超临界发泡制备泡沫炭及其泡孔形成机理

分别以中间相沥青和甲苯作碳质前驱体和发泡剂,采用超临界发泡技术制备出孔径为10~25μm的泡沫炭,并着重研究了超临界发泡条件对泡沫炭的孔形及韧带结构的影响。超临界发泡包括成核、扩散、聚集及膨胀过程,同时泡孔的形成也是热力学、动力学及力学行为综合作用的结果。由于中间相沥青中存在轻组分,超临界发泡过程伴随着自发泡过程,由此可获得层次孔结构的泡沫炭。     

预氧化对中间相沥青泡沫炭结构和性能的影响机制研究

研究了预氧化对萘系中间相沥青的表面化学性质、族组成分布以及对泡沫炭的发泡条件、泡孔形成、孔结构及微结构的影响机制.当中间相沥青经210℃预氧化2h后,其喹啉不溶物含量增加32.3%,族组成分布变窄.在600℃/3MPa发泡条件下,所制石墨化泡沫炭的平均孔径、压缩强度分别为200μm、2.8MPa.     

中间相沥青基泡沫炭的气泡生长过程

以AR合成中间相沥青为原料,在不同的温度下发泡制得了泡沫炭.采用扫描电镜和光学显微镜等分析手段对中间相沥青基泡沫炭的气泡生长机理进行了初步研究,讨论了温度对泡孔结构的影响.结果表明,当温度从480℃升至540℃时,平均泡孔直径从500μm升到800μm.最初形成的泡沫在熔融沥青中分布不均匀,汇集在沥青的上表面;气泡在Z轴方向的形状是椭球形,在Z轴垂直方向为球形.中间相沥青基泡沫炭气孔的形状和泡沫的体积密度密切相关.形成的泡沫体在z轴方向存在明显的体积密度梯度.     

中间相沥青基活性泡沫炭的制备及其电化学性能研究

以中间相沥青为前驱体,经自挥发发泡法、KOH活化法制备的中间相沥青基活性泡沫炭作为超级电容器电极材料。采用扫描电镜、X射线衍射和低温(77K)N2吸附法对中间相沥青基活性泡沫炭的表面形貌和微观结构进行表征。中间相沥青基活性泡沫炭的比表面积为2700m2/g,总孔孔容为1.487cm3/g。通过恒流充放电、循环伏安和交流阻抗测试,考察了中间相沥青基活性泡沫炭作为超级电容器电极材料的电化学性能。在电流密度为0.02A/g时,中间相沥青基活性泡沫炭的比容量为240.48F/g,能量密度为33.4Wh/kg;在电流密度为5A/g时,比容量为166.68F/g,具有良好的电化学特性。     

嵌段共聚物直接热解法制备介孔炭材料及其在超级电容器中的应用（英文）

以嵌段共聚物为前驱体,通过直接热解聚丙烯腈嵌段苯乙烯(PAN-b-PS-b-PAN)制备新型纳米多孔炭材料。炭材料制备依赖于嵌段共聚物分子的设计,而分子量可控、分布范围较窄的嵌段共聚物则通过可逆加成链转移(RAFT)聚合方法合成。所制炭材料不仅具有较高的比表面积(950 m2·g-1),且在2~4 nm的介孔范围内孔径得到良好的控制。此外,作为电极材料在2 mol/L KOH电解液中表现出高的比容量(185 F·g-1,电流密度为0.625 A·g-1),且显示较好的循环寿命,经10 000次循环后,能够保持初始比容量的97.5%。通过不同分子量聚合物的设计,制备结构新颖的多孔炭材料,可应用于高性能超级电容器。     

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。     

由中间相沥青制备泡沫炭:Fe(NO3)3的影响

以中间相沥青为前驱体制备高性能泡沫炭，在考察中间相沥青、Fe（NO3）3及其混合物热分解行为的基础上，着重研究了Fe（NO3）3对制备中间相沥青基泡沫炭的影响，揭示了Fe（NO3）3对泡沫炭孔泡结构的影响规律及其作用机制，初步研究了在泡沫炭炭化过程中形成的Fe／C之物相结构及其石墨化行为。结果表明，在不同的炭化温度下，Fe在泡沫炭中的存在形态各异；Fe物种的存在有利于提高泡沫炭的石墨化程度。     

模板炭化法制备沥青基中孔炭材料

以MgO为模板,采用低软化点(27℃)各向同性沥青为炭材料前驱体,采用程序升温一步炭化法制得了系列中孔炭材料。采用乙酸镁和柠檬酸镁为MgO的前驱体,沥青与MgO前驱体按照不同质量比混合,混合比例以得到的MgO为计算基准。采用低温N2吸附测得炭材料的比表面积和孔径分布,采用透射电镜观察炭材料的内部结构特征。结果表明,两种前驱体与沥青混合得到的炭材料比表面积均随MgO/沥青质量比例的增加呈线性增加趋势,柠檬酸镁体系中MgO/沥青质量比为8/2时最高比表面积达到1295m2/g,随MgO/沥青质量比的不同分别在2.5nm和5nm处有集中的孔分布;乙酸镁体系制得的炭最高比表面积也达到1199m2/g,并且在5nm和12nm处有集中的孔分布。     

中间相沥青表征研究进展

中间相沥青是光学各向异性的芳香类碳氢化合物的聚集体,是一种重要的炭材料前驱体。中间相沥青的性质表征及分析对中间相沥青及其衍生产品的制备、质量调控及应用具有重要意义。中间相沥青的分子结构、分子量及分布的有效测定有助于掌握反应机理和控制产品质量,聚集态结构直接决定着炭纤维和其它衍生炭材料的性能,中间相沥青的流变性是炭纤维研制和生产过程中最重要的参数。本文综述了中间相沥青性质表征方面的研究进展,重点介绍了中间相沥青分子量、聚集态结构、流变性方面的表征方法及结果,最后展望了中间相沥青表征的研发前景。     

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。     

沥青原料对沥青基碳纤维结构与性能的影响

以中间相茶沥青(AR树脂)和各向同性煤沥青(ICP)为原料,系统研究了沥青原料性质与由其制备的碳纤维结构、性能之间的关系.研究表明,AR树脂中的一维有序中间相结构在纺丝中被拉伸,形成不同中间相间的界面,成为应力集中区,在后续碳化过程因应力释放导致纤维开裂而损害其力学性能;而ICP沥青基本为无定形相结构,在纺丝过程中无明...     

印刻法制备中间相沥青基中孔炭

用中间相沥青作碳源,硅胶水溶液作造孔剂,采用胶体印刻法制得一系列中孔碳。实验发现当适量纳米级硅源添加到中间相沥青中,会在彼此颗粒间形成一定的纳米孔道,从而导致中间相沥青在炭化过程中没有沥青由固相向液相转化的过程。结果表明：碳硅比、印刻温度以及中间相沥青的基本物化性质都将对中孔碳的孔结构发生重要影响。且制得比表面积和孔容分别为482m2/g和1.62cm3/g的中孔碳。     

活性泡沫炭用于超级电容器电极材料

以酚醛树脂、煤沥青泡沫炭为原料,经水蒸气活化制得比表面积分别为961和953m2/g的活性泡沫炭。采用扫描电镜、BET吸附仪、恒流充放电法和循环伏安法对两种活性泡沫炭的结构进行了表征并研究其充放电性能。结果表明,酚醛树脂泡沫炭在1.0nm以下的孔较煤沥青泡沫炭丰富。在1.0mA充放电时,两者的充放电容量分别为106.28和105.1F/g,相差不大,当充放电电流增大到50mA时,前者容量为41.94F/g,后者为17.23F/g。可见,微孔的孔径分布对充放电性能具有很大影响,增大微孔的孔径有利于提高活性炭电极的充放电容量和功率。循环伏安法测试表明在100mV/min扫描速率下酚醛树脂泡沫炭粉的电化学窗口大于煤沥青泡沫炭粉。     

Comparative evaluation of mesophase pitches derived from coal tar and FCC-DO

Three kinds of mesophase pitches (MPs) derived from FCC-DO (P) and hydrogenated QI free coal tar (QIF) were comparatively evaluated in terms of their spinnability and stabilization reactivity based upon their structural characterizations. MP-P, which is meso-phase pitch from FCC-DO, preserved considerable amount of aliphatic and naphthenic hydrogens to show higher solubility, fusibility and softening temperature of as low as 245 °C in spite of its complete anisotropy. MP-C1 derived from catalytically hydrogenated QIF carried less hydrogen content and smaller molecular weight although its solubility and softening temperature were almost the same to those of MP-P. MP-C2 which was prepared from QIF treated with tetrahydro-quinoline (THQ) showed the least hydrogen content, the lowest solubility and the highest softening temperature of 290 °C. MP-P allowed smooth spinning for much longer time at the temperature from 320 to 350 °C. MP-C1 could be spun at the temperature from 340 to 370 °C, which was much higher than that of MP-P in spite of their similar softening temperatures. MP-C2 showed spinnability at the temperature from 340 to 390 °C, although evolved gases disturbed its smooth spinning at the higher temperature.MP-P showed the highest stabilization reactivity to require the shortest time (120 min) for the sufficient stabilization at 250 °C. Although much longer time of 180 min was necessary for the MP-C1 at 250 °C, a higher temperature of 270 °C accelerated the stabilization reactions to shorten the time to 60 min. MP-C2 showed the least reactivity, requiring 120 min at 270 °C. More aliphatic and naphthenic structure of FCC-DO derived mesophase pitch is related to its superiority as the pitch fibre precursor. The catalytic hydrogenation which can produce naphthenic or aliphatic structure is a better pre-treatment to modify the coal tar as the mesophase pitch precursor.     

同步氢化/热缩聚法制备中间相沥青的工艺研究

系统地研究了在氢化剂量固定情况下,反应温度与时间对同步氢化/热缩聚法所制得的中间相沥青(MP)性质的影响,并制得了可纺MP。研究表明反应时间同为4h时,MP的软化点和不溶分含量随反应温度的提高而升高;偏光结果显示,低温产物为中间相小球和各向同性基质的混合物,高温产物为连续中间相。反应温度同为410℃时,MP软化点和不溶分含量均随反应时间的延长而显著提高,经历了从中间相小球到小球发生融并,最后形成了马赛克织构的中间相。纺丝性能测试表明,反应温度为410或420℃,反应4h制得的中间相沥青,可以熔融纺丝,经氧化和碳化后制得两组碳纤维。     

炭/炭复合材料用高性能浸渍剂沥青的研究

根据原生QI杂质由微米级炭粒构成的特性,采用溶剂絮凝法对煤焦油进行了净化处理,以净化煤焦油为原料制备了低QI含量的高性能浸渍剂沥青,对比研究了高性能浸渍剂沥青的流变性能和渗透性能。结果证实:高性能浸渍剂沥青极大地改善了浸渍效果,并且使炭/炭复合材料的力学性能显著提高。     

加热条件对炭泡沫材料孔结构和性能的影响

以AR沥青为原料,利用高压釜在不同恒温条件下制备了炭泡沫,并测定了其孔结构、体积密度、显气孔率、压缩强度、常温热导率以及微晶参数.结果表明:相对于短恒温时间,长恒温时间制得的炭泡沫孔径大(412nm)、显气孔率高(83.82%)、体积密度小(0.34g/cm~3)、压缩强度高(4.92MPa),多孔连通结构更丰富.经过石墨化处理后,石墨泡沫呈现出较高的常温热导率(71.34W/(m·K))和较小的层片间距d_(002)(0.33556nm).石墨泡沫的常温比导热率能达到210(W·(m·K)~(-1)) /(g·cm~(-3)),是铜的5倍,铝的4倍.     

Structural changes during pitch-based carbon granular composites carbonisation

This article deals with the study of carbon composites behavior during their carbonization. Composites were prepared using four granular carbons (graphite, anthracite, green petroleum coke, and foundry coke) and four pitches (a commercial impregnating coal-tar pitch, an air-blown and two thermally treated pitches). The evolution of the optical microstructure, porosity, volume, and weight of carbon composites was monitored at different intermediate carbonization temperatures (350, 500, 700, and finally 1000 °C). The porosity of composites increases with carbonization due to volume changes and weight loss of pitches. Weight loss of carbon composites during their carbonization mainly depends on the pitch characteristics and it was slightly influenced by the presence of granular carbon. On the other hand, carbon composites with the commercial coal-tar pitch and foundry coke, anthracite, or graphite deform in the initial stages of carbonization (<350 °C) probably due to the lower porosity of the green pellets and the high amount of low-molecular weight compounds of the pitch. Carbon composites with green petroleum coke underwent important dimensional changes during their carbonization, expanding initially and then shrinking at temperatures above 700 °C. The type of granular carbon strongly influenced the microstructure of the final carbon composite, as a result of its effect on the development of mesophase. Graphite, anthracite and foundry coke delays mesophase development, whereas green petroleum coke accelerates mesophase formation.     

Physical characteristics of baked carbon mixes employing coal tar and petroleum pitches

A study of the physical characteristics of baked carbon mixes employing coal tar and petroleum pitches as the binder has been made to explore their relative suitability in the fabrication of carbon products. The study reveals that coal tar pitch is the most suitable binder and a petroleum pitch of the same softening point leads to a carbon product of much inferior characteristics. Raising the softening point of the petroleum pitch from 78 to 150° C or adding 10 parts of carbon black in the lower softening point pitch, increases the density, strength and also the electrical resistivity of the baked carbons. The addition of 10 parts of carbon black to the higher softening point petroleum pitch leads to a carbon product with further improved values of density and strength, which are comparable to those obtained with the coal tar pitch. However, the electrical resistivity also is marginally increased. It appears that a petroleum pitch of high aromaticity may fulfill the requirements expected of a good binder.     

Solubility of heat-resisting polymers in mesophase pitches at their spinning temperatures

Solubilities of two thermoresisting polymers (polyethylene telephthalatep-hydroxybenzoate, a liquid crystal polymer and polyethylene naphthalate) in mesophase pitches (MP) derived from coal tar (C1) and petroleum residues (P1 and P2) were examined to prepare blended fibre as the better precursor for the high-performance carbon fibre. MP-C1 and MP-P1 of high aromaticity dissolved 5 wt% of both polymers on mixing at 360 °C for 3 h, maintaining 100 vol% anisotropy which the parent mesophase pitches exhibited, although only MP-C1 did so at 340 °C. In a marked contrast, a number of isotropic droplets from both polymers dispersed in MP-P2 after the blending under the same conditions. The blends of MP-C1 with polymers were spinnable at around 370 °C into fibres of 10 to 20 m diameter although their spinnability was slightly inferior to that of the pitch alone. The blended fibre exhibited slightly higher stabilization reactivity at 270 to 300 °C than that of the parent mesophase pitch fibre. Structural factors of the mesophase pitch which influence their dissolving ability are discussed. Thermal stability of the polymers is also briefly examined.