石墨烯/炭气凝胶的制备及其结构与性能研究

以间苯二酚(R)和甲醛(F)为炭前驱体原料, 通过溶胶-凝胶法制备石墨烯/炭气凝胶复合材料。采用XRD、Raman、SEM和N₂吸附/脱附等对样品进行结构表征。结果表明: 石墨烯为R和F的聚合提供形核场所, R和F首先在氧化石墨烯(GO)表面聚合, 随着RF含量的增加, 复合炭气凝胶(RF)结构从石墨烯薄片层为骨架的三维网络, 经RF基炭球包裹于石墨烯的网络结构, 最终转变为球形团簇交联的三维网络。石墨烯/炭气凝胶复合材料的比表面积随着RF的增加先增大后减小。当GO与RF质量比为1︰100时, GO/RF-100用作超级电容器电极材料, 在6 mol/L KOH电解液中的比电容达169 F/g, 具有较好的电容特性。     

氧化前处理对炭气凝胶孔结构的影响

在110℃～170℃范围内对糠醛-酚醛基有机气凝胶进行氧化处理1h～7h,考察了氧化对有机气凝胶热裂解产生的炭气凝胶孔结构的影响.结果表明:氧化可避免有机气凝胶纳米骨架在裂解过程中的塑性阶段发生,有机气凝胶的适度氧化有利于纳米结构的稳定化;由于空气在大、中、微孑L中扩散的差别,氧化前处理对炭气凝胶的大、中、微孔有不同的影响,尤其对接近中孔的大孔影响最大.在所考察的氧化温度和时间内,130℃/7h时或150℃/3h时的适度氧化条件下,可显著提高中孔孔容、中孔比表面和BET比表面.     

亲水基团对有机和炭气凝胶孔结构的影响

热固型酚醛树脂、三聚氰胺、间甲酚和甲醛水溶液在碳酸钠催化下,通过溶液-溶胶-凝胶过程合成有机水凝胶,有机水凝胶经溶剂置换、超临界干燥和裂解形成了有机气凝胶和炭气凝胶.在固定酚醛树脂浓度、间甲酚/酚醛树脂、甲醛/三聚氰胺、碳酸钠/酚醛树脂比值,改变三聚氰胺/酚醛树脂比值的条件下,研究了亲水基团对有机气凝胶和炭气凝胶孔结构的影响.结果表明:亲水性的三聚氰胺可增加分子间作用力,有利于凝胶的稳定;但增加三聚氰胺会加大有机气凝胶裂解过程中的质量损失,不利于凝胶的稳定.二种因素协同作用决定着炭气凝胶的孔结构、孔容和比表面.     

稀释比对常压干燥制备炭气凝胶结构的影响

以间苯二酚和甲醛为原料,氢氧化钠为催化剂,采用溶胶-凝胶法及溶剂置换、常压干燥、炭化等后续工艺,实现了块状炭气凝胶的常压干燥法制备,并考察了稀释比对气凝胶结构性能的影响。采用XRD、BET、SEM及IR等方法对样品进行表征。结果表明:采用氢氧化钠为催化剂制备的炭气凝胶为非晶态,表观密度为1.10g/cm3,比表面积为620m2/g,平均孔径为16.0nm。实验表明,较低的稀释比更有利于制备出表观密度较小、比表面积较高的炭气凝胶。     

炭气凝胶结构的形成和控制

炭气凝胶是一种新型的多孔炭材料,具有可调控的独特的孔结构和良好的导电性,可应用于超级电容器、高效吸附材料、催化剂载体等.本文研究了酚醛基炭气凝胶纳米结构的形成过程和控制方法.炭气凝胶的孔结构主要取决于其前驱体--有机气凝胶.有机气凝胶结构源于溶胶-凝胶聚合中的微相分离过程,相分离经历了从成核--生长--亚稳分解的过渡,在成核--生长区停留时间的长短决定了气凝胶的骨架结构和孔结构.微相分离过程受到酚醛团簇的化学结构和溶剂环境的影响,通过调控酚醛团簇的化学结构和溶胶-凝胶聚合的溶剂环境,可以实现有机气凝胶的纳米结构调控,结合干燥和炭化控制,可以实现炭气凝胶结构的有效调控.     

炭气凝胶为电极的超级电容器电化学性能的研究

炭气凝胶电极的电化学测试表明,炭气凝胶具有性能稳定、充放电效率高、适合于大电流充放电等优良性能.炭气凝胶储电的影响因素主要来自于比表面积、孔容和孔结构分布的综合作用.孔容较大,平均孔径较宽时,储电能力较大,且大孔容对电极材料储电是相当有利的.在高比表面积活性炭中添加不同比例的炭气凝胶,可以提高电极的比电容,炭气凝胶含量为15％时,电极比电容最高.     

常压干燥法制备的炭气凝胶的电化学性能研究

采用常压干燥法制备了炭气凝胶,对所制得的炭气凝胶进行了电化学性能的测试,并与日本进口的超级电容器用超级活性炭进行比较.实验结果表明,炭气凝胶具有优良的电容性能,电双层比电容量和高扫描速度下(100mV/s)的质量比电容量分别达到21μF/cm2和89F/g,高于日本进口超级电容器用超级活性炭.     

常压干燥制备炭气凝胶及其电化学行为的研究

以甲酚为原料，添加适量的间苯二酚，在氢氧化钠催化作用下与甲醛聚合，经溶胶凝胶、溶剂置换、常压干燥和900℃炭化过程可制备纳米多孔材料炭气凝胶。N2吸附测试表明所制备炭气凝胶BET比表面积高于500m^2／g，在8nm～20nm范围具有集中的孔径分布，适合于做双电层电容器的电极材料。采用电化学阻抗谱测试电极的电化学行为，结果显示炭气凝胶电极在1mol／L的H2SO4电解液中的体积比电容接近70F／cm^3，质量比电容最高达97F／g。     

木质素酚醛基炭气凝胶的制备及电化学性能

以木质素、苯酚和甲醛为原料,NaOH为催化剂,溶胶凝胶法制备了木质素酚醛基有机凝胶,经CO2超临界干燥及高温炭化得到了炭气凝胶(LPCA)。采用扫描电镜(SEM)、比表面及孔结构分析仪表征了材料的结构,通过恒流充放电测试了炭材料的电化学性能。结果表明,制备得到的炭气凝胶以微孔和中孔为主,比表面积达356.6m2/g,首次放电比容量为583.94mAh/g,充放电循环30次比容量未见明显的衰减。     

炭气凝胶电极电吸附脱盐性能的研究

以间苯二酚和甲醛为原料,通过溶胶-凝胶反应、超临界干燥、炭化等工艺合成制备出炭气凝胶,对炭气凝胶的微观结构进行了表征,并研究了炭气凝胶电极在不同电压和在不同浓度NaCl溶液中的电吸附性能。实验结果表明炭气凝胶电极具有很高的吸附效率,在20min内基本达到吸附平衡。随着外加电压的加大,处理溶液浓度的升高,炭气凝胶电极吸附平衡时间减小,单位吸附量增加,吸附单元内电流增加。     

Organic aerogels from the polycondensation of resorcinol with formaldehyde

The polycondensation of resorcinol with formaldehyde under alkaline conditions results in the formation of surface functionalized polymer clusters. The covalent crosslinking of these clusters produces gels which are processed under supercritical conditions to obtain low density, organic aerogels ( 0.1 g cm^–3). The aerogels are transparent, dark red in colour, and consist of interconnected colloidal-like particles with diameters of approximately 10 nm. The polymerization mechanism, structure and properties of the resorcinol-formaldehyde aerogels are similar to the sol-gel processing of silica.     

The control of porosity at nano scale in resorcinol formaldehyde carbon aerogels

Organic aerogels were synthesized by sol–gel polymerization of resorcinol (R) with formaldehyde (F) catalyzed by sodium carbonate (C) followed by vacuum drying. The influence of the resorcinol/sodium carbonate ratio (R/C) on the porous structure of the resultant aerogels was investigated. The nitrogen adsorption–desorption measurements show that the aerogels possess a well developed porous structure and mesoporosity was found to increase with increasing the R/C ratio. Carbon aerogels were obtained by carbonization of RF aerogels. The carbonization temperature impacts the microstructure of the aerogels by pore transformations during carbonization probably due to the formation of micropores and shrinkage of the gel structure. The results showed that a temperature of 1073 K is more effective in the development of the pore structure of the gel. Activated carbon aerogels were obtained from the CO₂ activation of carbon aerogels. Activation results in an increase in the number of both micropores and mesopores, indicative of pore creation in the structure of the carbon. Activation at higher temperatures results in a higher degree of burn off and increases the pore volume and the surface area remarkably without change of the basic porous structure, pore size, and pore size distribution.     

Enhanced electrochemical performance of screen-printed carbon electrode by RF-plasma-assisted polypyrrole modification

Journal of Materials Science: Materials in Electronics - Screen-printed carbon electrode (SPCE) has been extensively used in electrochemical (EC) detections due to its excellent EC characteristics...     

炭气凝胶在电化学能源材料中的应用研究进展

炭气凝胶是一种新型、轻质、多孔的非晶态纳米材料,具有在纳米尺度可控和剪裁的连续三维网络结构.简单介绍了炭气凝胶的制备工艺,详细综述了炭气凝胶在电化学超级电容器、燃料电池和锂离子电池等电化学能量储存与转换系统中的主要应用研究进展.     

炭前驱体对活性炭孔结构和电化学性能的影响

分别以毛竹和石油焦为炭前驱体,采用KOH活化法制备超级电容器用高比表面积活性炭材料,考察了碱/炭比对不同炭前驱体所制得的活性炭的孔结构、吸附性能和电容性能的影响。结果表明,在相同的碱/炭比下,竹基活性炭孔径2nm的微孔较发达,而石油焦基活性炭孔径在2～50nm的中孔率较高。在适宜的工艺条件下,以毛竹为炭前驱体可制得比表面积为2610.7m2/g,比电容为206F/g的活性炭材料;以石油焦为炭前驱体可制得比表面积为2597.9m2/g,比电容为213F/g的活性炭材料。     

High-temperature preparation and electrochemical properties of TiO2 anatase phase-mounted carbon aerogels

TiO₂ anatase phase-mounted carbon aerogels (CAs) were synthesized via the sol–gel polymerization of a mixture of resorcinol, formaldehyde, and tetrabutyl orthotitanate, followed by gelation, supercritical drying, and carbonization in N₂ atmosphere. Ethanol was selected as the solvent in the sol–gel polymerization process. The morphology and microstructural characteristics of the TiO₂-mounted carbon aerogel sample were obtained using thermogravimetry, transmission electron microscopy, scanning electron microscopy, N₂ adsorption–desorption, and X-ray diffraction methods. The total pore volume and average pore sizes increased with TiO₂ addition. Titania phase in anatase form was found to be more homogeneously distributed in the CAs at 900 °C. The anatase–rutile transformation did not take place at carbonization temperatures from 500 to 1100 °C and cyclic voltammetry measurements showed that the TiO₂-mounted CAs exhibit good reversibility and high specific capacity as electrode materials, and the anatase in the carbon structure were not involved in the redox reactions. Electrochemical impedance spectroscopy demonstrated that the CA electrode behaves as an excellent capacitor with low resistance.     

Synthesis of β-SiC nanostructures via the carbothermal reduction of resorcinol–formaldehyde/SiO2 hybrid aerogels

The novel resorcinol–formaldehyde/SiO₂ (RF/SiO₂) hybrid aerogels were chosen to synthesize the cubic silicon carbide (β-SiC) nanostructures via a carbothermal reduction route. In this process, the in situ polymerized RF/SiO₂ aerogels were used as both the silicon and carbon sources. The morphologies and structures of SiC nanostructures were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), and high-resolution transmission electron microscope (HRTEM) equipped with EDS. The effects of C/Si atomic ratios in RF/SiO₂ aerogels and heat treatment temperatures on the formation of SiC nanomaterials were investigated in detail. It was shown that β-SiC nanowhiskers with diameters of 50–150 nm and high crystallinity were obtained at the temperatures from 1400 to 1500 °C. The role of the interpenetrating network of RF/SiO₂ hybrid aerogels in the carbothermal reduction was discussed and a possible mechanism was proposed.     

碳纳米管羧基化及其电化学性能研究

利用氧化剂对多壁碳纳米管(MWNTs)进行处理,成功的制备了羧基化的碳纳米管。分别通过TEM、XRD、全自动比表面及孔隙度分析仪及恒流充放电装置对它们的形貌、晶体结构、比表面积及电容性能进行了研究,电容性能结果显示羧基化的碳纳米管电容值明显增强,这应该归因于羧基化的碳纳米管拥有较大的比表面积和亲水性,有利于电解液离子的传输。     

Study of correlation of structural and surface properties with electrochemical behaviour in carbon aerogels

Carbon aerogel is a promising material for electrochemical double layer capacitors. In this paper carbon aerogels prepared by subcritical drying method are investigated for the change in the structure and surface properties at different pyrolysis temperatures. The important relations between structure, morphology, surface area and electrical properties were studied using X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), surface area measurement and cyclic voltametry. It is shown that structure and the surface functional groups play important role in enhancement of electrochemical capacitance. The specific capacitance achieved was 114 F/gm which is quite large value for subcritically prepared carbon aerogels without any kind of activation process.