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

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

田国才^{1, 2, ,},
袁青香²

1.
昆明理工大学省部共建复杂有色金属资源清洁利用国家重点实验室，昆明 650093
2.
昆明理工大学冶金与能源工程学院，昆明 650093

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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通讯作者:
E-mail：tiangc01@163.com

中图分类号: TF821
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出版历程
- 收稿日期: 2020-12-03
- 网络出版日期: 2021-03-01
- 刊出日期: 2021-08-25

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

TIAN Guo-cai^{1, 2
, ,},
YUAN Qing-xiang²

1.
State Key Laboratory of Complex Non-ferrous Metal Resources Clean Utilization, Kunming University of Science and Technology, Kunming 650093, China
2.
Faculty of Metallurgical and Energy Engineering, Kunming University of Science and Technology, Kunming 650093, China

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Corresponding author: E-mail: tiangc01@163.com

摘要

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。
- 离子液体 /
- 铝电沉积 /
- 添加剂 /
- 二氯甲烷 /
- 甲苯 /
- 第一性原理 /
- 分子动力学
Abstract: The electrodeposition of aluminum in ionic liquid has broad application prospects, and additives are an effective way to improve the performance of the aluminum coating. However, the relevant mechanism behind this remains to be clarified. In the present work, the effects of dichloromethane (DCM) and toluene (C₇H₈) on the microstructure, physicochemical properties, and aluminum electrodeposition with 1-butyl-3-methylimidazolium chloride/aluminum chloride ([BMIM]Cl/AlCl₃) were studied using quantum chemistry and molecular dynamics simulation. It is found that DCM easily forms hydrogen bonds with anions and cations of ionic liquids. Since DCM is distributed between anion and cation, the distance between the anion and cation increases, and the interaction energy decreases. As a result, the diffusion ability of anions and cations is enhanced, and the aluminum complex anions tend to exist in the form of ${\rm{A}}{{\rm{l}}_2}{\rm{Cl}}_7^ - $. The viscosity of the system decreases, and the conductivity increases, so the electrochemical properties of the system are significantly improved, which are in good agreement with the experimental values. C₇H₈ is adsorbed on the protruding part of the electrode surface in a flat way, which plays a leveling role and results in a flat white coating. Alternatively, DCM easily interacts with the electroactive ion ${\rm{A}}{{\rm{l}}_2}{\rm{Cl}}_7^ - $, which makes it difficult to reduce this electroactive ion. At the same time, the concentration of the electroactive ion decreases as the concentration of the additive is increased, which leads to a large overpotential in the electrochemical process, resulting in a decrease in the electrode reaction rate that plays a role in grain refinement. Moreover, the interaction between DCM and cations is also strong, and they can be adsorbed on the protruding part of the electrode surface during the electrochemical process, playing a certain leveling role. Therefore, the addition of DCM can obtain specular gloss deposits. The effect of C₇H₈ on the interaction between anions and cations is not as good as DCM, which consequently results in inferior electrochemical properties compared to DCM. Therefore, DCM is more favorable for the electrodeposition of aluminum than the aromatic hydrocarbon C₇H_8.
- ionic liquids /
- aluminum electrodeposition /
- additives /
- dichloromethane /
- toluene /
- first principles /
- molecular dynamics

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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

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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

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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

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图 4 MD模拟计算得到体系中离子间的径向分布函数g_A-B(r)。（a）[BMIM]⁺与${\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 g_A-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)

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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} $

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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

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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

M	Interaction energy/(kJ·mol⁻¹)
M	[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

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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

Type	μ/ (10⁻³⁰ ℃·m)	E_HOMO/ eV	E_LUMO/ eV	ΔE/ eV	χ/ eV
C₇H₈	1.343	−9.9132	−4.8584	5.0548	7.3858
DCM	6.081	−8.5991	−0.9064	7.6927	4.7528
[BMIM]Al₂Cl₇	51.152	−8.0239	−1.9718	6.0521	4.9978
[BMIM]Al₂Cl₇/C₇H₈	49.127	−9.3491	−4.8725	4.4766	7.1108
[BMIM]Al₂Cl₇/DCM	44.482	−8.1412	−1.9195	6.2217	5.0303

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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/AlCl₃	0.99	2.88
[BMIM]Cl/AlCl₃/C₇H₈	0.85	1.81
[BMIM]Cl/AlCl₃/DCM	0.68	1.54

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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

Type	η/(mPa·s)	κ/(mS·cm⁻¹)
[BMIM]Cl/AlCl₃/C₇H₈	11.61	7.59
[BMIM]Cl/AlCl₃/DCM	2.48	48.55

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参考文献(45)

[1]	Qiu Z X. World aluminum industry and development trend of new technology. Non Ferr Smelt, 2000, 29(2): 1 邱竹贤. 世界铝工业与新技术发展趋势. 有色冶炼, 2000, 29(2):1
[2]	Liu Y X, Li J. Modern Aluminum Electrolysis. Beijing: Metallurgical Industry Press, 2008 刘业翔, 李劼. 现代铝电解. 北京: 冶金工业出版社, 2008
[3]	Kan H M, Qiu Z X, Zhang G. Low Temperature Aluminum Electrolysis. Shenyang: Northeast University Press, 2009 阚洪敏, 邱竹贤, 张刚. 低温铝电解. 沈阳: 东北大学出版社, 2009
[4]	Lu H M, Qiu Z X. Research progress of low temperature aluminum electrolysis. Light Met, 1997(4): 24 卢惠民, 邱竹贤. 低温铝电解的研究进展. 轻金属, 1997(4):24
[5]	Deng Y Q. Ionic liquids —— Properties, Preparation and Application. Beijing: China Petrochemical Press, 2006 邓友全. 离子液体——性质, 制备与应用. 北京: 中国石化出版社, 2006
[6]	Zhang S J, LÜ X M. Ionic liquids: From Basic Research to Industrial Application. Beijing: Science Press, 2006 张锁江, 吕兴梅. 离子液体: 从基础研究到工业应用. 北京: 科学出版社, 2006
[7]	Wasserscheid P, Welton T. Ionic Liquids in Synthesis. New Jersey: John Wiley & Sons, 2008
[8]	Zhang M M, Kamavarum V, Reddy R G. New electrolytes for aluminum production: Ionic liquids. JOM, 2003, 55(11): 54 doi: 10.1007/s11837-003-0211-y
[9]	Tian G C, Li J, Hua Y X. Application of ionic liquids in metallurgy of nonferrous metals. Chin J Process Eng, 2009, 9(1): 200 doi: 10.3321/j.issn:1009-606X.2009.01.039 田国才, 李坚, 华一新. 离子液体在有色金属冶金中的应用. 过程工程学报, 2009, 9(1):200 doi: 10.3321/j.issn:1009-606X.2009.01.039
[10]	Tian G C, Li J, Hua Y X. Application of ionic liquids in hydrometallurgy of nonferrous metals. Trans Nonferrous Met Soc China, 2010, 20(3): 513 doi: 10.1016/S1003-6326(09)60171-0
[11]	Mohammad A, Inamuddin D. Green Solvents II: Properties and Applications of Ionic Liquids//Tian G C. Application of ionic liquids in extraction and separation of metals. Berlin: Springer Netherlands, 2012: 119
[12]	Tian G C. Ionic liquids as green electrolytes for aluminum and aluminum-alloy production. Mater Res Found, 2019, 54: 249
[13]	Zhong X W, Xiong T, Lu J, et al. Advances of electro-deposition and aluminum refining of aluminum and aluminum alloy in ionic liquid electrolytes system. Nonferrous Met Sci Eng, 2014, 5(2): 44 钟熊伟, 熊婷, 陆俊, 等. 离子液体电解质体系铝及铝合金电沉积与铝精炼研究进展. 有色金属科学与工程, 2014, 5(2):44
[14]	Liu Q S, Xue J L, Zhu J, et al. Effects of additives on the sodium penetration and expansion of carbon-based cathodes during aluminum electrolysis. J Univ Sci Technol Beijing, 2008, 30(4): 403 doi: 10.3321/j.issn:1001-053X.2008.04.015 刘庆生, 薛济来, 朱骏, 等. 添加剂对铝电解炭基阴极钠渗透膨胀过程的影响. 北京科技大学学报, 2008, 30(4):403 doi: 10.3321/j.issn:1001-053X.2008.04.015
[15]	Zheng Y, Wang Q, Zheng Y J, et al. Advances in research and application of aluminium electrolysis in ionic liquid systems. Chin J Process Eng, 2015, 15(4): 713 doi: 10.12034/j.issn.1009-606X.215194 郑勇, 王倩, 郑永军, 等. 离子液体体系电解铝技术的研究与应用进展. 过程工程学报, 2015, 15(4):713 doi: 10.12034/j.issn.1009-606X.215194
[16]	Fleury V, Kaufman J H, Hibbert D B. Mechanism of a morphology transition in ramified electrochemical growth. Nature, 1994, 367(6462): 435 doi: 10.1038/367435a0
[17]	Yue G K, Lu X M, Zhu Y L, et al. Surface morphology, crystal structure and orientation of aluminium coatings electrodeposited on mild steel in ionic liquid. Chem Eng J, 2009, 147(1): 79 doi: 10.1016/j.cej.2008.11.044
[18]	Abbott A P, Qiu F, Abood H M, et al. Double layer, diluent and anode effects upon the electrodeposition of aluminium from chloroaluminate based ionic liquids. Phys Chem Chem Phys, 2010, 12(8): 1862 doi: 10.1039/B917351J
[19]	Liu L, Lu X M, Cai Y J, et al. Influence of additives on the speciation, morphology, and nanocrystallinity of aluminium electrodeposition. Aust J Chem, 2012, 65(11): 1523 doi: 10.1071/CH12305
[20]	Ueda M, Hariyama S, Ohtsuka T. Al electroplating on the AZ121 Mg alloy in an EMIC-AlCl₃ ionic liquid containing ethylene glycol. J Solid State Electrochem, 2012, 16(11): 3423 doi: 10.1007/s10008-012-1801-9
[21]	Zhang Q Q, Wang Q, Zhang S J, et al. Effect of nicotinamide on electrodeposition of Al from aluminium chloride (AlCl₃)-1-butyl-3-methylimidazolium chloride ([Bmim]Cl) ionic liquids. J Solid State Electrochem, 2014, 18(1): 257 doi: 10.1007/s10008-013-2269-y
[22]	Wang Q, Zhang Q Q, Chen B, et al. Electrodeposition of bright Al coatings from 1-butyl-3-methylimidazolium chloroaluminate ionic liquids with specific additives. J Electrochem Soc, 2015, 162(8): D320 doi: 10.1149/2.1001507jes
[23]	Wang Q, Chen B, Zhang Q Q, et al. Aluminum deposition from lewis acidic 1-butyl-3-methylimidazolium chloroaluminate ionic liquid ([Bmim]Cl/AlCl₃) modified with methyl nicotinate. Chem Electro Chem, 2015, 2(11): 1794
[24]	Sheng P F, Chen B, Shao H B, et al. Electrodeposition and corrosion behavior of nanocrystalline aluminum from a chloroaluminate ionic liquid. Mater Corros, 2015, 66(11): 1338 doi: 10.1002/maco.201508272
[25]	Leng M H. Study on Morphology of Electrodeposition of Aluminum from Ionic Liquid [Dissertation]. Shenyang: Shenyang Normal University, 2015 冷明浩. 离子液体电沉积铝微观形貌研究[学位论文]. 沈阳: 沈阳师范大学, 2015
[26]	Li Z T, Tian G C. Simulation study of the effect of benzene on the structure and properties of 1-ethyl-3-methylimidazolium chloroaluminate. Comput Appl Chem, 2015, 32(9): 1044 李志涛, 田国才. 苯对1-乙基-3-甲基咪唑三氯化铝结构与性质影响的模拟研究. 计算机与应用化学, 2015, 32(9):1044
[27]	Lang H Y, Zhang J L, Kang Y H, et al. Effects of lithium bis (oxalato) borate on electrochemical stability of [Emim][Al₂Cl₇] ionic liquid for aluminum electrolysis. Ionics, 2017, 23(4): 959 doi: 10.1007/s11581-016-1889-5
[28]	Abbott A P, McKenzie K J. Application of ionic liquids to the electrodeposition of metals. Phys Chem Chem Phys, 2006, 8(37): 4265 doi: 10.1039/b607329h
[29]	Robinson J, Osteryoung R A. An electrochemical and spectroscopic study of some aromatic hydrocarbons in the room temperature molten salt system aluminum chloride-n-butylpyridinium chloride. J Am Chem Soc, 1979, 101(2): 323 doi: 10.1021/ja00496a008
[30]	Pulletikurthi G, Bödecker B, Borodin A, et al. Electrodeposition of Al from a 1-butylpyrrolidine-AlCl₃ ionic liquid. Prog Nat Sci:Mater Int, 2015, 25(6): 603 doi: 10.1016/j.pnsc.2015.11.003
[31]	Uehara K, Yamazaki K, Gunji T K, et al. Evaluation of key factors for preparing high brightness surfaces of aluminum films electrodeposited from AlCl₃-1-ethyl-3-methylimidazolium chloride-organic additive baths. Electrochimica Acta, 2016, 215: 556 doi: 10.1016/j.electacta.2016.08.125
[32]	Kang Y H, Chen S M, Wang Q, et al. Solvation effect of [BMIM]Cl/AlCl₃ ionic liquid electrolyte. Ionics, 2019, 25(1): 163 doi: 10.1007/s11581-018-2586-3
[33]	Frisch M J, Trucks G W, Schlegel H B, et al. Gaussian 09, Revision D. 01 [CP/OL]. Gaussian, Inc. (2009)[2020-11-06]. http://gaussian.com/glossary/g09/.
[34]	de Andrade J, Böes E S, Stassen H. Computational study of room temperature molten salts composed by 1-alkyl-3-methylimidazolium CationsForce-field proposal and validation. J Phys Chem B, 2002, 106(51): 13344 doi: 10.1021/jp0216629
[35]	Prampolini G, Campetella M, De Mitri N, et al. Systematic and automated development of quantum mechanically derived force fields: The challenging case of halogenated hydrocarbons. J Chem Theory Comput, 2016, 12(11): 5525 doi: 10.1021/acs.jctc.6b00705
[36]	Kim J H, Lee S H. Molecular dynamics simulation studies of benzene, toluene, and p-xylene in a canonical ensemble. Bull Korean Chem Soc, 2002, 23(3): 441 doi: 10.5012/bkcs.2002.23.3.441
[37]	Lyubartsev A P, Laaksonen A M. DynaMix - a scalable portable parallel MD simulation package for arbitrary molecular mixtures. Comput Phys Commun, 2000, 128(3): 565 doi: 10.1016/S0010-4655(99)00529-9
[38]	Allen M P, Tildesley D J. Computer Simulation of Liquids. Oxford: Oxford University Press, 2017
[39]	Tuckerman M, Berne B J, Martyna G J. Reversible multiple time scale molecular dynamics. J Chem Phys, 1992, 97(3): 1990 doi: 10.1063/1.463137
[40]	Morrow T I, Maginn E J. Molecular dynamics study of the ionic liquid 1-n-butyl-3-methylimidazolium hexafluorophosphate. J Phys Chem B, 2002, 106(49): 12807 doi: 10.1021/jp0267003
[41]	Dong K, Song Y T, Liu X M, et al. Understanding structures and hydrogen bonds of ionic liquids at the electronic level. J Phys Chem B, 2012, 116(3): 1007 doi: 10.1021/jp205435u
[42]	Marekha B A, Kalugin O N, Idrissi A. Non-covalent interactions in ionic liquid ion pairs and ion pair dimers: A quantum chemical calculation analysis. Phys Chem Chem Phys, 2015, 17(26): 16846 doi: 10.1039/C5CP02197A
[43]	Zheng Y. Application of Ionic Liquids in Low Temperature Aluminum Electrolysis [Dissertation]. Beijing: University of Chinese Academy of Sciences, 2013 郑勇. 离子液体在低温电解铝中的应用研究[学位论文]. 北京: 中国科学院大学, 2013
[44]	Xia S, Zhang X M, Huang K, et al. Ionic liquid electrolytes for aluminium secondary battery: Influence of organic solvents. J Electroanal Chem, 2015, 757: 167 doi: 10.1016/j.jelechem.2015.09.022
[45]	Zheng Y, Dong K, Wang Q, et al. Density, viscosity, and conductivity of lewis acidic 1-butyl- and 1-hydrogen-3-methylimidazolium chloroaluminate ionic liquids. J Chem Eng Data, 2013, 58(1): 32 doi: 10.1021/je3004904