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二氯甲烷和甲苯对咪唑离子液体结构和性质及铝电沉积的影响

田国才 袁青香

田国才, 袁青香. 二氯甲烷和甲苯对咪唑离子液体结构和性质及铝电沉积的影响[J]. 工程科学学报, 2021, 43(8): 1037-1046. doi: 10.13374/j.issn2095-9389.2020.12.03.002
引用本文: 田国才, 袁青香. 二氯甲烷和甲苯对咪唑离子液体结构和性质及铝电沉积的影响[J]. 工程科学学报, 2021, 43(8): 1037-1046. doi: 10.13374/j.issn2095-9389.2020.12.03.002
TIAN Guo-cai, YUAN Qing-xiang. Effect of dichloromethane and toluene on the structure, property, and Al electrodeposition in 1-butyl-3-methylimidazolium chloroaluminate ionic liquid[J]. Chinese Journal of Engineering, 2021, 43(8): 1037-1046. doi: 10.13374/j.issn2095-9389.2020.12.03.002
Citation: TIAN Guo-cai, YUAN Qing-xiang. Effect of dichloromethane and toluene on the structure, property, and Al electrodeposition in 1-butyl-3-methylimidazolium chloroaluminate ionic liquid[J]. Chinese Journal of Engineering, 2021, 43(8): 1037-1046. doi: 10.13374/j.issn2095-9389.2020.12.03.002

二氯甲烷和甲苯对咪唑离子液体结构和性质及铝电沉积的影响

doi: 10.13374/j.issn2095-9389.2020.12.03.002
基金项目: 国家自然科学基金资助项目(51774158,51264021);云南省中青年学术技术带头人后备人才培养资助项目(2011CI013)
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    E-mail:tiangc01@163.com

  • 中图分类号: TF821

Effect of dichloromethane and toluene on the structure, property, and Al electrodeposition in 1-butyl-3-methylimidazolium chloroaluminate ionic liquid

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  • 摘要: 离子液体电沉积铝技术具有广阔的应用前景,而添加剂是提高铝镀层性能的有效方法,但相关作用机制还有待明确。本文应用量子化学和分子动力学模拟研究了二氯甲烷(DCM)和甲苯(C7H8)对氯化-1-丁基-3-甲基咪唑/三氯化铝([BMIM]Cl/AlCl3)体系的微观结构、物理化学性质和铝电沉积的影响。发现DCM易与阴、阳离子形成氢键,分布在阴阳离子之间使得阴阳离子间距离增加、相互作用能减小, 导致阴阳离子扩散能力增强、铝配离子更倾向以${\rm{A}}{{\rm{l}}_2}{\rm{Cl}}_7^ -$形式存在,体系黏度降低电导率增加,因而对体系电化学性质提升很大,而且DCM起到了晶粒细化和整平作用,从而可以得到镜面光亮的沉积层,所得结果与实验值吻合较好。C7H8主要分布在阳离子周围,与阳离子有较强相互作用,在沉积过程中吸附于电极表面的凸出部分,抑制了电活性离子的还原而主要起到整平作用,其对阴离子和阳离子之间的相关作用的影响比DCM小,因而体系电化学性质提升不如DCM。

     

  • 图  1  模拟用到的阳离子和分子的结构以及相应原子的类型。(a)[BMIM]+;(b)AlCl3;(c)C7H8;(d)DCM

    Figure  1.  Structure of the molecules and cation, and the corresponding atom types: (a) [BMIM]+; (b) AlCl3; (c) C7H8; (d) DCM

    图  2  B3LYP/6-311++G(d,p)方法得到的离子液体与添加剂作用的稳定构型。(a)[BMIM]Al2Cl7/DCM;(b)[BMIM]Al2Cl7/C7H8

    Figure  2.  Stable structures of [BMIM]Al2Cl7 with additives and with B3LYP/6-311++G(d,p) method: (a) [BMIM]Al2Cl7/DCM; (b) [BMIM]Al2Cl7/C7H8

    图  3  B3LYP/6-311++G(d,p)方法得到的前线轨道图。(a)[BMIM]Al2Cl7;(b)C7H8;(c)DCM;(d)[BMIM]Al2Cl7/DCM;(e)[BMIM]Al2Cl7/C7H8

    Figure  3.  Frontier orbital distribution from B3LYP/6-311++G(d,p) method: (a) [BMIM]Al2Cl7; (b) C7H8; (c) DCM; (d) [BMIM]Al2Cl7/DCM; (e) [BMIM]Al2Cl7/DCM

    图  4  MD模拟计算得到体系中离子间的径向分布函数gA-B(r)。(a)[BMIM]+${\rm{Al}}_{x} {\rm{Cl}}_y^{3x-y} $;(b)${\rm{Al}}_{x} {\rm{Cl}}_y^{3x-y} $与Cl;(c)[BMIM]+与M(M=DCM、C7H8);(d)${\rm{Al}}_{x} {\rm{Cl}}_y^{3x-y} $与M(M=DCM、C7H8)

    Figure  4.  Calculated radial distribution functions gA-B(r) for particle A and B from MD simulation: (a) [BMIM]+-${\rm{Al}}_{x} {\rm{Cl}}_y^{3x-y} $; (b) ${\rm{Al}}_{x} {\rm{Cl}}_y^{3x-y} $-Cl; (c) [BMIM]+-M(M = DCM, C7H8); (d) ${\rm{Al}}_{x} {\rm{Cl}}_y^{3x-y} $-M(M = DCM、C7H8)

    图  5  计算得到的三维空间分布图。(a)[BMIM]+周围Cl(绿色)、C7H8(黄色)、DCM(红色)、${\rm{Al}}_{x} {\rm{Cl}}_y^{3x-y} $(蓝色)的三维空间分布;(b)${\rm{Al}}_{x} {\rm{Cl}}_y^{3x-y} $周围Cl(绿色)、DCM(红色)、C7H8(黄色)空间分布

    Figure  5.  Spatial distribution from simulation: (a) Cl (green), ${\rm{Al}}_{x} {\rm{Cl}}_y^{3x-y} $ (blue), DCM (red), and C7H8 (yellow) around the [BMIM]+; (b) Cl (green), DCM (red), C7H8 (yellow) around ${\rm{Al}}_{x} {\rm{Cl}}_y^{3x-y} $

    图  6  DCM和C7H8对体系中各粒子均方根位移(MSD)和扩散系数的影响。(a)[BMIM]+的MSD;(b)${\rm{Al}}_{x} {\rm{Cl}}_y^{3x-y} $的MSD;(c)DCM和C7H8的MSD; (d) 各粒子的扩散系数

    Figure  6.  Effects of DCM and C7H8 on the root-mean-square displacement MSD and diffusion coefficient of particles: (a) MSD of [BMIM]+; (b) MSD of ${\rm{Al}}_{x} {\rm{Cl}}_y^{3x-y} $; (c) MSD of DCM and C7H8; (d) diffusion coefficient

    表  1  B3LYP/6-311++G(d,p)方法得到的体系中各粒子间的相互作用能

    Table  1.   Interaction energy in the system with B3LYP/6-311++G(d,p) method

    MInteraction energy/(kJ·mol−1)
    [BMIM]+ and M${\rm{A}}{{\rm{l}}_2}{\rm{Cl}}_7^ - $ and M[BMIM]+M and ${\rm{A}}{{\rm{l}}_2}{\rm{Cl}}_7^ - $
    C7H8−27.69−7.27−260.76
    DCM−22.29−21.28−267.99
    下载: 导出CSV

    表  2  B3LYP/6-311++G(d,p)方法得到的体系的相关量化参数

    Table  2.   Quantitative parameters of the system from B3LYP/6-311++G(d,p) method

    Typeμ/
    (10−30 ℃·m)
    EHOMO/
    eV
    ELUMO/
    eV
    ΔE/
    eV
    χ/
    eV
    C7H81.343−9.9132−4.85845.05487.3858
    DCM6.081−8.5991−0.90647.69274.7528
    [BMIM]Al2Cl751.152−8.0239−1.97186.05214.9978
    [BMIM]Al2Cl7/C7H849.127−9.3491−4.87254.47667.1108
    [BMIM]Al2Cl7/DCM44.482−8.1412−1.91956.22175.0303
    下载: 导出CSV

    表  3  计算所得体系中主要粒子的配位数

    Table  3.   Calculated coordination number of the main particles in the system

    Type${\rm{C}}{{\rm{N}}_{({\rm{A}}{{\rm{l}}_x}{\rm{Cl}}_y^{3x - y} - {\rm{C}}{{\rm{l}}^ - })}}$${\rm{C}}{{\rm{N}}_{({{[{\rm{BMIM}}]}^ + } - {\rm{A}}{{\rm{l}}_x}{\rm{Cl}}_y^{3x - y})}}$
    [BMIM]Cl/AlCl30.992.88
    [BMIM]Cl/AlCl3/C7H80.851.81
    [BMIM]Cl/AlCl3/DCM0.681.54
    下载: 导出CSV

    表  4  计算得到的303.14 K和0.1 MPa下体系的黏度(η)与电导率(κ)

    Table  4.   Viscosity (η) and conductivity (κ) of the system from MD simulation at 303.14 K and 0.1 MPa

    Typeη/(mPa·s)κ/(mS·cm−1)
    [BMIM]Cl/AlCl3/C7H811.617.59
    [BMIM]Cl/AlCl3/DCM2.4848.55
    下载: 导出CSV
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