高容量超级电容器电极材料的设计与制备

超级电容器寿命长,安全性高,并可以实现快速充放电,是化学电源研究的热点之一。然而,超级电容器的能量密度较低限制了其更多的应用。因此,超级电容器领域的研究关注点在如何提高超级电容器的能量密度。其中,提高比容量是提高能量密度的一种有效途径。本文通过对电极材料和电解液的优化来研究制备得到高容量超级电容器的方法。电极材料的比表面积、孔道结构和导电性对其电化学性能有着直接的影响。一方面,通过优化电极材料的孔道结构和比表面积可以增加活性位点并提高电解液离子传导率,从而得到高比电容。另一方面,电极材料导电性的提高有利于提升其电子传导率从而得到较高的比容量。本文分别对碳材料和金属氧化物/氢氧化物的优化达到了增加双电层电容和赝电容的目的。不仅如此,还可以通过在电解液中增加氧化还原电对从而得到高比电容。这一方法为高容量超级电容器的制备提供了新的思路。     

电纺纤维在超级电容器中的应用

对高性能超级电容器不断增长的需求促进了电极隔膜和电极材料的快速发展。静电纺丝法制备的纳米纤维具有较高的孔隙率、较好电化学活性、较大的表面积以及良好的结构稳定性等优点,已被广泛应用于超级电容器的隔膜和电极材料。本文简要综述了近年来电纺纳米纤维在超级电容器用隔膜和电极材料的研究进展;着重讨论了通过静电纺丝和其他后处理方法制备的碳基纳米纤维、碳基复合纳米纤维、导电聚合物基复合纳米纤维和金属氧化物纳米纤维等用于超级电容器的电极材料。研究表明,多孔结构的构建、活化处理以及杂原子掺杂可以提高碳纳米纤维的比表面积、电化学活性、润湿性和石墨化程度,从而增强其电化学性能。此外,通过共混、化学沉积和电化学沉积等方法,将碳纳米纤维与金属氧化物、导电聚合物结合,可以改善其电容、倍率性能和循环稳定性。最后,提出上述研究中存在的问题,并对未来静电纺丝纳米纤维材料在超级电容器的发展前景进行了展望。     

碳基超级电容器电极材料的研究进展

超级电容器是近年迅速发展起来的一种新型储能元件,决定超级电容器性能的最重要因素是电极材料。碳材料以其比电容高、循环寿命长和资源丰富等优点,已经成为当前超级电容器电极材料的有力竞争者。用作超级电容器电极的碳材料主要包括活性炭、碳纳米管、石墨烯等。本文详细介绍了超级电容器用碳材料的特点、应用及发展状况,并指出制备具有大比表面积和高导电率的多孔碳是当前碳材料电极的主要研究方向。     

超级电容器用炭/导电聚合物复合材料*

炭/导电聚合物复合材料是近年来发展起来应用于超级电容器的一种新型电极材料。炭材料与氧化物的复合材料,或者炭材料与导电聚合物的复合材料,能够将双电层电容与法拉第电容结合,既可提高超级电容器的比电容,改变其充放电电压,又可提高其循环性能。本文综述了近年来国内外各种炭材料,如活性炭,碳纳米管等与导电聚合物复合材料的研究进展,认为炭与导电聚合物的复合材料,尤其是性能优良的炭气凝胶,模板法制备的中孔炭,以及由金属或非金属碳化物与氯气等刻蚀剂反应制备的骨架炭与导电聚合物的复合材料是超级电容器电极材料研究的一个重要发展方向。     

提高电容性电化学储能装置能量容量的一些尝试

本文从作者所在的课题组在超级电容器和超级电容电池方向的研究内容为基础,在电极材料和装置层面综述了电容性电化学储能装置的发展. 导电聚合物和过渡金属氧化物分别与碳纳米管复合后的复合物能显著提高前两者作为电容性法拉第储能电极的电容性能. 活性炭和碳黑等一类碳材料则可作为非法拉第储能的电极材料. 通过对超级电容器正负极电容做相应的匹配调整可以提高超级电容器的最大充电电压,从而提高超级电容器的能量容量. 此外,为了与实际设备相匹配,超级电容可以以双极板的方式串联堆积,满足高电压的需求. 超级电容电池作为新一代的电容性电化学储能装置,分别由具有电容性和法拉第电荷储存原理的电极组成,具有高比功率和高比能量的特点,也是近年来的研究热点.     

提高电容性电化学储能装置能量容量的一些尝试（英文）

本文从作者所在的课题组在超级电容器和超级电容电池方向的研究内容为基础,在电极材料和装置层面综述了电容性电化学储能装置的发展.导电聚合物和过渡金属氧化物分别与碳纳米管复合后的复合物能显著提高前两者作为电容性法拉第储能电极的电容性能.活性碳和碳黑等一类碳材料则可作为非法拉第储能的电极材料.通过对超级电容器正负极电容做相应的匹配调整可以提高超级电容器的最大充电电压,从而提高超级电容器的能量容量.此外,为了与实际设备相匹配,超级电容可以以双极板的方式串联堆积,满足高电压的需求.超级电容电池作为新一代的电容性电化学储能装置,分别由具有电容性和法拉第电荷储存原理的电极组成,具有高比功率和高比能量的特点,也是近年来的研究热点.     

二氧化锰与二维材料复合应用于超级电容器

现如今世界正面临着与能源相关的一系列问题与挑战,科学家们致力于研究绿色高性能的能量存储器件以适应当前乃至以后长久可持续创新发展的需要。超级电容器作为一种新型的绿色能源储存装置,具有功率密度大、理论比电容高、充放电速度快、循环寿命长、安全性高、环境友好且经济等优点,为人类解决能源危机提出了可能。电极材料是影响超级电容器性能的重要因素。近些年,由于二氧化锰基超级电容器具有理论比电容高、化学稳定性好、环境友好等特点被广泛研究。同时多种二维材料也继石墨烯后被相继用作超级电容器电极材料,具有二维结构特征材料在提高双电层电容器的能量密度、改善赝电容电容器方面发挥着重要作用。实现高比电容和高倍率性能,将二氧化锰与二维材料复合将不失为一个有前景的选择。本文系统介绍了以石墨烯为代表的各类二维材料与二氧化锰复合物在超级电容器中的应用研究,并聚焦于这些二维材料与二氧化锰复合后所展现的优异电化学性能。     

新型碳纳米材料在电化学中的应用

由于碳纳米材料具有良好的力学、电学及化学性能而被人们广泛研究,特别是对于具有大比表面积、高的电导率和良好生物相容性的碳纳米管、碳纳米纤维和石墨烯更是研究的热点。这些新型碳材料具有许多优异的物理和化学特性,被广泛地应用于诸多领域,特别是在电化学领域中显示出其独特的优势。本文主要阐述了碳纳米材料在电化学领域包括生物传感器、超级电容器和燃料电池中的应用。碳纳米材料由于高的比表面积和其较好的生物相容性,在生物电催化反应中起着重要作用,能够提高酶的直接电子传递速率,因而基于碳纳米材料构建的生物传感器灵敏度高、线性范围宽、重复性和稳定性能好。碳纳米材料是超级电容器研究最早和最成熟的一种,由其制备的超级电容器循环稳定性好,再通过和一些赝电容型电极材料复合,可使其比电容得到提高。另外,碳纳米材料作为燃料电池中的催化剂,能够提高燃料电池的能量密度、燃料利用率和抗中毒能力。     

碳纳米管/石墨烯复合结构及其电化学电容行为

本文综述了超级电容器电极材料碳纳米管/石墨烯复合结构的制备方法,以及由该结构和赝电容活性物质形成的三元复合体系的电化学电容行为研究进展,并提出合理设计的碳纳米管和石墨烯复合结构可以有效发挥其高电导率、高比表面积和合理孔隙结构的优势,实现活性物质的高密度负载,从而获得具有高容量、良好倍率特性和长寿命的电化学超级电容器电极材料。     

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.     

Design and synthesis of ternary composite of polyaniline-sulfonated graphene oxide-TiO<Subscript>2</Subscript> nanorods: a highly stable electrode material for supercapacitor

Supercapacitor is an important energy storage device. Nature of electrode material plays an important role in the performance of supercapacitor. Carbon, metal oxide, and conducting polymer-based materials are being used as electrode materials. Each type of material has its own advantages and disadvantages. To improve the energy density and cycle life performance of conducting polymer, in this work, metal oxide (TiO₂) and carbon (sulfonated graphene oxide) materials were incorporated on to polyaniline. Presence of polyaniline, titanium dioxide, and sulfonated graphene oxide in the composite material was supported by Fourier transform infrared, XRD, FE-SEM, and EDAX techniques. Composite material of nanorods with sphere morphology in excellent yield and reasonably good conductivity was obtained. Electrochemical performances of the composite material were carried by cyclic voltammetry, charge-discharge, and impedance measurements. Composite material showed much better performances than that of its individual components in terms of specific capacitance, energy density, power density, and cycle life.     

碳纳米管的修饰及其在超级电容器中的应用

碳纳米管以其窄孔径分布、高有效比表面积、良好导电性能、良好力学性能、优良化学稳定性和良好热稳定性以及较低成本等优点,被认为是超级电容器的理想电极材料之一.本文结合碳材料具有的双电层电容和金属氧化物、导电聚合物具有的准法拉第电容,综述了碳纳米管的修饰处理技术及碳纳米管/金属氧化物、碳纳米管/导电聚合物复合材料、碳纳米管原位再生长技术的研究进展,指出碳纳米管的修饰能更好地改善其电化学性质,因此碳纳米管复合材料是超级电容器电极材料研究的一个重要发展方向.     

导电高分子在神经界面电极中的应用

神经界面电极作为人体和外部器件间信息融合的媒介, 为人们进一步探究神经系统高级功能的机制提供了有效工具. 传统的神经电极多以金属和半导体材料为主, 这两类材料因具有惰性材料的特性及优越的 导电性能而成为早期神经电极的主要制备材料, 但由于其刚性过大和光滑表面导致的机械失配及与生物组织间过高的电化学阻抗限制了神经电极的进一步发展. 导电高分子作为一种有机导电材料, 同时具备柔软性 (杨氏模量约在0.01~10 GPa)和导电性(高掺杂度的导电高分子的电导率在金属范围, 10⁰~10⁵ S/cm)的特征, 是制备神经电极的有效材料. 近年来, 人们利用导电高分子材料对传统电极材料进行改性甚至替代, 以提高电极比表面积、 减小界面阻抗, 并提高电极检测的灵敏性; 同时减小电极与组织间的应变失配, 减少炎症反应, 并进一步在导电高分子中引入功能性生物大分子, 减少生物组织对电极的排异反应, 增加电极在体内长期植入的稳定性. 本文讨论和总结了导电高分子材料在神经电极中的应用, 分别对导电高分子作为涂层修饰神经电极、 全导电高分子材料神经电极及导电高分子复合材料神经电极等展开讨论, 分析了导电高分子在神经界面电极中的应用前景及存在的问题, 以期对神经界面电极在脑科学和生物电子医疗等前沿领域的进一步发展提供参考.     

基于碳纳米管的超级电容器研究进展

综述了基于碳纳米管及其复合材料作超级电容器的电极材料的研究现状,通过对碳纳米管的改性或与其它材料复合,能有效地提高电容器的电容特性。总结了近几年来在开发超级电容器电极材料领域中对碳纳米管的活化和提高碳纳米管的分散性技术、碳纳米管与过渡金属氧化物复合材料、碳纳米管与导电聚合物复合材料以及碳纳米管与石墨烯复合材料研究的进展。     

Research Progress on Nitrite Electrochemical Sensor

Nitrite has been widely used in industrial and agricultural production and is commonly found in food, drinking water, biology and environment. However, nitrite is a toxic inorganic pollutant that is very harmful to the health of human and other organisms. A variety of strategies have been proposed for nitrite detection in recent years. Among which, electrochemical approaches have gained more and more attention owing to the characteristics of simplicity, speediness, high sensitivity, and low cost, etc. The principle of nitrite electrochemical sensor is recommended in this review. The research progresses of nanocomposite material sensor for electrochemical nitrite detection based on carbon material, metal material, metal organic framework, conducting polymer and enzyme in recent years are also introduced from the perspective of composite electrode modification layer. The construction approaches and sensing performances of modified electrode are put special emphasis. At last, future trends of nitrite electrochemical sensor are discussed.     

Photochromism and electrochemistry of a dithienylcyclopentene electroactive polymer

A bifunctional substituted dithienylcyclopentene photochromic switch bearing electropolymerisable methoxystyryl units, which enable immobilization of the photochromic unit on conducting substrates, is reported. The spectroscopic, electrochemical, and photochemical properties of a monomer in solution are compared with those of the polymer formed through oxidative electropolymerization. The electroactive polymer films prepared on gold, platinum, glassy carbon, and indium titanium oxide (ITO) electrodes were characterized by cyclic voltammetry, X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM). The thickness of the films formed is found to be limited to several monolayer equivalents. The photochromic properties and stability of the polymer films have been investigated by UV/vis spectroscopy, electrochemistry, and XPS. Although the films are electrochemically and photochemically stable, their mechanical stability with respect to adhesion to the electrode was found to be sensitive to both the solvent and the electrode material employed, with more apolar solvents, glassy carbon, and ITO electrodes providing good adhesion of the polymer film. The polymer film is formed consistently as a thin film and can be switched both optically and electrochemically between the open and closed state of the photochromic dithienylethene moiety.     

非酶葡萄糖传感器电极材料构建策略

电化学传感器因具有灵敏度高、检测限低等优点而得到广泛应用,将非酶电化学传感器应用于葡萄糖浓度的检测具备重要的研究价值。以金属有机骨架、碳材料和导电聚合物为基底与金属及其衍生物复合,构建的纳米复合材料修饰电极对于葡萄糖的检测具有极高的灵敏度、较低的检测限和快速响应的能力,可应用于实际样品的检测。本文综述了近年来非酶葡萄糖电化学传感器的研究进展,通过对纳米复合材料的性能比较,为非酶葡萄糖传感器的构建提供思路。     

The Electrochemical Detection of Certain Tricyclic Drugs at Polymer Electrodes: A Preliminary Report

Abstract

The development of a polymer electrode using reticulated vitreous carbon (RVC) as a support material is described. A conducting layer of (poly)carbazole or (poly)thiophene is el eletrochemically plated onto a RVC surface and the system is applied to the study of the electrochemistry of certain tricyclic drugs. An electrochemical response is seen for amitriptyline, nortriptyline and protriptyline all of which were previously reported to be electrochemically inactive while iminostilbene, imipramine and carbamazepine demonstrate similar electrochemical behaviour at both polymer and conventional carbon electrodes. The advantages of such electrodes and their use as working electrodes in hydrodynammic electrochemical detectors is presented.     

Template synthesis of tin-doped indium oxide (ITO)/polymer and the corresponding carbon composite hollow colloids

SnO₂, In₂O₃, and Sn-doped In₂O₃ (ITO)/polymer and the corresponding carbon composite hollow colloids are template synthesized. It is essential that the sulfonated gel shell of the cross-linked polystyrene hollow colloid can favorably induce adsorption of target precursors. After being calcined in air to remove the template, SnO₂, In₂O₃, and ITO hollow colloids are obtained. Because the cross-linked polymer gel can be transformed into carbon in nitrogen at higher temperature such as 800 °C, metal oxide/carbon hollow colloids are consequently derived, whose shells are mesoporous. The SnO₂-, In₂O₃-, and ITO-containing polymer or carbon composite hollow colloids will be promising in sensors, catalysts, and fuel cells as electrode materials. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Hybrid organic/inorganic films of conducting polymers modified with phthalocyanines. I—Film preparation and voltammetric studies

Conducting polymers were deposited on the surface of platinum and glassy carbon electrodes. The monomers used were N-methyl pyrrole and 3-methyl thiophene. The electrochemical synthesis of the polymer was achieved using constant applied potential or cyclic polarization techniques in acetonitrile as a solvent and tetra-alkyl ammonium salts as supporting electrolyte. The resulting conducting polymeric film was modified with an inorganic metal complex, namely, Cu–phthalocyanine or Co–phthalocyanine. Two different approaches were adopted for the modification: (1) the first was to directly apply the metal–phthalocyanine layer on the surface of the polymer, and (2) the second was by the inclusion of the metal–phthalocyanine in a sol–gel matrix that was in turn applied to the conducting polymer film. In the first part of this work, we studied the effect of changing the type of polymer matrix and the central metal of the inorganic complex on the electrochemical behavior of the resulting film. We also found that changing the method of metal–phthalocyanine application to the polymer film affected the electrochemical response and kinetics at the electrode surface. The new electrode was tested for the reduction of hydrogen peroxide and showed better conversion efficiency compared to conventional surfaces, which suggests its use in fuel cell applications.