中间相沥青基碳电极材料的制备工艺优化与性能

以煤焦油沥青为原料,采用"中间相调制-化学活化"工艺制备了超级电容器用活性碳电极材料,考察了中间相调制温度对活性碳晶体结构、孔径分布、电容量特性的影响,并分析了中间相沥青的调制过程及不同实验条件对活性碳晶体结构、孔径分布、电容量特性的影响。结果表明,中间相沥青调制温度主要集中在190～492.5℃,随中间相调制温度升高,活性碳电极材料的振实密度明显增大,在500℃条件下制备的活性碳材料具有最高的比电容量,达到103F/g,较高的调制温度能提升活性碳中碳的边缘层含量,从而提高材料的面积比电容量。     

NaY分子筛模板法合成多孔炭材料

采用NaY沸石分子筛作模板,乙酰丙酮为炭前驱体,使用液相浸渍-气相沉积工艺合成了富含微孔和中孔结构的多孔炭材料并对其进行了表征.所合成的多孔炭比表面积1351m2/g,孔容0.892cm3/g,微孔率0.63,孔径分布多在0.8nm～3.0nm之间.     

利用线性酚醛树脂制备有序介孔碳

三嵌段共聚物F127为模板剂,线性酚醛树脂为碳前驱体,采用溶剂挥发诱导有机-有机自组装法(EI-SA)制备了具有二维六方结构的有序介孔碳。利用FT-IR、XRD、TEM、N2吸附/脱附等方法对有序介孔碳的结构进行了表征,研究了不同焙烧温度和模板剂用量对有序介孔碳结构的影响。结果表明,当模板剂的用量一定时,有序介孔碳的孔径、孔容和孔壁厚度都随着焙烧温度的升高而降低,但比表面积却随着微孔含量的增加而增大。随着模板剂用量的增加,介孔碳的有序性降低。有序介孔碳PF-2-500的比表面积、孔径、孔容、孔壁厚度和微孔比表面积比分别为583.82m2/g、3.05nm、0.31cm3/g、3.40nm和361.18m2/g,而有序介孔碳PF-1-500的比表面积、孔径和孔容相对于PF-2-500有所提高,分别为647.79m2/g、3.44nm和0.41cm3/g,但微孔比表面积和孔壁厚度分别降低为309.46m2/g和3.35nm。     

软模板催化法合成石墨化碳微球及其吸附性能研究

以甲醛、2,4-二羟基苯甲酸、L-赖氨酸为碳源,F127作为软模板剂,采用软模板催化法制备出材料GM。通过碳前驱体的TG和FT-IR测试确定材料煅烧温度为950℃,XRD和Raman谱图证实材料具有典型石墨化结构,SEM和TEM照片说明材料具有空心微球结构,BET结果表明材料呈双孔分布,平均孔径为3.04nm,比表面积为450.59m2/g。材料对苯蒸气有良好的吸附性能,静态吸附容量为835.26μmol/g,穿透时间τ0为9.86min。     

前驱体对炭泡沫孔结构的影响

分别以煤沥青、石油中间相沥青和AR沥青为前驱体制备炭泡沫材料。采用GPC测定前驱体分子量,SEM观察所制炭泡沫的孔结构,光学显微镜测量所制炭泡沫的孔径及其分布。结果发现,由于煤焦油沥青不含中间相,且QI含量较高,导致在实验条件下不能直接制备出合格的炭泡沫。以石油中间相沥青和AR沥青为原料均能制备出具有分布均匀开孔结构,且微观各向异性的炭泡沫。由AR沥青制备的炭泡沫呈现平均孔径较小(212μm)、孔壁较薄、孔径分布较窄(180μm~300μm)、开孔率较高、以及韧带排列较规整等特点,表明低QI含量、低分子量且分布较窄的前驱体有利于发泡。     

Development of titanium-doped carbon–carbon composites

The development of titanium-doped carbon matrix–carbon fibre reinforced composites (CCCs) via liquid impregnation of carbon fibre preforms using mesophase pitch is studied. Two different approaches for introducing the dopant into the carbon material are investigated. One consists of doping the matrix precursor followed by the densification of the preform with the doped precursor. The second approach consists of doping the porous preform prior to densification with the undoped mesophase pitch. Titanium-doped CCCs with a very fine distribution of dopant (in the nanometric scale) are obtained by adding TiC nanoparticles to the matrix precursor. Thermal decomposition of titanium butoxide on the carbon preform prior to densification yields doped CCCs with higher titanium content, although with larger dopant size. The combination of these two methods shows the best results in terms of dopant content.     

中孔炭的水玻璃模板法制备、结构调控及球形功能化

以廉价水玻璃为原料, 通过控制水解条件, 合成出具有不同尺寸的SiO₂溶胶, 并与间苯二酚-甲醛(RF)溶胶形成均相的凝胶复合物, 经常压干燥、炭化、酸洗, 得到具有可控结构的中孔炭材料。考察了水解温度、水解时间和反应物组成对孔结构的影响, 并通过氮气吸附、扫描电镜和透射电镜对材料的微观结构进行了表征。结果表明: 中孔炭的孔隙反相复制于SiO₂凝胶网络, 其平均孔径随水解时间的延长或水解温度的升高而增大, 并在6~12 nm范围内精细调控, 而其总孔隙率可以通过改变炭、SiO₂前驱体比例调节。对液相复合溶胶通过悬浮聚合法和喷雾干燥法处理, 分别制备出毫米级和微米级的中孔炭球, 进而实现了中孔炭在宏观形貌上的调控。本工作为中孔炭的低成本制备、精细结构调控以及球形功能化提供了重要参考。     

结构有序、双重孔隙中孔炭材料的合成与表征

采用纳米涂层技术,以介孔分子筛SBA 15为模板,在其纳米孔道内引入糠醇/草酸溶液,经原位聚合,炭化后制得炭/SBA 15复合物。采用化学法脱除模板后制得具有规则结构的中孔炭。高分辨TEM表征结果显示该中孔炭是由纳米炭管相互联接、堆积而成,且具有六方对称结构。氮吸附结果显示其比表面积高达2000m2/g,孔径呈双峰分布。孔径相对较大的孔隙来源于SBA 15孔道经纳米涂层后所保留的孔隙;孔径相对较小的孔隙来源于SiO2移除后遗留的纳米孔空间。该方法可应用于以其他多孔氧化硅为模板制备新型纳米复合物的研究过程。     

On the use of mesophase pitch for the preparation of hierarchical porous carbon monoliths by nanocasting

Abstract

A detailed study is given on the synthesis of a hierarchical porous carbon, possessing both meso- and macropores, using a mesophase pitch (MP) as the carbon precursor. This carbon material is prepared by the nanocasting approach involving the replication of a porous silica monolith (hard templating). While this carbon material has already been tested in energy storage applications, various detailed aspects of its formation and structure are addressed in this study. Scanning electron microscopy (SEM), Hg porosimetry and N₂ physisorption are used to characterize the morphology and porosity of the carbon replica. A novel approach for the detailed analysis of wide-angle x-ray scattering (WAXS) from non-graphitic carbons is applied to quantitatively compare the graphene microstructures of carbons prepared using MP and furfuryl alcohol (FA). This WAXS analysis underlines the importance of the carbon precursor in the synthesis of templated porous carbon materials via the nanocasting route. Our study demonstrates that a mesophase pitch is a superior precursor whenever a high-purity, low-micropore-content and well-developed graphene structure is desired.     

制备条件对炭泡沫结构的影响

利用沥青在热解过程中产生挥发性气体自发泡和高压渗氮的原理，以石油中间相沥青为原料，采用高压反应釜制备炭泡沫材料。用SEM和偏光显微镜观察了材料的孔结构，分析了制备条件对炭泡沫结构的影响。结果表明，温度和压力是影响炭泡沫材料结构的重要因素，在实验条件范围内，较高的反应温度和压力有利于制备出较高性能的炭泡沫，其气孔率较高，韧带炭层排布规则。     

聚酰亚胺基高比表面活性炭及其电化学性能研究

以聚酰亚胺(PI)薄膜边角料为前驱体, 采用CO₂物理活化法制备高比表面活性炭。研究了活化工艺对PI活性炭孔结构性能的影响及其活化机理, 探讨了活性炭孔结构对其电化学性能的影响。结果表明, PI薄膜可以在相对较低的温度下经CO₂活化制备出具有无定型微晶质炭结构、孔隙结构发达的活性炭, 比表面积最高可达2809 m²/g, 总孔容积达1.423 cm³/g; 通过控制CO₂活化工艺, 可实现对PI活性炭的孔道尺度与分布的调控。作为超级电容器电极材料, PI活性炭在100 mA/g条件下, 比电容高达237 F/g, 电容保持率为86%。孔径集中于0.7~2 nm, 并存在适量介孔的活性炭具有极佳的电化学性能。     

中间相沥青制备高密度高强度炭/石墨材料

以在不同氧化温度下制备的氧化中间相沥青为原料制备了具有不同密度的炭/石墨材料, 根据对样品物理性能和微观结构的研究得出最佳的工艺条件. 以150MPa压制的坯体经过2200℃石墨化后得到具有高密度(2.02g/cm³)、低孔率(2.03%)、大体积收缩(44.86%)、高的弯曲强度和压缩强度(70.3和123.3MPa)的样品. 该样品具有均匀致密的结构. 实验证明, 氧化中间相沥青是制备高性能炭石墨材料良好的前驱体.     

基于结构调节碳材料的掺氮种类和含量及其超级电容器储能应用

碳材料是极具潜力的超级电容器电极材料, 但是其容量较低。异质原子掺杂, 尤其是氮掺杂, 是大幅度提高碳材料电化学性能的有效方法。但是在碳材料中实现高含量的活性氮掺杂仍极具挑战。本研究通过Si-O-Si网络和氧化铝之间的相互作用成功调节碳材料的掺氮种类及其含量。除此之外, 通过调节前驱体组成, 碳材料的结构可以从珊瑚状转变为三维结构。在反应中, 氧化物中的氧原子可以和碳材料中氮原子成键, 氮原子不易逃离, 从而实现高含量氮掺杂(5.29at%@1000 ℃)。另一方面, 相互作用使碳材料孔体积增大(1.78 m³·g^-1)和孔径分布加宽(0.5~60 nm)。因此, 获得的富氮掺杂碳材料具有302 F·g^-1@1 A·g^-1的高容量和177 Fg^-1@120 A·g^-1的杰出倍率性能。此独特的固氮方法是一种有潜力的制备高性能超级电容器电极材料的策略。     

Preparation of nanoporous carbons via a grafting method for the application to electrochemical double layer capacitors

Nanoporous carbon materials with a controlled pore size and surface area were prepared using grafting method. The use of 3-mercaptopropyltrimethoxysilane (MPTMS) as a grafting material played an important role in producing a porous structure by linking the silica to the polymer, with the subsequent formation of a silica-polymer composite. Importantly, the use of an organic solvent, compared to an aqueous solvent, has a positive effect in forming uniform and well-developed carbon structures, due to the high degree of dispersion with well-mixing of the carbon and silica precursors. The amounts of MPTMS and carbon precursor used determined the pore size and surface area of resulting carbon materials. The optimum ratio of MPTMS and carbon precursor for achieving a high surface area in excess of 2000 m2/g was determined. The use of a large amount of carbon precursor resulted in carbons with a relatively small surface area and an increase in MPTMS content led to an increase in the microporous structures. The capacitance value of the porous carbon prepared using the optimum ratio was determined to be 150 F/g.     

Observation of carbonaceous mesophase behaviors in phenolated sawdust using polarized light microscopy

The phenolated sawdust had been proved to be a new kind of carbon precursor with excellent self-sintering ability. As a part of research on characterizing the structure and composition of the new kind of carbon precursor, the self-made sinterable phenolated sawdust was observed with polarized light optical microscope in this paper. It was found that the derivative contained some mesocarbon microbead-like optical anisotropic phase which might flow under pressure. The phenolated sawdust was also observed with hot-stage polarized light optical microscope. The results showed that anisotropic phase could be further formed from the phenolated sawdust and then transformed into carbon during the heat treatment. According to the observed results, it was concluded that the self-sinterable phenolated sawdust contained carbonaceous mesophase and component being transformable into carbonaceous mesophase. To some extent, the phenolated sawdust could be described as a new kind of carbonaceous mesophase.     

Large-scale ultraflat nanopatterned surfaces without template residues

Ultraflat surfaces are required for many studies of single molecules, and the need for both a wide choice of surface materials and the ability to pattern these surfaces has led to the development of different template-stripping approaches. The fabrication of nanopatterned ultraflat surfaces is particularly challenging, because more than one material is present in the surface. We demonstrate a new template-stripping strategy that allows us to fabricate large-area nanopatterned surfaces, solving the problem of incomplete template removal by introducing a sacrificial carbon layer and a sandwich structure for the template. The thin residual carbon film transferred from the template is removed from the nanopatterned surface by dry etching, as demonstrated by x-ray photoelectron spectroscopy and, for metal nanoparticles embedded in a glass surface, by a shift in the absorption of the localized surface plasmon resonance. We show that gold nanoparticles in a glass surface can be selectively functionalized with thiols yielding about 2?nm height increase. Atomic force microscopy and localized surface plasmon resonance spectroscopy both indicate that the nanoparticle shape is preserved well.     

Na_2HPO_4活化木材液化物碳纤维孔隙结构与表面化学结构

为了探究Na2HPO4活化处理引起的木材苯酚液化物碳纤维微细结构的变化,以Na2HPO4溶液为活化剂对杉木苯酚液化物碳纤维原丝进行了浸渍、干燥和不同温度的活化处理,对活性碳纤维的晶体结构、孔隙结构和表面化学结构进行了表征。结果表明:随着活化温度的上升,活性碳纤维的得率逐渐减小。活性碳纤维的晶体结构属于类石墨结构;随着活化温度上升,微晶层间距d002减小,而石墨片层平面尺寸Lc和Lc/d002增加。活化温度在600℃或700℃时,微孔率小于48vol%;当活化温度为800℃或900℃时,微孔率大于60vol%。活性碳纤维的微孔孔径主要集中在0.5~1.6nm范围内,中孔孔径主要分布在2.0~4.0nm范围内。随着活化温度的上升,纤维的比表面积和孔容积均逐渐增加,900℃时二者均达到最大值,此时的比表面积为1 306m2/g。C和O是活性碳纤维的基本元素,纤维表面大部分的含碳基团为石墨碳,含有少量的C—OH、CO和—COOH。研究为制备新型活性碳纤维和进一步探明活化剂同碳纤维分子之间相互作用提供参考。     

The effect of size and shape variation in discotic liquid crystals based on triphenylene cores

The triphenylene core provides a versatile platform from which discotic liquid crystals can be constructed. Synthetic advances permit the effect that substantial or subtle variation on structure has on mesophase formation. Through comparison of many derivatives, from our studies and others, it appears that the discotic core should be viewed as the triphenylene unit plus the attached polarizable substituents. Disruption of these extended cores discourages mesophase formation.     

Electron microscopy study of mesophase pitch-based graphite fibres

A comprehensive electron microscopic investigation of the structure of the graphitic sheet in mesophase pitch-based fibres is presented.In situ brightfield and (00l) darkfield observation of the sheets in sub micrometre fibres reveals a finely striated structure, associated with three-dimensional order. (hkl) darkfield imaging of the sheets in their edge-on and face-on orientations indicates that the striations correspond to the edge view of a mosaic of graphite grains. The grains have lateral dimensions of 100 to 200 nm on average but are only a few atomic layers thick.In situ lattice imaging of the fibre edges indicates a very high level of lattice perfection of the (00l) domains below the fibre surface, quite in line with the outstanding mechanical and thermal properties of this type of fibres. A variety of surface defects are revealed. Preferential orientation effects of the sheet texture on the fibre electron diffraction pattern are described.     

磷酸法活化煤焦油渣制备活性炭研究

研究了以陕西煤焦油渣作为原料,用磷酸作为活化剂,在400～1000℃的条件下经一步炭活化法制备活性炭。研究了炭活化温度、时间、料剂比对煤焦油渣制备活性炭吸附性能及孔结构的影响。实验结果表明炭活化温度、炭活化时间主要影响活性炭产品的得率,高温和长时间会导致更多的碳损失;活性炭的吸附性能及孔结构主要受炭活化温度和料剂比影响。最佳活化工艺条件为850℃、3h、1∶3。通过其活性炭表面孔径分布及表面官能团含量变化表征,用磷酸浸泡煤焦油渣制备活性炭有利于大、中孔结构的产生,其最佳活化条件下孔径分布约在20～100nm。