同步合成模板炭化法制备双电层电容器电极用中孔炭材料的研究

以正硅酸乙酯为模板硅源，间苯二酚—甲醛凝胶为炭前驱体，采用同步合成模板炭化(SSTCM)法制备了具有可控结构的中孔炭材料。炭材料的比表面积可达1500m^2/g，平均孔径在3nm～10nm之间。经过酸催化水解预处理的二氧化硅模板前驱体溶液与间苯二酚—甲醛溶液混合，碱性条件下使两者的溶胶凝胶反应同步发生，得到有机，无机凝胶混合物。再经炭化、HF去模，制得SSTCM炭材料。N2等温吸脱附研究表明，与炭前驱体聚合物同步合成的结构可调的二氧化硅模板，导致了SSTCM炭材料可控中孔结构的形成。循环伏安研究表明，采用这种同步合成模板炭化法制备的SSTCM炭材料质量比容量达270F／g，炭材料具有的典型中孔结构使其可能成为一种理想的双电层电容器电极材料。     

聚硅氧烷制备高比表面积微介孔炭材料(英文)

通过对聚甲基(苯基)硅树脂(SR249)在1250～1350℃、真空气氛下裂解以及氢氟酸酸洗处理制备得到具有高比表面积的纳米多孔炭材料。采用X-ray衍射光谱、拉曼光谱、元素分析、透射电镜及氮气吸附法对不同温度所制样品进行元素组成及结构研究。裂解产物中的SiO2相作为一种天然模板经腐蚀处理除去。裂解温度和酸洗处理对多孔炭材料的成分和结构变化影响较大。HF酸处理前,裂解产物的比表面积小于55m2/g;而酸洗后产物比表面积和总孔容量显著增加,而最高值是裂解温度为1300℃时获得,分别为1148m2/g、0.608 cm3/g。经酸洗处理得到的多孔炭,孔径分布均相对较窄,在1～4 nm。透射电镜结果显示炭材料中的自由碳相和少量的SiC纳米晶及SiOC陶瓷彼此相互包裹。     

管状多孔炭膜的研究

介绍了管状多孔炭膜的制备方法及应用,探讨了不同材料制备支撑体炭膜和炭－炭复合膜的效果及影响炭膜孔结构性能的主要因素。研究表明,煤和酚醛树脂均是良好的制膜材料,制得的支撑体炭膜不仅具有较高的孔隙率和气体通量,而且孔隙结构均一,机械强度高。膜材料的种类,粒度及炭化工艺条件等因素对炭膜的孔结构性能影响较显著。以酚醛树脂等高分子聚合物及煤热解产物为涂膜液制得的炭－炭复合膜其孔径明显的变小,孔径分布变窄。炭     

一步浸渍合成具有多重孔隙的铸型炭体

以多孔块状硅体为模板,通过一步浸渍、炭化、酸处理工艺,制备出结构可控、孔隙联通且具有多重孔隙的铸型炭体。分别采用氮吸附技术、高分辨透射电镜和扫描电镜对模板硅、硅碳复合物及相应炭体进行了结构表征。从微米尺度分析,该炭体是由高度联接的枝状结构单元为骨架构筑而成。与模板硅相比较,此炭体是硅体的正复本。从纳米尺度分析,这种炭体枝状骨架是由分布均匀且相互连接的中孔构成,此中孔及其孔壁对应于模板硅的孔壁及中孔,是多孔硅的负复本。此外构成中孔的炭骨架本体又含有大量炭化过程产生的微孔。因此该法合成的铸型炭具有孔隙高度发达和结构层层嵌套的特点。     

1,3,5-三甲苯扩孔改性硼掺杂有序介孔炭

以F108为模板剂,1,3,5-三甲苯(TMB)为有机扩孔剂,采用溶剂挥发诱导自组装的方法成功制备出了具有较大孔径、比表面积和有序性高的硼掺杂有序介孔炭。探究了扩孔剂用量对硼掺杂介孔炭结构的影响,并对其电化学性能和扩孔机理进行了分析。结果表明,当扩孔剂与模板剂的用量比为1.5时,所得的介孔炭TMB-1.5的孔径最大(4.2nm),比表面积最高(666m~2/g)。相对于未扩孔改性的介孔炭,孔径和比表面积分别提高了5%和10%。扩孔改性后的硼掺杂介孔炭具有良好的电化学性能,在0.2A/g电流密度下的比电容高达235F/g。     

纳米浇注法制备有序介孔WC/C复合材料及电催化性能

以介孔SiO2为硬模板,通过纳米浇注法在模板孔道中引入不同质量配比的碳源和钨源前驱物,经过高温碳化还原反应,刻蚀除去模板后得到了介观结构有序的SBA-15和KIT-6介孔碳化钨/炭(WC/C)复合材料。采用XRD、TEM、EDX、TGA、CV和N2吸附-脱附等测试手段,对所得复合材料进行了物化性质分析和结构表征。结果表明,该介孔WC/C复合材料具有有序的介观结构(p6mm,Ia3d)、高的比表面积(约500m2/g)和较大的孔径(约4nm)。CV测试表明,三维贯通的有序TC/C-KIT-6为载体负载Pt催化剂,对甲醇的催化氧化具有更优异的作用。     

有序介孔复合炭膜的制备及其性能研究

采用软模板法合成有序介孔炭(OMC),利用XRD、TEM及SEM等分析方法对其进行结构性能分析,探讨了催化剂和模板剂的种类及用量、反应温度等合成工艺条件对形成OMC结构性能的影响。以最佳工艺条件制备的OMC前驱体为涂膜液涂敷在管状微滤炭膜表面,经炭化制得有序介孔复合炭膜,而后考察了复合炭膜的气体渗透性能。结果表明:以盐酸为催化剂、模板剂F127/间苯二酚摩尔比为0.0081、反应温度为30℃时,可合成有序程度最佳的OMC前驱体。用该OMC前驱体涂敷微滤炭膜制备的有序介孔复合炭膜,改善了微滤炭膜的孔结构,最大孔径由0.530μm减小至0.299μm,同时提高了炭膜的气体渗透通量。其中,由混煤微滤炭膜所制有序介孔复合炭膜,N2气渗透通量达1.18·10-8m3·m-2·s-1·Pa-1,是未经修饰烟煤微滤炭膜的4倍。     

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。     

异介质甘蔗渣基水热炭对Cr(Ⅵ)的吸附特性

采用甘蔗渣分别成功制得草酸条件下的甘蔗渣基水热炭(OBC)和硫酸条件下的蔗渣基水热炭(SBC),研究草酸和硫酸2种酸性条件下甘蔗渣水热炭对模拟废水中的六价铬离子[Cr(Ⅵ)]的吸附效果。制得的OBC、SBC的BET比表面积分别为19.5767m~2/g、20.086m~2/g,总孔容分别为0.108316cm~3/g、0.158686cm~3/g,平均孔径分别为22.1316nm、31.6004nm,具有较好的孔隙结构。在Cr(Ⅵ)溶液pH=2.0,浓度为50mg/L,SBC用量为0.7g,吸附时间为90min条件下,SBC对Cr(Ⅵ)的去除率最高达到99.8%,具有较好的去除效果。     

逐步升压法制备大面积小孔径阳极氧化铝模板

在酸性电解液中,采用逐步升压法制备了高度有序的大面积阳极氧化铝（anodic aluminumoxide,AAO）模板．与传统方法制得的AAO模板相比,其有效氧化面积提高了20多倍扫描电子显微镜（scanning electron microscope,SEM）对模板微观结构的表征结果表明,二者几乎具有相同的有序度和孔密度,且孔洞分布均匀．但相比之下,采用逐步升压法制备的模板孔径要小得多,电压为42V时制得的模板的平均孔径（32．4nm）约为传统方法制得的模板平均孔径（63．2nm）的1／2．     

高性能超级电容器有序中孔炭材料的研制

采用微湿含浸法制备了一系列具有不同比表面积和孔径分布的超级电容器有序中孔炭材料。采用液氮吸附脱附等温线、小角XRD以及TEM表征了有序中孔炭的孔结构,在1MEt4NBF4|PC电解液中测试了其电化学性能。结果表明,所制得的有序中孔炭的BET比表面积随糠醇加入量的增加先增加后减小,糠醇加入量少制得具有CMK-5结构的有序中孔炭,加入量多制得的CMK-3结构。电化学性能测试结果表明,在1mA·cm-2的充放电电流密度下各有序中孔炭材料比电容的大小顺序与其BET比表面积的大小顺序基本一致,具有CMK-3结构的有序中孔炭的倍率性能最好,并且也好于无序中孔炭的。     

Synthesis of polyaniline-coated ordered mesoporous carbon and its enhanced electrochemical properties

Pore surface of ordered mesoporous carbon (OMC) was coated with a thin layer of polyaniline by chemical polymerization of aniline monomers. Structure characterizations, such as N₂ adsorption analysis, small angle X-ray diffraction and transmission electron microscopy, demonstrate that polyaniline is well distributed on the pore surface of OMC. As evidenced by constant current charge–discharge test, specific capacitance of polyaniline-coated ordered mesoporous carbon (PCOMC) reaches as high as 602.5 F/g, which is much higher than that of OMC, due to the incorporation of polyaniline onto the pore surface of OMC. However, the capacitive behavior deteriorated somewhat due to the narrowed pore size and extra faradiac reactions caused by the incorporation of polyaniline.     

Mesoporous carbon nanosheets derived from tubular halloysite and furfuryl alcohol with different concentrations

Mesoporous carbon nanosheets with high surface areas and large total pore volumes were prepared using tubular halloysite as inorganic matrix and furfuryl alcohol (FA) as carbon precursor by a template-like method. Field emission scanning electron microscope, high-resolution transmission electron microscopy (HRTEM) and nitrogen adsorption analysis were employed to characterize the morphologies and pore structures of the samples. It is found that tunable mesoporous carbons can be obtained by adjusting FA volume concentration. Lowering FA concentration leads to an increase in the BET specific surface area and narrowing of the mesopore size distribution.     

N-doped ordered mesoporous carbon spheres derived by confined pyrolysis for high supercapacitor performance

Herein, we report a confined pyrolysis strategy to prepare mesoporous carbon nanospheres by which surface area of carbon spheres is increased, pore size is enlarged and effective N-doping is achieved. In this method, the mesoporous polymer sphere as carbon precursor and 2-methylimidazole as nitrogen precursor are encapsulated in a compact silica shell which provides a confined nano-space for the pyrolysis treatment. The in situ generated gases from mesoporous polymer sphere and 2-methylimidazole under pyrolysis diffuse into the pores of mesoporous polymer sphere in the confined compact silica shell, resulting in increased surface area, larger pore size and N-doping due to self-activation effect. As electrodes in supercapacitor, the N-doped mesoporous carbon nanospheres exhibit a significantly enhanced specific capacitance of 326 F g⁻¹ at 0.5 A g⁻¹, which is 2 times higher than that of mesoporous carbon spheres under unconfined pyrolysis condition, exhibiting its potential for electrode materials with high performance.     

Hollow Mesoporous Carbon Microparticles and Micromotors with Single Holes Templated by Colloidal Silica‐Assisted Gas Bubbles

A simple, new synthetic method that produces hollow, mesoporous carbon microparticles, each with a single hole on its surface, is reported. The synthesis involves unique templates, which are composed of gaseous bubbles and colloidal silica, and poly(furfuryl alcohol) as a carbon precursor. The conditions that give these morphologically unique carbon microparticles are investigated, and the mechanisms that result in their unique structures are proposed. Notably, the amount of colloidal silica and the type of polymer are found to hugely dictate whether or not the synthesis results in hollow asymmetrical microparticles, each with a single hole. The potential application of the particles as self‐propelled micromotors is demonstrated.     

Preparation and electrochemical characteristics of mesoporous carbon spheres for supercapacitors

Mesoporous carbon spheres serving as electrode materials for supercapacitors were synthesized by a facile polymerization-induced colloid aggregation method using melamines as a carbon precursor and commercial colloidal silica as a silica source for hard template. After the carbonization of as-formed resins-template composites at 1000 °C and the removal of the silica template by hydrofluoric acid, the resulting mesoporous carbon spheres with a diameter size of ∼5 μm, specific surface area (up to 1280 m²/g) and uniform pore size as large as 30 nm could be obtained. Due to the enriched nitrogen content and the large pore size of the mesoporous carbon spheres affecting the surface wettability, resistance, and ion diffusion process in the pores, the mesoporous carbon spheres showed a high specific capacitance of 196 F/g in 5 mol/l H₂SO₄ electrolytes at a discharge current density of 1 A/g.     

Simple and efficient CVD synthesis of graphitic P-doped 3D cubic ordered mesoporous carbon at low temperature with excellent supercapacitor performance

Heteroatom doping is a promising strategy for improving the electrochemical performance of carbon materials. Herein, we spotlight an advantageous, simple, and efficient CVD synthesis of P-doped 3D cubic ordered mesoporous carbon (POMC) for the first time. The POMC was prepared by pyrolysis of acetylene/triphenylphosphine (C₂H₂/Ph₃P) mixture at relatively low temperature over Fe-KIT-6 as a sacrificial template. The ensuing P-doped OMC showed an enhanced porous texture than an undoped counterpart with a specific surface area of 403.5 m²/g, pore volume of 0.545 cm³/g, average pore size of 4.64 nm and suitable heteroatom functionalities with P and O contents of 0.13% and 9.83%, correspondingly. The obtained POMC exhibited a much higher specific capacitance of 288F/g at 0.2 A/g (175F/g for OMC), good cyclic stability of 97.6 %, and good rate capability than pristine OMC in 6 M KOH. It is equivalent to or improved than various stated mono doped and even dual doped porous carbon electrodes. Furthermore, a symmetric supercapacitor (POMC//POMC) was fabricated with 1 M Na₂SO₄ aqueous neutral electrolyte exhibits high cycling stability (89.3%) even with a wide potential window (2.0 V) and offers a relatively high energy density (10.01 Wh/kg) with a power density of 300 W/kg.     

Pore structure control of mesoporous carbon as supercapacitor material

The pore structure and electrochemical performances of mesoporous carbons prepared by silica sol template method as electrode material for supercapacitor were investigated in this work. The pore size distribution of the mesoporous carbons changes from unimodal to bimodal and the mean pore size increases with the increase of silica sol/glucose ratio. The specific capacitance of the mesoporous carbons also increases with the increase of silica sol/glucose ratio. A novel technique named as template–chemical activation method, combining both template and chemical activation methods, is proposed, which can effectively control the pore structure, improving the electrochemical properties of the mesoporous carbon with improved porosity especially microporosity.     

The size modulation of hollow mesoporous carbon spheres synthesized by a simplified hard template route

Hollow mesoporous carbon spheres (HMCSs) have been prepared by a simplified replication route from a solid silica core/mesoporous silica shell aluminosilicate (SCMS-Al) template, which was synthesized by directly incorporating aluminum species into the mesoporous framework during template synthesis. The size of HMCSs can be tuned between 80 and 470 nm by simply changing the diameters of SCMS-Al. The HMCSs have uniform mesopores with a narrow pore size distribution (3.4-4.1 nm), and high surface area, (890-1150 m²/g) and total pore volumes (0.75-1.15 cm³/g). The techniques of N₂ sorption isotherms, TEM, EDX and SEM were used to characterize the as-synthesized spheres.     

Ordered Mesoporous Carbons

Ordered mesoporous carbons have recently been synthesized using ordered mesoporous silica templates. The synthesis procedure involves infiltration of the pores of the template with appropriate carbon precursor, its carbonization, and subsequent template removal. The template needs to exhibit three‐dimensional pore structure in order to be suitable for the ordered mesoporous carbon synthesis, otherwise disordered microporous carbon is formed. MCM‐48, SBA‐1, and SBA‐15 silicas were successfully used to synthesize carbons with cubic or hexagonal frameworks, narrow mesopore size distributions, high nitrogen Brunauer–Emmett–Teller (BET) specific surface areas (up to 1800 m² g^–1), and large pore volumes. Ordered mesoporous carbons are promising in many applications, including adsorption of large molecules, chromatography, and manufacturing of electrochemical double‐layer capacitors.