Electrolytic preparation of nanosized Cu/Ni-Cu multilayered coatings

The electrolytic deposition of nanosized Cu/Ni-Cu multilayer coatings on a paraffin-impregnated graphite substrate was performed from an electrolyte consisting of sulphate salts of the above metals and a complex-forming agent, sodium citrate. The multilayer Cu/Ni-Cu coatings were prepared using the potentiostatic method, in which the potential was alternately pulsed between the reduction potentials of the components. Suitable deposition potentials were selected from the polarisation curves. The presence of the thin films was confirmed by atomic absorption spectroscopy (after dissolution) and by optical microscopy. The resulting images show a layered structure of Cu/Ni-Cu coatings formed by Cu, Ni and/or Ni-Cu layers.     

Structures and magnetic properties of iron- and cobalt-containing oxide coatings on an aluminum alloy formed in electrolytes via plasma electrolytic oxidation

The effect of the nature of the supporting electrolyte in the composition of electrolytic suspensions containing dispersed particles of Fe(III) and Co(II) hydroxides, and of anodic and bipolar anodic-cathodic polarization on features of the formation, composition, and magnetic characteristics of oxide coatings is studied. In all cases, iron and cobalt are incorporated into the coatings and are concentrated predominantly in pores. The pores of the coatings include particles consisting of the reduced metals, presumably surrounded by oxide or hydroxide shells. The electrolyte composition affects the concentration and ratio of the metals in the particles. A correlation is observed between the ferro- or ferrimagnetism of the coatings and the content and ratio of cobalt and iron in the pores.     

Anodic oxidation of complex shaped items of aluminum and aluminum alloys with subsequent electrodeposition of copper coatings

It was shown that the method of anodization of aluminum and aluminum alloys can be applied for subsequent plating of highly adherent copper coating instead of the known zincate treatment with additional annealing. Fluorine-containing additives in anodizing electrolyte were proposed as activator of oxide film. The parameters of the anodic film (thickness, porosity, and microroughness) were calculated. The plated quality copper coatings have high adhesion to the aluminum support, and no additional heat treatment is required. This considerably reduces the processing time for deposition of multilayer coatings and decreases the material costs.     

LiBOB基电解液成膜性及其循环性能

通过循环伏安(CV)、电化学阻抗谱(EIS)、扫描电子显微镜(SEM)、X射线光电子能谱(XPS)和傅立叶变换红外(FTIR)光谱研究了双乙二酸硼酸锂(LiBOB)基电解液在石墨表面的成膜性及其在常温(25 ℃)和高温(70 ℃)下对石墨循环性能的影响. 结果表明, LiBOB基电解液的成膜电位在1.7 V, 其中BOB-离子还原形成的草酸盐是固体电解质相界面(SEI)膜的有效成分之一. 电化学阻抗谱显示, 膜阻抗在循环过程中呈现减小趋势, 这有利于提高循环稳定性. 在常温和高温条件下, 石墨在该电解液体系中均表现出优于其在LiPF6基电解液体系中的循环性能.     

Initiating electropolymerization on graphene sheets in graphite oxide structure

Because of its special chemical composition, graphite oxide has peculiar influences on electrochemical processes. The existence of various functional groups significantly affects electropolymerization processes and the formation of conductive polymers. Electrochemical synthesis of polyaniline (as a prototype of conductive polymers) on a paste‐based substrate of graphite oxide was investigated. In this case, the electropolymerization is significantly different from conventional cases, and the polymer is generated just during the first potential cycle. This can be attributed to the fact that graphite oxide can assist the monomer oxidation. Alternatively, electropolymerization was successfully performed inside the graphite oxide layers via electrochemical treatment of aniline‐intercalated graphite oxide in the supporting electrolyte. Although these phenomena are related to the chemical composition of graphite oxide, the graphite prepared by the reduction of graphite oxide also displayed some advantages for the electropolymerization (over natural graphite). There is an emphasis on the morphological investigations throughout this study, because novel morphologies were observed in the system under investigation. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2204–2213, 2010     

Structural aspects of the deposition of metal coatings on polymer films

An electron-microscopic study of the formation of thin metal coatings (gold and aluminum) on a PET film is performed. During the deposition of gold coatings, a well-pronounced interfacial polymer/metal layer is formed, while, in the case of aluminum coatings, the polymer/metal interface is well-defined. The assumption is made that this effect is caused by different chemical activities of metals deposited on the polymer.     

Irreversible processes during the lithium intercalation into graphite: the passive film formation

Comparative studies of three type of carbonaceous materials—the modified oxidized graphite, thermoexpanded graphite, and carbon paper—prior to and after galvanostatic cycling in 1 M LiClO₄ solution in propylene carbonate-dimethoxyethane mixture are carried out using standard porosimetry. It was shown that the mean (effective) thickness of the passive film [solid electrolyte interface (SEI)] at the electrodes of the modified oxidized graphite and thermoexpanded graphite equals a few nanometers. The comparison of porosimetric and electrochemical data shows that the passive film comprises both lithium carbonate and alkylcarbonates. Additionally, this comparison allows corroborating the concept on the formation of polymer (or oligomer) component of the passive film at least at the thermoexpanded graphite electrodes.     

Electrodeposition of Co–W coatings from boron gluconate electrolyte with a soluble tungsten anode

Conditions were determined in which an active anodic dissolution of tungsten is observed in a borongluconate electrolyte used to obtain Co–W coatings (pH ~6.5) and the nature of critical currents of transition to the passivation was found, which makes it possible to use the tungsten anode as a soluble electrode. The anodic dissolution of tungsten occurs under these conditions with a current efficiency of 90–100%, which, in contrast to the case of a graphite anode, does not lead to an additional oxidation of the electrolyte components and polymerization in solution; in combination with the decrease in the concentration of tungstate ions, this reduces the electrolyte performance. It was shown that the use of a soluble tungsten anode in obtaining nanocrystalline cobalt–tungsten coating can improve the electrolyte performance due to the rise in the current efficiency of electrodeposition and to the increase in the microhardness of the coatings in comparison with the case of an insoluble graphite anode.     

Approach to excellent superhydrophobicity and corrosion resistance of carbon-based films by graphene and cobalt synergism

A new series of carbon-based films doped with graphene oxide and cobalt (G-Co/a-C:H films) were successfully prepared on Si substrate via one-step electrochemical deposition of methanol as the carbon source and graphene oxide/cobalt as the dopant. G-Co/a-C:H films were fabricated at various graphene oxide concentration for comparative experiments. It can be found that the graphene oxide and cobalt were well embedded in amorphous carbon matrix to form superhydrophobic G-Co/a-C:H film at the doping GO concentration of 0.007 mg/mL, which was confirmed by transmission electron microscopy (TEM). It was noted that the superhydrophobicity of the resulting surface derives from its rough surface with hierarchical micro-nanostructures and the presence of the low-surface-energy GO components on it. The hierarchical micro-nanostructures are attributed to the corporate joint of GO and cobalt to form the multilevel nanoscale composite interface. Specially, the as-fabricated superhydrophobic G-Co/a-C:H film could exhibit excellent self-cleaning ability and corrosion resistance, revealed by the self-cleaning and corrosion tests.     

An iridium-based mercury-film electrode: Part I. Selection of substrate and preparation

A mercury-film electrode with iridium as the substrate has been developed. Various metals were considered as potential electrode substrates, but only iridium was found to possess the desirable properties as a Hg-film substrate. After testing several pretreatment procedures the recommendation is to polish with 1 μm diamond, rinse with chromic acid and cathodize at −2.0 V vs. SCE. Different deposition conditions and solutions were tested for optimizing the conditions of film formation. The use of a square-wave deposition potential and 0.1 M HClO₄ as electrolyte resulted in a dramatic improvement in the formation of a stable Hg film. Finally a complete procedure is given for the formation of a stable Hg film on iridium.     

Comparison of characteristics of solid oxide fuel cells with YSZ and CGO film solid electrolytes formed using magnetron sputtering technique

The work describes the methods of manufacturing single cells of solid oxide fuel cell (SOFC) with thin–film YSZ and CGO electrolytes and also with the bilayer YSZ/CGO electrolyte. Formation of YSZ and CGO films on the supporting NiO–YSZ anode of SOFC was carried out using the combined electron–ionic–plasma deposition technique. The microstructure and phase composition of the formed coatings are studied and also comparative analysis of electrochemical characteristics of single fuel cells with different electrolytes is performed. It is shown that the maximum power density of 1.35 W/cm² at the temperature of 800°C is obtained for the cell with bilayer YSZ/CGO electrolyte. However, the highest performance at lower working temperatures (650–700°C) is characteristic for the fuel cell with single–layer CGO electrolyte; its power density is 600–650 mW/cm².     

Formation and Properties of Nickel–Phosphorus–Graphite Composite Coatings in Autocatalytic Deposition

It is shown that nickel–phosphorus–graphite composite coatings can be deposited by the autocatalytic deposition method. The optimal concentration of graphite and the duration of ultrasonic treatment of a graphite suspension in solution for deposition of composite coatings based on the nickel–phosphorus alloy were determined. The influence exerted by thermal treatment parameters on the properties of the deposits was examined. The optimal process conditions are suggested.     

Formation of oxide layers modified with polytetrafluoroethylene or graphite on aluminum and titanium alloys by plasma electrolytic oxidation

For one-stage formation of coatings containing polytetrafluoroethylene or graphite, it was proposed to use Na₂SiO₃ + NaOH aqueous electrolyte containing siloxane-acrylate emulsion and dispersed powders of polytetrafluoroethylene or graphite. The phase and elemental composition and surface morphology of the formed coatings were determined. It was shown that the introduction of polytetrafluoroethylene markedly increases the hydrophobic and wear-resistant properties of coatings.     

Electrochemical oxide film formation at noble metals as a surface-chemical process

The mechanisms of electrochemical oxide film formation at noble metals are described and exemplified by the cases of Pt and Au, especially in the light of recent experimentation by means of cyclic voltammetry, ellipsometry and vacuum surface-science studies using LEED and AES.

Unlike the mechanisms of base-metal oxidation, e.g., in corrosion processes, anodic oxide film formation at noble metals proceeds by surface chemical processes involving, initially, sub-monolayer, through monolayer, formation of 2-dimensional OH/O arrays. During such 2-d processes, place-exchange between electrosorbed OH or O species on the surface, and Pt or Au atoms within the surface lattice, takes place leading to a quasi-2-d compact film which then grows ultimately to a multilayer hydrous oxide film, probably by continuing injection of ions of the substrate metal and their migration through the growing film under the influence of the field.

The initial, sub-monolayer stage of electrosorption of OH involves competitive chemisorption by anions, e.g. HSO₄⁻, ClO₄⁻, Cl⁻, which inhibits onset of the first stage of surface oxidation. These processes are demonstrable in experiments on single-crystal surfaces. The combination of such anion effects with place-exchange during the extension of the film, leads to a general mechanism of noble metal oxide film formation.

The formation of the oxide films can be examined in detail by recording the distinguishable stages in the film's electrochemical reduction in linear-sweep voltammetry which is sensitive down to OH/O fractional coverages as low as 0.5% and over time-scales down to 50μs in experiments on time-evolution and transformation of the states of the oxide films.

By means of LEED, AES and STM or AFM experiments, the reconstructions and perturbations (e.g. generation of stepped terraces) which oxide films cause on singlecrystal surfaces can be followed.     

Toward a quantitative description of the anodic oxide films on aluminum

A method to quantify the composition of anodic oxide films on aluminum using Infrared Spectroscopic Ellipsometry (IRSE) is proposed. It consists of obtaining the absorption coefficient of the film as a function of wavelength. Using values of the absorption coefficients for the pure components of the film, the percentages (mole or wt%) of each component in the sample can be calculated.The method is demonstrated in a study of the structure of the oxide film on electropolished aluminum and the anodically formed barrier layer film. Both surface oxides were found to be initially a form of amorphous Al₂O₃. While the barrier film is essentially free of water as prepared, the film on electropolished aluminum contained about 25 wt% water. Hydration of both types of films by immersion in boiling water results in the formation of pseudoboehmite (AlOOH). The technique may have more general applicability to the quantitative determination of the composition of corrosion films and other surface layers on metals.     

Effects of current densities on the formation of LiCoO<Subscript>2</Subscript>/graphite lithium ion battery

The activation characteristics and the effects of current densities on the formation of a separate LiCoO₂ and graphite electrode were investigated and the behavior also was compared with that of the full LiCoO₂/graphite batteries using various electrochemical techniques. The results showed that the formation current densities obviously influenced the electrochemical impedance spectrum of Li/graphite, LiCoO₂/Li, and LiCoO₂/graphite cells. The electrolyte was reduced on the surface of graphite anode between 2.5 and 3.6 V to form a preliminary solid electrolyte interphase (SEI) film of anode during the formation of the LiCoO₂/graphite batteries. The electrolyte was oxidized from 3.95 V vs Li⁺/Li on the surface of LiCoO₂ to form a SEI film of cathode. A highly conducting SEI film could be formed gradually on the surface of graphite anode, whereas the SEI film of LiCoO₂ cathode had high resistance. The LiCoO₂ cathode could be activated completely at the first cycle, while the activation of the graphite anode needed several cycles. The columbic efficiency of the first cycle increased, but that of the second decreased with the increase in the formation current of LiCoO₂/graphite batteries. The formation current influenced the cycling performance of batteries, especially the high-temperature cycling performance. Therefore, the batteries should be activated with proper current densities to ensure an excellent formation of SEI film on the anode surface.     

Deposition of protective-decorative coatings onto aluminum alloys

Technique for deposition of a nickel coating onto various aluminum alloys was developed. This coating can be used both independently and as a sublayer under multilayer coatings and, in particular, under those of nickel, tin–bismuth, lustrous nickel, and lustrous chromium. The technique includes anodization, chemical treatment, and electrodeposition of nickel in a special solution. The working modes of the anodization electrolyte were chosen and the necessity for a preliminary chemical treatment of the oxide film being formed was substantiated. A composition of the acid electrolyte for the subsequent nickel plating was developed with buffer and improving additives. The thus deposited electroplated nickel coatings exhibit a high adhesion to the aluminum base without additional thermal treatment. This makes it possible not only to reduce the technological time for deposition of the subsequent multilayer coatings, but also to fully automate the whole process.     

Cracking and Decohesion of Sol-Gel Hybrid Coatings on Metallic Substrates

Thin film coatings based on organically modified silanes were synthesized using sol-gel technology. Various mixtures of tetraethoxysilane and glycidoxypropyltrimethoxysilane precursors were used to produce sol-gel coatings on as-received and thermally oxidised copper, aluminium and titanium substrates. The mechanical properties and adhesion behaviour of the coatings were assessed using nano-indentation and microtensile testing, respectively. The relationship between the film structure and its mechanical response is examined. It is shown that the mechanical properties (hardness and Young's modulus) of the coatings are influenced dramatically by the organic substituent and the presence of an oxide layer thermally grown on the substrate material prior to deposition plays an important role on the film/substrate adhesion behaviour.     

Creation of thin oxide coatings and oxide nanopowders by anodic oxidation of metals in molten salts

We studied the feasibility of synthesizing ultrafine oxide powders by anodic oxidation of metals, such as zirconium and tantalum, in chloride + nitrate melts at temperatures above 830K. We showed that, varying the electrolyte composition, oxidation temperature, and anodic current density, one obtains either compact protective coatings on the specified metals or oxide powders with particle sizes of 50 to 200 nm.     

二氟草酸硼酸钠作为电解液添加剂对石墨负极性能的影响

锂离子电池日益广泛的应用对其性能提出越来越高的要求,而在电解液中加入适当的添加剂能够显著提升电极材料的电化学性能. 本文首次在1 mol·L^-1 LiPF₆/EC + DMC + EMC（体积比1:1:1）的电解液中添加一定量的二氟草酸硼酸钠(NaDFOB),并通过循环伏安（CV）、电化学阻抗图谱（EIS）和扫描电子显微镜（SEM）等分析考察了其对石墨负极材料性能的具体影响. 结果显示,添加NaDFOB的电解液显著提高了石墨材料在常温下的可逆充放电容量和循环性能,同时明显改善了石墨材料的高温循环性能. 其机理在于NaDFOB的阴阳离子同时参与了石墨表面固体电解质界面膜（SEI）的形成,形成高稳定性的电解液/电极界面.