黏结剂沥青的制备及成焦性研究:改性方法的影响

Preparation and coking property of binder pitch: effects of modification methods

  • 摘要: 黏结剂沥青是炭素/石墨电极和锂离子电池负极的重要原料之一,黏结剂沥青的性质在很大程度上决定着炭/石墨制品的品质和应用,高品质黏结剂沥青对高品质炭/石墨材料的制备意义重大。本研究以净化处理后的中温沥青为原料沥青,考察了改性方法对黏结剂沥青的性质(沥青分子结构和沥青热稳定性和沥青光学显微结构)和成焦性(沥青焦光学显微结构、沥青炭微晶结构和沥青炭表面形貌等)的影响。研究结果表明,原料沥青通过氧化聚合和热缩聚两步法处理(第一步:原料沥青在280 ℃温度下恒温空气氧化3 h;第二步:在N2气氛下迅速升温至360 ℃恒温缩聚1 h),能够得到高品质各向同性黏结剂沥青(软化点144 ℃,QI含量0.46%,TI含量26.74%,结焦值51.53%,挥发分56.65%),且该黏结剂沥青芳香缩合程度较高,小分子支链结构较少。将此黏结剂沥青热转化和炭化处理后得到的黏结剂沥青焦的光学显微结构中片状和纤维结构含量达到了83.92%,黏结剂沥青焦的无序化程度较低,微晶结构规整有序(趋于规整碳微晶含量高达90.89%,理想石墨微晶含量IG/IAll为18%)。

     

    Abstract: Binder pitch was recognized as one of the important raw materials for the production of carbon/graphite electrode and anode of lithium-ion battery. The quality and application of carbon/graphite products was generally determined by the properties of the binder pitch. Thus, the high-quality binder pitch act a key role on the quality of carbon/graphite materials. In this work, the refined medium pitch was used as role material, the effects of modification methods on the properties of binder pitch (molecular structure, thermal-stability and the optical microstructure of pitch) and coking properties (optical microstructure of pitch coke, carbon microcrystalline structure and carbon surface morphology of pitch carbon, etc.) were detailed studied. The research results show that, the high-quality isotropic binder pitch (with softening point of 144 ℃, QI content of 0.46%, TI content of 26.74%, coking value of 51.53%, volatile matter of 56.65%) was obtained by two-step method, named oxidation polymerization- mild thermal polymerization method (first step: refined pitch was oxidized at temperature of 280 ℃ for 3 hours; second step: rapidly heated to the temperature of 360 ℃ and hold for 1 hour under N2 atmosphere). The degree of aromatic condensation of the binder pitch was high and have fewer small molecule branched structures. The optical microstructure of the binder pitch coke obtained by thermal conversion and carbonization treatment had a leaflet and fibrous structure content of 83.92%. The disorder degree of the binder pitch coke was relatively low, and the microcrystalline structure was regular and orderly (the content of carbon microcrystals tends to be regular was as high as 90.89%, and the ideal graphite microcrystal content IG/IAll was 18%).

     

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