石墨烯/聚吡咯导电复合材料超级电容器电极的制备研究

超级电容器与锂电池相比具有更高的循环稳定性以及更高的能量密度。提高超级电容器电极材料化学稳定性,增大离子吸附比表面积,以获得更好的电化学性能,成为超级电容器研究领域的热点。以湿化学还原法制备的石墨烯为基底,采用原位电化学沉积法制成了石墨烯/聚吡咯导电复合材料超级电容器电极。通过扫描电子显微镜(SEM)对电极的微观形貌进行了观察,利用电化学工作站对组装的超级电容器电化学性能进行了系统表征,同时探讨了沉积浓度和沉积时间对电化学性能的影响。结果表明,在0.2 mol/L吡咯溶液中沉积时间为22.5 min制备出的石墨烯/聚吡咯导电复合材料电极的比电容可达388 F/g,表现出优良的超级电容器电化学性能。     

石墨烯/聚吡咯导电复合材料超级电容器电极的制备研究

超级电容器与锂电池相比具有更高的循环稳定性以及更高的能量密度。提高超级电容器电极材料化学稳定性,增大离子吸附比表面积,以获得更好的电化学性能,成为超级电容器研究领域的热点。以湿化学还原法制备的石墨烯为基底,采用原位电化学沉积法制成了石墨烯/聚吡咯导电复合材料超级电容器电极。通过扫描电子显微镜(SEM)对电极的微观形貌进行了观察,利用电化学工作站对组装的超级电容器电化学性能进行了系统表征,同时探讨了沉积浓度和沉积时间对电化学性能的影响。结果表明,在0.2mol/L吡咯溶液中沉积时间为22.5min制备出的石墨烯/聚吡咯导电复合材料电极的比电容可达388F/g,表现出优良的超级电容器电化学性能。     

微波法煤基活性炭的制备及其电化学性能研究

以内蒙古优质褐煤为原料,KOH为活化剂,采用微波加热活化法制备超级电容器用活性炭,利用低温氮气吸附及恒流充放电、循环伏安等方法测定活性炭的孔结构及其用作电极材料的电化学性能,并与日本商业化超级电容器用活性炭在结构及性能方面进行对比分析。结果表明,在碱炭比为3,微波活化时间为20min的条件下,可制备出比表面积达2593m2/g、总孔容达1.685cm3/g、孔径主要分布在0.5～10nm之间、中孔率达67.3%、平均孔径为2.61nm的优质活性炭。该活性炭用作超级电容器电极材料在3mol/L KOH电解液中具有优异的电化学性能,电流密度由50mA/g提高到10A/g时,其比电容由346F/g降低到273F/g,显示出良好的功率特性,经1000次循环后,比电容保持率为93.2%。与商业活性炭相比,微波法活性炭的性能更加优良。     

柠檬酸盐为碳前驱体制备介孔炭及其在电化学电容器中的应用(英文)

热解柠檬酸镁或柠檬酸钡,制备了两种介孔炭(MgC或BaC),并将其用作双电层电容器电极材料。采用氮气吸附、扫描电子显微镜和傅里叶红外光谱对所制介孔炭进行表征。结果表明:所制介孔炭孔结构与柠檬酸盐所含金属阳离子有关。其中,BaC呈典型的双峰孔径分布,最可几孔径分别为3.8nm和15nm;而MgC的孔道主要是小尺寸的介孔或微孔。通过循环伏安、恒流充放电法测试所制介孔炭作为电化学电容器电极材料时的电化学性质。测试表明,在离子液体中MgC和BaC都具有很高的比电容值,分别达到180F.g-1和171F.g-1。其中,BaC的倍率性能良好,能量密度可达到53.3Wh.kg-1,最大功率密度为20kW.kg-1。BaC优良的电容特性主要归因于其孔径双峰分布的孔结构和亲水性表面化学性质。     

孔结构对煤基活性炭电极材料电化学性能的影响(英文)

以太西无烟煤为前驱体,NaOH为活化剂制备电化学电容器电极材料。采用N2吸附法及电化学测试对活性炭的孔结构和电化学性能进行了表征。在1mol/L(C2H5)4NBF4/碳酸丙烯酯有机电解液体系中,研究了孔结构对活性炭电极材料的电化学性能的影响。结果表明:以NaOH为活化剂可制备出比表面积943mol/L～2479mol/L、比电容57F/g～167F/g的活性炭电极材料。活性炭电极材料的比电容不仅取决比表面积,而且与活性炭的孔径分布有关。孔径为2nm～3nm的中孔的存在可以有效降低电解液的扩散阻力,提高电极材料比表面积的利用率,从而使电容器的电化学性能得到增强。     

碳布负载的PI-MWCNTs柔性电极材料的合成及其电容性能

以超级电容器的电极材料制备、性质研究及对组装非对称超级电容器的性能研究为核心内容,提高超级电容器电化学性能为主要目的,采用原位聚合法制备羧基化多壁碳纳米管(PI-MWCNTs)接枝的聚酰亚胺溶液,将其作为氮掺杂碳的前驱体,实现复合物在碳布表面的生长,并作为电极材料.以二氧化锰-碳布(MnO2-CC)为正极,多壁碳纳米管接枝的聚酰亚胺-碳布为负极(PI-MWCNTs-CC),构建非对称超级电容器.采用扫描电子显微镜、拉曼光谱、X射线衍射、比表面积及孔径测试、循环伏安、恒电流充放电及电化学阻抗谱对电极材料的结构和电化学性能进行表征.结果表明:当扫描速率为20 mV/s时,非对称电容器的电势窗口可增至1.3 V,其体积比容量为1.80 F/cm3;当功率密度为14.08 mW/cm3时,能量密度可达到0.423 mWh/cm3.     

纳米碳材料负载过渡金属氧化物用作超级电容器电极材料

与传统能量存储设备相比,超级电容器因具备比电容高、充放电快、绿色环保并且循环稳定性能优异等优点,在移动通信、电动汽车、国防和航空航天领域具有广阔的应用前景,已成为世界范围内的研究焦点。其中,超级电容器的电极材料是其性能的决定因素,常见的超级电容器电极材料包括碳材料、过渡金属氧化物和导电聚合物等。不同的电极材料的电荷储存机理不同,过渡金属氧化物具有典型的赝电容行为,依赖可逆的氧化还原反应和化学吸附/脱附过程来储存电荷,理论比电容高。然而,过渡金属氧化物同时存在导电性能差,循环稳定性不佳的缺点。碳材料主要表现双电层电容特性,依靠材料表面和电解质离子间的可逆物理吸附/脱附过程储存电荷,具有优异的倍率性能,符合实际生产和应用中对于超级电容器器件高寿命的要求,但其自身比电容相对较低。与单一属性的材料相比,复合材料往往表现出更加优异的电化学性能,大量的研究表明,过渡金属氧化物与碳材料的复合是解决上述问题的有效途径。碳材料因具有来源丰富、价格低廉、质量轻盈、比表面积高以及热稳定性好与电化学性能稳定等优点,日益受到重视,是构建赝电容电容器电极的首选基底材料。碳材料结构多样,近年来,零维的碳量子点、碳球,一维的碳纳米管、碳纳米纤维,二维的石墨烯、氧化石墨烯,三维的石墨烯泡沫、碳泡沫/海绵等均被成功地用于构建碳基复合电极材料,并取得了丰硕的成果。零维碳纳米材料具有高比表面积,提供了调节多孔性的灵活度,可以获得适合各自电解质溶液的最优化条件。一维碳纳米结构一般具有高长宽比和良好的电子传输性能,可以促进超级电容器电极的电荷转移。二维碳纳米结构具有比表面积大与导电性高、力学性能优良等特点,具备潜在赝电容行为,并且能增强超级电容器电极间的充放电反应动力学。利用三维导电材料作为模板,沉淀赝电容材料,可以构建高性能超级电容器电极。本文概述了不同维度碳材料负载过渡金属氧化物作为赝电容的电极材料及其电容性能,并对电极材料储能方面存在的不足和未来的研究方向做出了总结和展望,以期为制备性能优良、环境友好和高寿命的超级电容器提供参考。     

废弃复材树脂高值化利用：超级电容器电极应用

近年来，废弃碳纤维复合材料数量急剧增加，对人类的生存环境造成了严重破坏。为了实现废弃复材中树脂的高值化利用，本研究采用一步碳化法制备了废弃树脂基碳材料，研究了碳化温度对碳材料结构与性能的影响，并将碳材料制备成超级电容器电极，研究电极的电化学性能。分别采用扫描电子显微镜(SEM)、比表面积测试仪、傅里叶红外光谱仪(FTIR)、X射线光电子能谱(XPS)、拉曼测试仪(Raman)、差示扫描量热仪(DSC)和热重分析仪(TGA)对碳材料的表面形貌、孔性能、化学组分、石墨化程度以及形成原理进行了分析。结果表明：当碳化温度为800℃时制备的碳材料具有分级多孔的结构，孔性能和石墨化程度达到最佳，所制备的超级电容器电极表现出优异的电化学性能，在1 A/g电流密度下比电容高达299 F/g,经10 000次充放电循环后，比电容仍高达296.6 F/g,循环稳定性优异。     

离子液体在中孔炭中的电化学性能研究

对以离子液体(1-乙基-3-甲基咪唑四氟硼酸盐)做电解液,热固性酚醛树脂为前驱体添加纳米硅颗粒制备的中孔炭做电极构成的电化学双电层电容器的电化学行为进行了探讨.循环伏安和恒流充放电测试结果表明,离子液体在中孔炭中表现为优秀的电化学行为,大电流充放电时具有良好的电容特性,其比电容在1mA/cm2时为120F/g,充放电效率达92%,表明中孔炭非常适合离子液体电解液.     

酒糟纤维素碳气凝胶的制备及在超级电容器中的 应用

电极材料是决定超级电容器性能的主要因素,因此,合成具备特定形貌、组成以及性能优异的电极材料是构建高性能超级电容器的关键。从酒糟中提取植物纤维素,再通过冷冻干燥和热碳化处理,制备具有乱层石墨结构的纤维素碳气凝胶功能材料,并将其应用于超级电容器。研究结果表明,最优碳化温度700 ℃下制备的纤维素碳气凝胶作为电极材料,在浓度为6 mol/L的 KOH溶液和1 A/g的电流密度下,其比电容为183.5 F/g;而且该电极材料在20 A/g高电流密度下,仍保持90.0 F/g的比电容,展现出优异的倍率性能。交流阻抗拟合结果表明,CA-700组装的超级电容器界面传质电阻和扩散电阻分别为0.2829 Ω和5.7210 Ω;CA-700展现出较低的传质、扩散阻力和优异的电化学储能特性。     

纳米多孔光波导漏模共振传感器的折射率灵敏度分析(英文)

在玻璃基片上射频溅射50 nm厚的金膜,然后利用TiO2胶体溶液在金膜表面制备了厚度约为320 nm的TiO2纳米多孔薄膜.以此双层膜为漏模光波导芯片,构建了基于Kretschmann结构的波长调制型光波导漏模共振(LMR)传感器.利用扫描电子显微镜(SEM)观测了TiO2纳米多孔薄膜的表面和横截面形貌.实验研究了在纳米多孔光波导中给定漏模的共振波长及折射率灵敏度与入射角的依赖关系.结果表明,随着入射角的增大,共振波长逐渐蓝移,折射率灵敏度随之下降.此外,与传统的表面等离子体共振(SPR)传感器进行了对比,结果表明在相同的共振波长下,纳米多孔光波导LMR传感器折射率灵敏度大于SPR传感器.     

Fabrication and textural characterization of nanoporous carbon electrodes embedded with CuO nanoparticles for supercapacitors

Abstract

We introduce a novel strategy of fabricating nanoporous carbons loaded with different amounts of CuO nanoparticles via a hard templating approach, using copper-containing mesoporous silica as the template and sucrose as the carbon source. The nature and dispersion of the CuO nanoparticles on the surface of the nanoporous carbons were investigated by x-ray diffraction (XRD), high-resolution scanning electron microscopy (HRSEM) and high-resolution transmission electron microscopy (HRTEM). XRD results reveal that nanoporous carbons with embedded CuO nanoparticles exhibit a well-ordered mesoporous structure, whereas the nitrogen adsorption measurements indicate the presence of excellent textural characteristics such as high surface area, large pore volume and uniform pore size distribution. The amount of CuO nanoparticles in the nanochannels of the nanoporous carbon could be controlled by simply varying the Si/Cu molar ratio of the mesoporous silica template. Morphological characterization by SEM and TEM reveals that high-quality CuO nanoparticles are distributed homogeneously within the nanoporous carbon framework. The supercapacitance behavior of the CuO-loaded nanoporous carbons was investigated. The material with a small amount of CuO in the mesochannels and high surface area affords a maximum specific capacitance of 300 F g^-1 at a 20 mV s^-1 scan rate in an aqueous electrolyte solution. A supercapacitor containing the CuO-loaded nanoporous carbon is highly stable and exhibits a long cycle life with 91% specific capacitance retained after 1000 cycles.     

The preparation of nanoporous gold electrodes by electrochemical alloying/dealloying process at room temperature and its properties

A novel method of preparing nanoporous gold has been developed: nanoporous gold materials have been prepared on the bulk gold substrates by galvanostatic electrochemical alloying and galvanostatic electrochemical dealloying processes at 0.05 mA in 1 M LiPF₆, EC/DMC(1:1, v/v) solution at room temperature. The result shows that the particle size ranges from 50 nm to 100 nm on the surface of the prepared nanoporous gold by Quanta 200FEG scanning electron microscope. And it is determined that the maximum anodic current for the nanoporous gold electrode is 50 times higher than that of the polished gold electrode in 0.5 M KOH by the cyclic voltammograms.     

简易合成不同孔径尺寸的半石墨化有序介孔炭

以SBA-15介孔硅为模板,硼酸为扩孔剂,调控合成出不同孔径尺寸的半石墨化有序介孔炭.采用X射线衍射仪(XRD)、氮气吸附、透射电子显微镜(TEM)、扫描电子显微镜(SEM)、热重(TG),以及拉曼(Raman)光谱等手段对样品的成分、结构和形貌进行了分析.结果表明:通过合成过程添加硼酸的方法可以实现对介孔炭材料的孔径在3nm～7nm范围内精确调控,而且合成的介孔炭材料具有半石墨化的墙壁结构.该方法简单易行,对介孔炭材料的孔结构调控合成具有很好的应用价值.     

埃洛石为模板合成中孔炭

以天然矿物埃洛石为模板, 蔗糖为碳源合成了具有“壳-核”结构的中孔炭。通过SEM、TEM、N₂吸附、XRD、Raman、TG对样品进行了形貌和结构表征。结果表明: 模板炭具有一维管状结构, 与埃洛石具有相似的形貌。经过700℃和900℃炭化后的模板炭比表面积达到了945 m²/g和1147 m²/g, 孔容和中孔率也较埃洛石有了很大的提高。去除模板后得到的模板炭具有很高的纯度, 为无定形炭。升高炭化温度, 模板炭的拉曼特征参数R值降低, 热分解温度由563℃提高到623℃。同时, 对模板炭的形成过程及孔道形成机理进行了分析和讨论。     

Nanoporous Carbons Derived from Metal‐Organic Frameworks as Novel Matrices for Surface‐Assisted Laser Desorption/Ionization Mass Spectrometry

Surface‐assisted laser desorption/ionization mass spectrometry (SALDI‐MS) represents a powerful tool for the analysis of biomolecules, synthetic polymers, and even small organic compounds; its performances largely depend on the type of matrix materials utilized. Here, for the first time the employment of nanoporous carbons derived from metal‐organic frameworks (MOFs) as novel matrices for SALDI‐MS is demonstrated. The nanoporous carbons derived from MOFs not only circumvent the shortcomings of existing matrix materials but also demonstrate much higher efficiency of laser desorption/ionization for various compounds than any other nanoporous carbons reported so far. A new perspective for the development of matrix materials for SALDI‐MS application is therefore provided.     

鼠李糖脂碳吸附剂的制备及其吸附性能的研究

以蔗糖和硅酸钠分别作为碳、硅凝胶的前驱体, 经溶胶-凝胶反应形成硅凝胶和蔗糖聚合物的混合网络结构, 高温炭化后将二氧化硅刻蚀去除, 制备了一种以中孔径为主的多孔碳材料, 其孔径可以通过反应条件的改变控制在8~25nm范围内, 经过扫描电子显微镜的观察以及低温氮气吸附等温线分析发现, 在蔗糖/硅摩尔比为0.33、溶胶pH值为3、凝胶温度为80℃、炭化温度为850℃时, 所制得的中孔碳BET表面积为597.63 m²/g、孔容及中孔率好, 对鼠李糖脂有良好的吸附性.     

Electron beam effects on amorphous molybdenum oxide nanostructures grown by condensation in hydrogen

Molybdenum trioxide (MoO₃) was evaporated from a tungsten resistive source in presence of hydrogen as carrier gas at pressures from 100 Pa to 600 Pa. Crystalline samples of molybdenum oxide were obtained at source temperatures below 950 °C. However, at source temperatures above 1000 °C, nanoporous structures were obtained, with porosity in the range of 10–85 nm. As shown by X-ray diffraction as well as selected area electron diffraction (SAED), the nanoporous material was amorphous. Under transmission electron microscopy (TEM) examination, and due to the electron beam, progressive formation of crystalline clusters was observed, as revealed by sequential changes of SAED and dark field images and corroborated in the high resolution TEM images (HRTEM). The growth of crystalline clusters at the nanometer scale occurs without destruction of the nanoporous structures.     

Enhanced hydrogen storage capacity of nanosized copper loaded active carbons treated under CO2

A kind of composites with nanosized Cu loaded on activated active carbons was prepared. The materials were characterized by X-ray diffraction (XRD) patterns, transmission electron microscope (TEM) and nitrogen adsorption. The highest surface area of 2746 m2/g was obtained for the optimized activated active carbon. TEM image and size distribution analyses show that the ball-like Cu(0) particles are dispersed homogeneously in the composites with diameters of 10-30 nm. The electrochemical hydrogen storage properties were determined and an optimized discharge capacity of 605.5 mAh/g was gotten, which corresponds to 2.24 wt% of hydrogen uptake capacity.     

Electrochemical Fabrication of Metallic Nanowires and Metal Oxide Nanopores

A nuclear track etched polycarbonate membrane filter with numerous cylindrical nanopores was applied as a nanoporous template for growing metallic nanowires. Nickel, cobalt, and iron nanowires were electrodeposited into the cylindrical nanopores. Cathodic polarization curves were measured to determine an optimum condition for growing nanowires. The shape of nanowires was observed using scanning electron microscope (SEM) and the crystal structure was analyzed using transmission electron microscopy (TEM). Diameter and length of nanowires corresponded to those of nanopores and each nanowire was composed of a single crystal. Anodized aluminum oxide films were also fabricated as a novel nanoporous template. The pore length and diameter was controlled changing anodizing conditions. Ordering behavior of nanopores array in an anodized aluminum oxide film was also investigated to make a novel nanoporous template with a highly ordered honeycomb array of nanopores.