常温下从离子液体电解液中电沉积金属钴

研究了离子液体镀液中Co、Zn的共沉积行为。ZnCl2-EMIC -CoCl2电解液的循环伏安曲线上出现了三个电流峰,对应的电极电位分别为250mV、50mV、-200mV（vs. Zn2+/Zn）。结合EDS成分分析,可断定这三个电流峰分别对应着Co的电沉积、Co电极上Zn的欠电位沉积和Co-Zn合金的电沉积。恒电位沉积表明,当控制阴极电位在100 mV（vs. Zn2+/Zn）左右时,可得到高纯度的钴镀层;若进行恒电流沉积,则当电流密度为85mA/cm2左右时能够得到高纯度的钴镀层。对Co、Zn的共沉积机理研究表明,Co的电沉积过程和Zn 在Co上的欠电位沉积过程均受扩散过程控制。     

硫化镉纳米线的电沉积制备及表征

以不同孔径的多孔阳极氧化铝为模板,采用直流电沉积的方法,在含CdCl2和S的DMSO溶液中制备出了CdS纳米线．SEM、TEM表征的结果表明,在不同孔径的多孔阳极氧化铝模板中,通过沉积时间等条件的控制,制得直径不同、长度可达5μm的平行结构、均匀而连续的CdS纳米线阵列．电子衍射和能谱结果显示所得的纳米线属于六方晶系CdS,线中Cd和S原子比接近1：1．     

化学沉积法制备Ni-P纳米线与纳米管有序阵列

以多孔氧化铝膜为模板, 在室温下的酸性化学镀镍槽中通过化学沉积法生长出纳米线与纳米管有序阵列. 分别用X射线衍射仪(XRD)与透射电子显微镜(TEM)对纳米线、纳米管阵列进行表征. 并通过对纳米线与纳米管的生长方式进行分析比较, 系统地研究了多孔氧化铝模板的前处理对纳米阵列生长的影响. 结果表明, 生成的纳米线与纳米管均为非晶态的镍磷合金. 室温下镍纳米管的生成主要取决于敏化、活化过程, 而当纳米管的厚度达到一定程度后就不再随时间变化.     

氧化铝模板中直流电沉积镍纳米线

氧化铝模板中直流电沉积镍纳米线;多孔阳极氧化铝模板;镍纳米线;电沉积     

添加剂对离子液体中电沉积金属钴的影响

在含有氯化钴的室温离子液体氯化1-甲基-3-乙基咪唑(EMIC)和乙二醇(EG)体系中,采用扫描电子显微镜(FE-SEM）、阴极极化曲线、循环伏安及X射线衍射等方法研究了添加剂对电沉积金属钴的影响。结果表明,在EMIC-EG-CoCl₂熔盐中加入丁炔二醇能够有效地改善钴镀层的外观质量,丁炔二醇的加入量在0.3～0.7 g·L^-1范围内,能够得到银灰色、具有金属光泽的良好镀层。从FE-SEM照片可以看出,在EMIC-EG-CoCl₂熔盐中加入丁炔二醇后,使金属钴的结晶变得更加细致;阴极极化曲线表明,丁炔二醇的加入不仅增大了阴极极化,而且还消除了钴的欠电势沉积;循环伏安测试证明,添加剂的加入对阴极沉积过程有阻化作用;XRD分析证实,丁炔二醇的加入使金属钴的衍射峰变宽,晶粒尺寸为纳米级。     

铅纳米线阵列的制备

使用电化学沉积方法,在有序的氧化铝模板(AAO)孔洞中制备了铅纳米线有序阵列。用X射线衍射仪(XRD)、场发射扫描电子显微镜(FE-SEM)、透射电子显微镜(TEM)对样品的结构、形貌、进行表征和观测。XRD的结果表明所制备的样品为纯的立方面心铅,且纳米线生长沿<220>有很好的取向。FE-SEM的图片清晰地说明铅纳米线阵列是大面积、高填充率和高度有序的。TEM的结果显示纳米线直径均匀、表面光滑且长径比大。     

循环伏安法制备Ag纳米线阵列

In this paper, highly ordered anodic aluminum oxide (AAO) template with hexagonal close-packed arrays was successfully fabricated through a two-step anodization process. Ag nanowire arrays with high aspect ratio were prepared using cyclic voltammetry within the confined nanochannels of AAO template. In addition, standing Ag nanowire arrays free-support of templates were also fabricated successfully by cyclic voltammetry method. The micrographs and crystal structures of Ag nanowires were studied by field emission scanning electron microscope (FESEM) and X-ray diffraction (XRD). FESEM observation showed that the Ag nanowire arrays with high aspect ratio lie orderly on the surface of the substrate. The diameter of the Ag nanowire is about 60 nm and the length up to 30 μm or more. While the controlled nanowire arrays exhibit highly ordered structure in large area and the standing Ag nanowire in the array has the length of 1 μm and good orientation. XRD results illustrated that the Ag nanowires in the arrays deposited by cyclic voltammetry method have a face centered cubic structure and are preferentially oriented in the (220) direction.     

离子液体AlCl3/Et3NHCl中电沉积法制备金属铝

在AlCl3/Et3NHCl型离子液体中铝电极上通过恒电位电解沉积制备出金属铝. 测定了不同摩尔比的AlCl3/Et3NHCl离子液体在不同温度下的电导率, 考察了离子液体AlCl3/Et3NHCl摩尔比为2/1中Al电极上铝沉积的晶核成核过程, 以及恒电位电解沉积铝的工艺条件对电流效率和沉积铝表面形貌的影响. 结果表明, 不同比例AlCl3/Et3NHCl离子液体的电导率随温度升高而升高, 符合Arrhenius规律; 在Al电极上铝沉积的成核机理为三维瞬时成核过程; 恒电位电解沉积结果表明, 室温下在电位-2.4 V(vs Pt)和电解时间20 min条件下, 沉积铝的表面形貌比较平整致密,电流效率达73%, 沉积铝的纯度达96%(w).     

离子液体中钴的电沉积行为

在含有氯化钴的室温离子液体氯化1-甲基-3-乙基咪唑(EMIC)和乙二醇(EG)体系中研究了金属钴的电沉积. 循环伏安法测试表明, 在EMIC-CoCl2熔盐中, 乙二醇的加入促进了EMIC的解离, 从而使氧化还原电流增大, 在EMIC-CoCl2-EG体系中钴的电沉积是受扩散控制的非可逆电极过程, 在该电解液体系中, Co(II)在Pt电极上的传递系数α为0.30, 扩散系数D0为4.16×10^-6 cm·s^-1; 计时电流法研究表明, 钴在铂电极上的电结晶过程符合三维连续成核的生长机理; 场发射扫描电子显微镜(FE-SEM)观察镀层的微观形貌显示, 金属钴的结晶细小. XRD分析证实, 镀层为纯钴, 沉积的钴是晶态和微晶态的混合物, 并且晶粒尺寸为纳米级.     

共晶基离子液体的钴电化学沉积

通过恒电流和恒电位方法,研究了不同温度下脲-氯化胆硷（氯仿）基或乙二醇-氯化胆硷（氯仿）基离子液体中氯化钴溶液在铜和钢阴极上的钴电化学沉积行为. 采用扫描电子显微镜和X射线衍射技术,考察了不同试验条件对钴电沉积行为及钴沉积层形貌的影响. 结果表明,当沉积电位达到-0.8 V和沉积电流密度达到-6.0 A·m^-2时,温度范围从30 °C到90 °C,添加0.05 mol·L^-1的五氧化二磷,可以从脲基和乙二醇基离子液体中沉积得到光滑、发亮和良好结合力的金属光泽钴层. 电化学沉积钴的阴极电流效率达到98%.     

Free-standing aluminium nanowire architectures made in an ionic liquid

We report on the electrochemical synthesis of free‐standing aluminium nanowire architectures through a template‐assisted electrodeposition technique. For this purpose, nuclear track‐etched polycarbonate membranes were employed as templates. One side of the template was sputtered with a thin gold film to serve as a working electrode. Subsequently the nanowires were made in the ionic liquid 1‐ethyl‐3‐methylimidazolium chloride ([EMIm]Cl)/AlCl₃ (40/60 mol %) under potentiostatic conditions. Two different electrodeposition procedures were employed to fabricate strongly adherent Al nanowire structures on an electrodeposited Al layer. In the first procedure, electrodeposition simultaneously occurs along the pores of the template and on the Au‐sputtered side of the template. In the second procedure, electrodeposition takes place in two different steps: first a thick supporting film of Al is deposited on the sputtered side of the membrane and second Al nanowires are grown within the pores. After chemical dissolution of the membrane in dichloromethane, an aluminium foil of a controlled thickness with a three‐dimensional nanowire structure on one side was obtained. Different nanowire architectures, such as free‐standing nanowires, vertically aligned tree‐shaped arrays, and bunched nanowire films, were obtained. Such nanowire architectures are of particular interest for applications in Li‐ion micro‐batteries.     

离子液体在电沉积铝及铝合金中的应用

离子液体具有不挥发、不燃烧、热稳定性高、电化学窗口宽等特点,被认为是一种满足可持续发展和绿色化学需求的溶剂介质,因其在室温下可以电沉积出多种活泼金属及合金而备受关注。本文系统地介绍了近年来离子液体在电沉积铝及铝合金中的应用进展,分类概括了用于电沉积铝及铝合金的离子液体类型;综述了电沉积机理;对不同形貌的金属铝以及二元、三元铝合金的电沉积技术进行了详细的阐述;最后探讨了当前离子液体在电沉积铝及铝合金理论与技术研究中存在的问题,并对其发展方向进行了展望。     

镁合金于离子液体中电镀铝之研究

本研究利用AlCl3-EMIC离子液体在AZ91D镁合金表面电镀铝金属,探讨离子液体组成及电流密度对电镀层性质的影响.研究结果显示铝金属可以成功地电镀于AZ91D镁合金表面上.在-0.2 V的电位下,在60 m/o AlCl3离子液体中可以获得较佳的电镀铝层.另外,在低定电流密度下进行电镀,电流效率较佳,镀层较厚.于3.5%NaCl(by mass)溶液中,铝金属镀层可以大幅提升镁合金之开路电位,并使其表面活性下降.电化学交流阻抗频谱分析显示,镁合金裸材于3.5%NaCl(by mass)水溶液中之极化阻抗值约为470~510Ω.cm2,镀铝之镁合金极化阻抗值则可提升至5200Ω.cm2.极化曲线则显示,镀铝之镁合金可以被钝化,其钝化电流密度低至5×10-5A/cm2.     

Electrodeposition in Ionic Liquids

Due to their attractive physico‐chemical properties, ionic liquids (ILs) are increasingly used as deposition electrolytes. This review summarizes recent advances in electrodeposition in ILs and focuses on its similarities and differences with that in aqueous solutions. The electrodeposition in ILs is divided into direct and template‐assisted deposition. We detail the direct deposition of metals, alloys and semiconductors in five types of ILs, including halometallate ILs, air‐ and water‐stable ILs, deep eutectic solvents (DESs), ILs with metal‐containing cations, and protic ILs. Template‐assisted deposition of nanostructures and macroporous structures in ILs is also presented. The effects of modulating factors such as deposition conditions (current density, current density mode, deposition time, temperature) and electrolyte components (cation, anion, metal salts, additives, water content) on the morphology, compositions, microstructures and properties of the prepared materials are highlighted.     

Cobalt(II) Complexes of Nitrile‐Functionalized Ionic Liquids

A series of nitrile‐functionalized ionic liquids were found to exhibit temperature‐dependent miscibility (thermomorphism) with the lower alcohols. Their coordinating abilities toward cobalt(II) ions were investigated through the dissolution process of cobalt(II) bis(trifluoromethylsulfonyl)imide and were found to depend on the donor abilities of the nitrile group. The crystal structures of the cobalt(II) solvates [Co(C₁C_1CNPyr)₂(Tf₂N)₄] and [Co(C₁C_2CNPyr)₆][Tf₂N]₈, which were isolated from ionic‐liquid solutions, gave an insight into the coordination chemistry of functionalized ionic liquids. Smooth layers of cobalt metal could be obtained by electrodeposition of the cobalt‐containing ionic liquids.     

Hybrid Platforms of Silicon Nanowires and Carbon Nanotubes in an Ionic Liquid Bucky Gel

Silicon nanowires (NWs) are appealing building blocks for low-cost novel concept devices with improved performances. In this research paper, we realized a hybrid platform combining an array of vertically oriented Si NWs with different types of bucky gels, obtained from carbon nanotubes (CNT) dispersed into an ionic liquid (IL) matrix. Three types of CNT bucky gels were obtained from imidazolium-based ionic liquids (BMIM-I, BIMI-BF₄, and BMIM-Tf₂N) and semiconductive CNTs, whose structural and optical responses to the hybrid platforms were analyzed and compared. We investigated the electrical response of the IL-CNT/NW hybrid junctions in dark and under illumination for each platform and its correlation to the ionic liquid characteristics and charge mobility. The reported results confirm the attractiveness of such IL-CNT/NW hybrid platforms as novel light-responsive materials for photovoltaic applications. In particular, our best performing cell reported a short-circuit current density of 5.6 mA/cm² and an open-circuit voltage of 0.53 V.     

Robust Aluminum Electrodeposition from Ionic Liquid Electrolytes Containing Light Aromatic Naphta as Additive

Aluminum electrodeposition can be carried out from several ionic liquid electrolyte formulations. Nevertheless, this plating process has not been industrialized so far because of the durability of the electrolytes and because the Al coatings obtained are non-fully homogeneous in terms of coating morphology and thickness distribution. In this work we electrodeposited Al coatings from a 3-butyl-1-ethylimidazolium tetrachloroaluminate electrolyte additivated with increasing concentrations of a new cost-effective additive: light aromatic naphtha solvent. Firstly, electrolytes were characterized by cyclic voltammetry, where changes in the electrochemistry of the process were identified. Then, surface characterization showed that Al coatings morphology turned out to be smoother, more homogeneous and more compact with increasing additive concentration. Furthermore, the process was scaled up to flat plates of 18 cm² area and also on 25 cm² parts designed with straight corners to demonstrate both the optimization of the electrolytic bath performance and its throwing power enhancement.