二氯甲烷和甲苯對咪唑離子液體結構和性質及鋁電沉積的影響

田國才; 袁青香

doi:10.13374/j.issn2095-9389.2020.12.03.002

二氯甲烷和甲苯對咪唑離子液體結構和性質及鋁電沉積的影響

doi: 10.13374/j.issn2095-9389.2020.12.03.002

田國才^{1, 2, ,},
袁青香²

1.
昆明理工大學省部共建復雜有色金屬資源清潔利用國家重點實驗室，昆明 650093
2.
昆明理工大學冶金與能源工程學院，昆明 650093

基金項目: 國家自然科學基金資助項目（51774158，51264021）；云南省中青年學術技術帶頭人后備人才培養資助項目（2011CI013）

詳細信息

通訊作者:
E-mail：tiangc01@163.com

中圖分類號: TF821
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出版歷程
- 收稿日期: 2020-12-03
- 網絡出版日期: 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: 離子液體電沉積鋁技術具有廣闊的應用前景，而添加劑是提高鋁鍍層性能的有效方法，但相關作用機制還有待明確。本文應用量子化學和分子動力學模擬研究了二氯甲烷（DCM）和甲苯(C₇H₈)對氯化-1-丁基-3-甲基咪唑/三氯化鋁([BMIM]Cl/AlCl₃)體系的微觀結構、物理化學性質和鋁電沉積的影響。發現DCM易與陰、陽離子形成氫鍵，分布在陰陽離子之間使得陰陽離子間距離增加、相互作用能減小, 導致陰陽離子擴散能力增強、鋁配離子更傾向以${\rm{A}}{{\rm{l}}_2}{\rm{Cl}}_7^ -$形式存在，體系黏度降低電導率增加，因而對體系電化學性質提升很大，而且DCM起到了晶粒細化和整平作用，從而可以得到鏡面光亮的沉積層，所得結果與實驗值吻合較好。C₇H₈主要分布在陽離子周圍，與陽離子有較強相互作用，在沉積過程中吸附于電極表面的凸出部分，抑制了電活性離子的還原而主要起到整平作用，其對陰離子和陽離子之間的相關作用的影響比DCM小，因而體系電化學性質提升不如DCM。
- 離子液體 /
- 鋁電沉積 /
- 添加劑 /
- 二氯甲烷 /
- 甲苯 /
- 第一性原理 /
- 分子動力學
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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圖 1 模擬用到的陽離子和分子的結構以及相應原子的類型。（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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圖 2 B3LYP/6-311++G(d,p)方法得到的離子液體與添加劑作用的穩定構型。（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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圖 3 B3LYP/6-311++G(d,p)方法得到的前線軌道圖。（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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圖 4 MD模擬計算得到體系中離子間的徑向分布函數g_A-B(r)。（a）[BMIM]⁺與${\rm{Al}}_{x} {\rm{Cl}}_y^{3x-y} $；（b）${\rm{Al}}_{x} {\rm{Cl}}_y^{3x-y} $與Cl^?；（c）[BMIM]⁺與M(M=DCM、C₇H₈)；（d）${\rm{Al}}_{x} {\rm{Cl}}_y^{3x-y} $與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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圖 5 計算得到的三維空間分布圖。（a）[BMIM]⁺周圍Cl^?(綠色)、C₇H₈（黃色）、DCM（紅色）、${\rm{Al}}_{x} {\rm{Cl}}_y^{3x-y} $（藍色）的三維空間分布；（b）${\rm{Al}}_{x} {\rm{Cl}}_y^{3x-y} $周圍Cl^?（綠色）、DCM（紅色）、C₇H₈（黃色）空間分布

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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圖 6 DCM和C₇H₈對體系中各粒子均方根位移（MSD）和擴散系數的影響。（a）[BMIM]⁺的MSD；（b）${\rm{Al}}_{x} {\rm{Cl}}_y^{3x-y} $的MSD；（c）DCM和C₇H₈的MSD; (d) 各粒子的擴散系數

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)方法得到的體系中各粒子間的相互作用能

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)方法得到的體系的相關量化參數

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 計算所得體系中主要粒子的配位數

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 計算得到的303.14 K和0.1 MPa下體系的黏度(η)與電導率(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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