郭天瑞, 陈荣起, 高伟, 王艳莉, 詹亮. 由乙烯焦油制备锂离子电池负极材料用碳质前驱体的氧化反应机理与反应动力学[J]. 新型炭材料, 2024, 39(2): 354-366. DOI: 10.1016/S1872-5805(22)60597-3
引用本文: 郭天瑞, 陈荣起, 高伟, 王艳莉, 詹亮. 由乙烯焦油制备锂离子电池负极材料用碳质前驱体的氧化反应机理与反应动力学[J]. 新型炭材料, 2024, 39(2): 354-366. DOI: 10.1016/S1872-5805(22)60597-3
GUO Tian-rui, CHEN Rong-qi, GAO Wei, WANG Yan-li, ZHAN Liang. The oxidation reaction mechanism and its kinetics for a carbonaceous precursor prepared from ethylene tar for use as an anode material for lithium-ion batteries[J]. New Carbon Mater., 2024, 39(2): 354-366. DOI: 10.1016/S1872-5805(22)60597-3
Citation: GUO Tian-rui, CHEN Rong-qi, GAO Wei, WANG Yan-li, ZHAN Liang. The oxidation reaction mechanism and its kinetics for a carbonaceous precursor prepared from ethylene tar for use as an anode material for lithium-ion batteries[J]. New Carbon Mater., 2024, 39(2): 354-366. DOI: 10.1016/S1872-5805(22)60597-3

由乙烯焦油制备锂离子电池负极材料用碳质前驱体的氧化反应机理与反应动力学

The oxidation reaction mechanism and its kinetics for a carbonaceous precursor prepared from ethylene tar for use as an anode material for lithium-ion batteries

  • 摘要: 为了得到优质的碳质前驱体,研究了乙烯焦油在空气中的氧化反应机理及其反应动力学,并制备出高软化点沥青应用于锂离子电池负极石墨材料的包覆改性。根据热重曲线将乙烯焦油的氧化过程分成350−550、550−700和700−900 K三个阶段,并采用质谱和红外技术对不同反应温度下的尾气成份进行在线分析以揭示乙烯焦油在空气中的氧化反应机理。根据不同反应温度下乙烯焦油与氧气的热失重曲线,整个反应过程被分为4个阶段,进一步利用Coats-Redfern等转化率法分析17种常用反应动力学模型与实验数据的拟合度,筛选出最适宜表达乙烯焦油与氧气的反应动力学模型。结果表明:(1)在乙烯焦油的氧化过程中,芳香化合物的支链先与氧气反应生成醇类、醛类小分子化合物和含有过氧自由基的芳香化合物,然后含有过氧自由基的芳香化合物进行热缩聚反应形成分子量更大的芳香族化合物;(2)可采用四级反应模型描述乙烯焦油的前3阶段反应动力学,活化能分别为47.33、18.69和9.00 kJ·mol−1;可采用三维扩散模型描述第4阶段的反应动力学,其活化能为88.37 kJ·mol−1。(3)经所制沥青包覆改性后,石墨负极循环300圈后的容量保持率由51.54%增长为79.07%。

     

    Abstract: The oxidation reaction mechanism and its kinetics for ethylene tar were investigated in order to obtain a suitable anode material for Li-ion batteries. The oxidation of ethylene tar was divided into 3 stages (350–550, 550–700 and 700–900 K) according to the thermogravimetric curve. To reveal the oxidation reaction mechanism, the components of the gases evolved at different stages were analyzed by mass spectrometry and infrared technology. Based on these results the reaction was divided into 4 stages (323–400, 400–605, 605–750 and 750–860 K) to perform simulation calculations of the kinetics. Using the iso-conversion method (Coats-Redfern) to analyze the linear regression rates (R2) between 17 common reaction kinetics models and experimental data, an optimum reaction kinetics model for expressing the oxidation of ethylene tar was determined and the results were as follows. (1) During oxidation, the side chains of aromatic compounds first react with oxygen to form alcohols and aldehydes, leaving peroxy-radicals on aromatic rings. Subsequently, the aromatic compounds with peroxy-radicals undergo polymerization/condensation reactions to form larger molecules. (2) A fourth-order reaction model was used to describe the first 3 stages in the oxidation process, and the activation energies are 47.33, 18.69 and 9.00 kJ·mol1 at 323–400, 400–605, 605–750 K, respectively. A three-dimensional diffusion model was applied to the fourth stage of the oxidation process, and the activation energy is 88.37 kJ·mol1 at 750–860 K. A high softening point pitch was also produced for use as a coating of the graphite anode, and after it had been applied the capacity retention after 300 cycles increased from 51.54% to 79.07%.

     

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