本文探索了PPy膜对铜腐蚀保护性能。然而，铜较低的腐蚀电位使得在其表面现场电化学制备PPy成为难题，为此，首先在金属铜电极表面预先循环伏安法合成PPy-CO衬底层，实现了在铜电极上电化学制备HD-PPy和PPy-DBS膜。在3.5wt, NaCl溶液24 中防腐性能测试表明，由于有效的物理阻隔作用，HD-PPy电极的腐蚀电流比LD-PPy低一个数量级。与PPy-CO和PPy-TOS相比，PPy-DBS的有效保护时间为三倍以上，腐蚀电流低两个24 --2-数量级。其原因在于DBS体积较大而固定在PPy网格内，通过对腐蚀离子(Cl)和CO的静24 -2-电排斥作用，既可以阻碍Cl穿透PPy膜而腐蚀金属基底，也可以阻碍CO从膜中逃逸而长24时间维持电极的“自愈”能力。 最后，探讨了PPy在铝电解电容器中的应用。经由长期的发展，铝电解电容器凭借其大容量、低等效串联电阻和低成本等优势，已经占据了所有电容器30,以上的市场。然而，一般铝电解电容器阴极为液体电解质，使用温度范围窄，且不能承受表面贴装工艺(SMT)中的 再流焊而难于实现片式化。更重要的是，由于工作电解液的电导率较低 (常小于0 .01 S/cm)，使得电容器的频率特性差(电容量在10KHz就有很大的下降)。如果采用PPy作为铝电解电容器的阴极材料，由于PPy的高电导率(σ?100S/ cm)和高热稳定性，可以获得高性能并易于片式化固体铝电解电容器。然而，铝阳极体为多孔复杂表面并形成了绝缘的介质氧化膜(AlO)，难以原位电化学合成均匀PPy膜，并且PPy对AlO的修复能力不如传统电解液，2323 因此该类电容器漏电流较大的问题难以解决。本文通过在铝阳极体表面用高锰酸钾氧化吡咯单体制备一层导电衬底层以及控制氧化剂浓度和相应的浸渍次数，掌握了在绝缘铝阳极体表面均匀现场电化学被覆PPy的关键技术，采用有效的阻隔材料和优化的电流 方案 气瓶 现场处置方案 .pdf气瓶 现场处置方案 .doc见习基地管理方案.doc关于群访事件的化解方案建筑工地扬尘治理专项方案下载 缩短电化学聚合时间突破了该类电容器漏电流大的瓶颈问题。在中试线上，通过引入热处理和后期补形成工艺，进一步降低了该电容器的漏电流。基于上述关键技术的突破，获得了四种电压规格(4、6.3、10和16V)，八种容量规格的具有自主知识产权的高性能片式化铝固体电解电容器(PA-Cap)。技术指标(如损耗<0.06, 漏电流小于0.04CV或2μA)达到了国际先进水平，并通过了教育部组织的专家组鉴定。本文的研究成果已经在福建国光电子科技股份有限公司转化为高科技产品，并形成了规模化工业生产。 关键词: 聚吡咯;电化学合成;电解电容器;超级电容器;离子传输 Electrical Properties and Application of Polypyrrole Films Prepared by Electrochemical Method Wang Jie ABSTRACT Electronic conducting polymer (ECP) is a kind of material possessing nearly metallic conductivity under its doped state, a good reversibility between the doped state and undoped state (no decomposition due to dopant, the solvent or any other agents), a good stability in air and good mechanical properties allowing easy handling. Conducting polypyrrole (PPy) has been extensively investigated and is considered as one kind of the most promising ECP, due to its excellent properties and advantages including environmentally friendly feature, high room-temperature conductivity, low cost and facile synthesis. -In the studies, the high density PPy films (HD-PPy) doped by p-toluenesulfonate (TOS), were -2 prepared on tatanum electrodes at the current density of 10 mA•cmin AN/HO solution with a 2 -3temperature of 0?. Its density was up to 1.42 g•cm, which was slightly larger than the maximum -2reported value abtained on glass carbon electrodes by 0.02,0.05 mA•cm at -40?. The method in the studies was of more practical value from the view of application, because it is easy to perform, low cost, time saving, and especially independent of the electrode surface. X-ray photoelectron spectra analysis revealed that the high density of PPy might be resulted from the formation of plane-type two dimensional (2D) structure of molecular chains. The room-temperature conductivity -1 of HD-PPy was demonstrated to be up to 200 S•cmby four-probe methods. Furthermore, the thermal stability of HD-PPy films was significantly superior to that of conventional PPy films. In additional, HD-PPy could hinder ions insertion more effectively. It can be concluded that HD-PPy would be an excellent electrode material and anticorrosion material. Micro/nanostructured materials have attracted great interest in recent years because of the exceptional structural and physical properties endowed by confining dimensions and the combination of bulk and surface properties to the overall behavior. Up to now, micro/nanostructures of conducting polymers have been generally prepared using hard or soft templates. Aiming to explore free-template method to relize micro/nano-PPy, the effects of pH and current density of polymerization on the morphology and structure of PPy were investigated. The horn-like PPy films (h-PPy) with horns in micro/nano size were obtained at pH=9 aqueous solution with current density -2larger than 3mA•cm. X-ray photoelectron spectra analysis showed that the horn might be a kind of non-plane 2D structure of molecule chains resulted from high current density in polymerization process. Furthermore, h-PPy was characterized as great specific area and highly ordering. The length of crystalline domain of h-PPy films was up to 32.9 nm, which was larger than the reported value by one order of magnitude. In addition, the room-temperature conductivity of h-PPy was up -1to 90 S•cm, although the conductivity of usual PPy prepared in the alkaline solution was about 1 -1-Scm due to a large number of defects in the PPy chain resulted from the attack of OH to free β-C of pyrrole ring. The storage of electrical energy at high charging and discharging rate is a very important technology in the twenty-,rst century. It enables electric vehicles and provides back-up for wind and solar energy, both of which are vital to meet the challenge of global warming and the finite nature of fossil fuels. Therefore, electrochemical capacitors (supercapacitors), which combine the advantages of the high power of dielectric capacitors and the high specific energy of rechargeable batteries, have attract considerable attention in the last decade. Thanks to the high conductivity and large pseudo-capacitance, especial the potential to fabricate flexible solid supercapacitors, electronically conducting polymers (ECPs) have been the focus of interest of supercapacitor studies. Among the ECPs, conducting polypyrrole (PPy) is considered one of the prominent electrode materials of supercapacitors due to its low cost, ease of synthesis, environmentally friendly feature, and relatively high conductivity. To improve the charge/discharge rate and cycling stability of PPy-based electode of supercapacitor, the PEDOT/h-PPy composites and the composites of PPy and functionalized single-walled carbon nanotubes (F-SWNTs) were prepared by electrochemical methods. Their morphology was observed by using Field Emission Scanning Electron Microscope (SEM). The electrochemical capacitance properties of the composites were investigated with cyclic voltammetry (CV), galvanostatic charge-discharge and electrochemical impedance spectroscopy (EIS) techniques in the two- or three-electrode cell system. The two kinds of composites were characterized with highly porous structure, which leads to their specific capacitance up to 290 and -1 230 F•gin 1M KCl aqueous solutions, respectively. Furthermore, they have very fast charge/ discharge rate and good cycle stability at potential window of 1V and 0.8 V, respectively. More importantly, their discharge efficiency (discharging capacitance divided by charging capacitance) is almost 100% during the 1000 cycles. The porous PPy films were also obtained in the optimized conditions, whose electrochemical properties can be tailored by doping ions. Specific capacitance of -2-1-1PPy-Cl (polymerization charge 2 mAh•cm) could reach 270 F•g (scanning rate 5 mV•s) or 175 -1-1-1F•g (scanning rate 200 mV•s) and its specific energy could reach 37.5 Wh•kg. With heaver --2doping ion (TOS), PPy-TOS (polymerization charge 2 mAh•cm) had a slightly smaller specific -1-1capacitance (146 F•g, scanning rate 5 mV•s) but a very rapidly charge/discharge ability (specific -1-1capacitance 123.6 F•g at scanning rate 200 mV•s) and its specific power could reach 10 -1kW•kg. In addition, both PPy-TOS and PPy-Cl electrodes had a good cycleability. To obtain polypyrrole (PPy) films with high area specific capacitance as the electrode material of supercapacitors, the multiple-step polymerization method was proposed for preparing thick PPy -2-films with polymerization charge of 8, 10 and 12 mAh•cm, doped with Cl and p-toluenesulfonate -(TOS), respectively. The two kinds of even porous PPy films, PPy-Cl and PPy-TOS with area -2specific capacitance up to 5 F•cm were obtained by the method. Moreover, their mass specific -1-1-2capacitance could reach 330 F•g and 191 F•g at discharge current of 1 mA•cm. In conclusion, PEDOT/h-PPy, PPy/F-SWNTs, PPy-Cl and PPy-TOS will be four kinds of promissing electrode materials for supercapacitors. Polypyrrole films doped with dodecylbenzenesulfonate (PPy-DBS) were prepared for effective copper protection by galvanostatical method on an underlayer of polypyrrole doped with oxalate (PPy-CO), because PPy-DBS could not be obtained directly on copper surface by electrochemical 24 methods. Their anticorrosion performance in 3.5% NaCl solution was compared with that of the bilayer PPy-CO coatings with equal thickness by using open circuit potential-time (E-t) 24oc diagrams, anodic polarization curves, and electrochemical impedance spectroscopy (EIS). The well-protected time is more than 500 h even the PPy-DBS films with thickness only 15 μm, which is 5 times longer than that of PPy-CO films. Furthermore, the corrosive current on PPy-DBS 24 electrode drops by two orders of magnitude compared with PPy-CO electrode. It could be that 24 -DBS is difficult to eject from PPy films because of its large size. Consequently, it obstructs the -corrosion ions (Cl) from penetrating the PPy films, and hinders the oxalate from escaping so that the healing ability of PPy could be maintained for a long term. The obstructing effect was confirmed by electrochemical impedance spectroscopy (EIS) and energy dispersive x-ray -spectroscopy (EDS). HD-PPy films doped by TOS were also obtained by electrochemical method on PPy-CO modified copper electrode in acetonitrile/water (volume ratio 99/1) solution under 24 -20 ? condition with high current density (such as 10 mAcm). Compared with conventional low -3density PPy-TOS films (0.6~0.8 gcm), The HD-PPy films can further improve the corrosive potential of copper and reduce the corrosive current by one order of magnitude. Its well-protecting time was three times than that of LD-PPy film. The reason is that HD-PPy with more compact -structure can obstruct corrosive ions Cl from penetrating the PPy films, and hinder the escape of 2-CO from the underlayer, which can maintain the healing ability of PPy films for a long term. Its 24 obstruct ability was confirmed by EIS and EDS. The results demonstrate that HD-PPy and PPy-DBS films on an underlayer of PPy-CO have potential application to protect copper. 24 In recent years high performance characteristics, including low impedance at high frequencies, thermal stability in molten solder to enable its use in surface mounting technology and improved reliability, have become of great importance for electrolytic capacitors. Conventional aluminium electrolytic capacitors present many disadvantages such as high impedance and thermal unstability, owing to the use of a low-conductive and thermally unstable liquid electrolyte, although it processes about 30% capacitor market thanks to its high specific capacitance and low cost. In this study, PPy was used as cathode material of aluminium electrolytic capacitor to low its impedance and thermal stability. The challenge of electropolymerization of pyrrole on the surface of insulative AlO was 23 overcome by preparing an underlayer of PPy/MnO composite prepared by chemical method. The 2 effect of the concentration of KMnO and the dip times on the properties of resulted PPy aluminum 4 solid electrolytic capacitors (PA-Cap) was studied. The results show that high capacitance and low dissipation factor can be obtained by dipping the anode three times in the 0.2 M KMnO aqueous 4 solution. The leakage current can be effectively decreased by using coating silicon rubber to avoid the short circuit between the anode and the cathode and shortening polymerization process by using high current density. The leakage current was further decreased by thermal treatment during pilot production. The high performance aluminum electrolytic capacitors with the dissipation less than 0.06 and the leak current less than 0.04CV or 2μA were achieved and had been put into manufacture in GUOGUANG ELECTRONIC SCE-TEC Co., Ltd. Key words: Poplypyrrole; Electrochemical; Electrolytic capacitors; Supercapacitors; Ions transportation