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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

GUO Tian-rui CHEN Rong-qi GAO Wei WANG Yan-li ZHAN Liang

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. 新型炭材料(中英文), 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. 新型炭材料(中英文), 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. 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. 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

doi: 10.1016/S1872-5805(22)60597-3
基金项目: 国家自然科学基金(51472086、51002051、U1710252、50730003、50672025、20806024、22075081)
详细信息
    通讯作者:

    詹 亮, 教授. E-mail:zhanliang@ecust.edu.cn

  • 中图分类号: TQ152

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

Funds: This work was financially supported by the National Natural Science Foundation of China (51472086, 51002051, U1710252, 50730003, 50672025, 20806024 and 22075081)
More Information
  • 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%。
  • FIG. 3070.  FIG. 3070.

    FIG. 3070..  FIG. 3070.

    Figure  1.  (a) GC-MS and (b) LDI TOF/MS spectrogram of ET-HR

    Figure  2.  (a) TG, (b) DTG and DSC curves of ET-HR

    Figure  3.  (a) Ion current intensity of various mass units in the temperature range from 300 to 900 K. (b-d) Mass spectra

    Figure  4.  Possible reactions to generate H2

    Figure  5.  Possible reactions to generate CH4, H2O, and HCHO

    Figure  6.  Possible reactions to generate CH3CHO and CO2

    Figure  7.  (a) 3D FTIR spectra of evolved gaseous products from oxidation process of ET-HR. (b) FTIR spectrum of evolved gases recorded at 450 K

    Figure  8.  (a) Function of ln[G(a)/T2] with respect to 1/T for the first part of oxidation. (b) The second part of oxidation. (c) The third part of oxidation. (d) The fourth part of oxidation

    Figure  9.  SEM images of (a) NG and (b) ETP@NG

    Figure  10.  (a) XRD patterns of NG and ETP@NG and (b) Partial enlarged view of the XRD patterns

    Figure  11.  Long cycle performance of NG and ETP@NG

    Table  1.   A series of frequently-used mechanism models defining G(α)[33-34]

    MechanismsSymbol$ f\left(\alpha \right) $$ G\left(\alpha \right) $
    Order of reactionFirst order$ {\mathrm{F}}_{1} $$ 1-\alpha $$ -\mathrm{l}\mathrm{n}\left(1-\alpha \right) $
    Second order$ {\mathrm{F}}_{2} $$ {\left(1-\alpha \right)}^{2} $$ {\left(1-\alpha \right)}^{-1}-1 $
    Third order$ {\mathrm{F}}_{3} $$ {\left(1-\alpha \right)}^{3} $$ \left[{\left(1-\alpha \right)}^{-2}-1\right]/2 $
    Fourth order$ {\mathrm{F}}_{4} $$ {\left(1-\alpha \right)}^{4} $$ \left[{\left(1-\alpha \right)}^{-3}-1\right]/3 $
    DiffusionOne-way transport$ {\mathrm{D}}_{1} $$ 0.5\alpha $$ {\alpha }^{2} $
    Two-way transport$ {\mathrm{D}}_{2} $$ {\left[-\mathrm{l}\mathrm{n}\left(1-\alpha \right)\right]}^{-1} $$ \alpha +\left(1-\alpha \right)\mathrm{l}\mathrm{n}\left(1-\alpha \right) $
    Three-way transport$ {\mathrm{D}}_{3} $$ 1.5{\left(1-\alpha \right)}^{2/3}{\left[1-{\left(1-\alpha \right)}^{1/3}\right]}^{-1} $$ {\left[1-{\left(1-\alpha \right)}^{1/3}\right]}^{2} $
    Contracting geometryContracting cylinder$ {\mathrm{R}}_{2} $$ 2{\left(1-\alpha \right)}^{1/2} $$ 1-{\left(1-\alpha \right)}^{1/2} $
    Contracting sphere$ {\mathrm{R}}_{3} $$ 3{\left(1-\alpha \right)}^{2/3} $$ 1-{\left(1-\alpha \right)}^{1/3} $
    Random nucleation and nuclei growthAvrami-Erofeev$ {\mathrm{A}}_{3/2} $$ 1.5\left(1-\alpha \right){\left[-\mathrm{l}\mathrm{n}\left(1-\alpha \right)\right]}^{1/3} $$ {\left[-\mathrm{l}\mathrm{n}\left(1-\alpha \right)\right]}^{3/2} $
    Avrami-Erofeev$ {\mathrm{A}}_{2} $$ 2\left(1-\alpha \right){\left[-\mathrm{l}\mathrm{n}\left(1-\alpha \right)\right]}^{1/2} $$ {\left[-\mathrm{l}\mathrm{n}\left(1-\alpha \right)\right]}^{1/2} $
    Avrami-Erofeev$ {\mathrm{A}}_{3} $$ 3\left(1-\alpha \right){\left[-\mathrm{l}\mathrm{n}\left(1-\alpha \right)\right]}^{2/3} $$ {\left[-\mathrm{l}\mathrm{n}\left(1-\alpha \right)\right]}^{1/3} $
    Avrami-Erofeev$ {\mathrm{A}}_{4} $$ 4\left(1-\alpha \right){\left[-\mathrm{l}\mathrm{n}\left(1-\alpha \right)\right]}^{3/4} $$ {\left[-\mathrm{l}\mathrm{n}\left(1-\alpha \right)\right]}^{1/4} $
    Exponential nucleationPower law$ {\mathrm{P}}_{3/2} $$ 2/3{\alpha }^{-1/2} $$ {\alpha }^{2/3} $
    Power law$ {\mathrm{P}}_{2} $$ 2{\alpha }^{1/2} $$ {\alpha }^{1/2} $
    Power law$ {\mathrm{P}}_{3} $$ 3{\alpha }^{2/3} $$ {\alpha }^{1/3} $
    Power law$ {\mathrm{P}}_{4} $$ 4{\alpha }^{3/4} $$ {\alpha }^{1/4} $
    下载: 导出CSV

    Table  2.   The fundamental properties of ethylene tar and ET-HR

    Elemental analysis/%2C/H3TS/%Four components8SO/°C9CV/%
    CHNS1O4S5Ar6R7As
    ET92.2807.32400.0270.3691.0501005.63390.5013.4230.443<257.740
    ET-HR92.8206.86900.0220.2891.130100091.9117.1620.927<2514.10
    Note: 1SO: By difference. 2C/H: Atomic ratio. 3TS: Toluene soluble components. 4S: Saturated fraction. 5Ar: Aromatic fraction. 6R: Resin. 7As: Asphaltene. 8SP: Softening point. 9CV: Coking value.
    下载: 导出CSV

    Table  3.   Possible compounds distinguished by GC-MS in ET-HR

    Peak No.Names or typesRetention time/minArea percentage/%
    1(Z)-1-Phenylpropene8.1402.689
    2Indene9.0156.919
    3Naphthalene,1,2-dihydro-10.7083.874
    4Cycloprop[a]indene,1,1a,6,6a-tetrahydro-10.7983.095
    5Benzene, (1-methylene-2-propenyl)-10.9401.143
    6Naphthalene11.33242.252
    7Benzocycloheptatriene12.90912.971
    8Benzocycloheptatriene13.1548.688
    9Naphthalene,2-ethenyl-14.0232.430
    10Naphthalene,2-ethyl-14.2221.167
    11Naphthalene, 1-ethyl-14.2740.844
    12Naphthalene,1,6-dimethyl-14.5701.651
    13Naphthalene,2-ethenyl-14.6991.066
    14Biphenylene14.9821.395
    151,1’-Biphenyl,4-methyl-15.3740.970
    16Naphthalene,2-ethenyl-15.4261.780
    17Fluorene16.6301.987
    18Phenanthrene18.8954.355
    19Anthracene18.9850.724
    下载: 导出CSV

    Table  4.   Evolved gases analysis

    Fragment Molecular formulaMolecule
    2H2Hydrogen
    16CH4Methane
    18H2OWater
    26C2H2Acetylene
    28C2H4Ethylene
    30HCHOFormaldehyde
    44CH3CHO/CO2Acetaldehyde/carbon dioxide
    64SO2Sulfur dioxide
    128C10H8Naphthalene
    下载: 导出CSV

    Table  5.   Linear regression rates (R2) of different models of 4 parts in the process of oxidation

    Model${ {R}^{2} }_{{\rm{stage}}1}$(323-400 K)${ {R}^{2} }_{{\rm{stage}}2}$(400-605 K)${ {R}^{2} }_{{\rm{stage}}3}$(605-750 K)${ {R}^{2} }_{{\rm{stage}}4}$(750-860 K)
    $ {\mathrm{F}}_{1} $ 0.99195 0.92258 NA 0.96740
    $ {\mathrm{F}}_{2} $ 0.99372 0.97629 NA 0.91237
    $ {\mathrm{F}}_{3} $ 0.99525 0.98949 0.77979 0.89775
    $ {\mathrm{F}}_{4} $ 0.99653 0.99102 0.92887 0.89578
    $ {\mathrm{D}}_{1} $ 0.99152 0.9389 NA 0.94713
    $ {\mathrm{D}}_{2} $ 0.99211 0.95419 NA 0.97933
    $ {\mathrm{D}}_{3} $ 0.99268 0.9667 NA 0.98793
    $ {\mathrm{R}}_{2} $ 0.99097 0.85181 NA 0.98390
    $ {\mathrm{R}}_{3} $ 0.99131 0.88105 NA 0.98385
    $ {\mathrm{A}}_{3/2} $ 0.99283 0.96561 NA 0.97099
    $ {\mathrm{A}}_{2} $ 0.98835 NA NA 0.95101
    $ {\mathrm{A}}_{3} $ 0.98236 NA NA 0.91699
    $ {\mathrm{A}}_{4} $ 0.97154 NA NA 0.82846
    $ {\mathrm{P}}_{3/2} $ 0.99103 0.90477 NA 0.92539
    $ {\mathrm{P}}_{2} $ 0.99103 0.90477 NA 0.92539
    $ {\mathrm{P}}_{3} $ 0.97785 NA NA NA
    $ {\mathrm{P}}_{4} $ 0.96399 NA NA NA
    下载: 导出CSV

    Table  6.   Oxidation kinetics parameters of ET-HR

    Reaction sectionModel$ k $$ b $${E}_{ {\rm{a} } }({\rm{kJ} } \cdot { {\rm{mol} } }^{-1})$$A({ {\rm{min} } }^{-1})$$ {R}^{2} $
    ET-HRpart 1$ {\mathrm{F}}_{4} $−5692.779280.8493947329.7669366554.854760.99653
    ET-HRpart 2$ {\mathrm{F}}_{4} $−2247.94165−7.7402818689.386884.8887085420.99102
    ET-HRpart 3$ {\mathrm{F}}_{4} $−1083.02397−9.463549004.2612870.4203827350.92887
    ET-HRpart 4$ {\mathrm{D}}_{3} $−10628.96641−1.5121588369.2267311715.009310.98793
    下载: 导出CSV
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  • 收稿日期:  2021-08-30
  • 修回日期:  2021-11-04
  • 网络出版日期:  2022-01-05
  • 刊出日期:  2024-04-20

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