Effect of organic extractants on the electrocrystallization of nickel from aqueous sulphate solutions

The effect of the presence of commercial organic extractants LIX 84I, Cyanex 272, D2EHPA, Versatic 10 and TBP with or without Mg²⁺ on various electrodeposition parameters for nickel deposition on stainless steel cathode from aqueous sulphate solutions was investigated. The parameters included cathodic current efficiency, deposit morphology, crystal orientation and cathodic polarization. There was no significant variation in the current efficiency in the presence of these additives, but changes were observed in the deposit morphologies and crystal orientations even though all the deposits were bright, smooth and coherent. Changes were also observed in the cathodic polarization behaviour during nickel electrocrystallization in the presence of these additives. The effect of the additives on the electrokinetic parameter, exchange current density (i ₀) has also been investigated.     

PEM fuel cell reaction kinetics in the temperature range of 23-120 °C

The performance of a Nafion 112 based proton exchange membrane (PEM) fuel cell was tested at a temperature range from 23 °C to 120 °C. The fuel cell polarization curves were divided into two different ranges based on current density, namely, <0.4 A/cm² and >0.4 A/cm², respectively. These two ranges were treated separately with respect to electrode kinetics and mass transfer. In the high current density range, a linear increase in membrane electrode assembly (MEA) power density with increasing temperature was observed, indicating the advantages of high temperature operation.Simulation based on electrode reaction kinetic theory, experimental polarization curves, and measured cathodic apparent exchange current densities all gave temperature dependent apparent exchange current densities. Both the calculated partial pressures of O₂ and H₂ gas in the feed streams and the measured electrochemical Pt surface areas (EPSAs) decrease with increasing temperature. They were also used to obtain the intrinsic exchange current densities. A monotonic increase of the intrinsic exchange current densities with increasing temperature in the range of 23-120 °C was observed, suggesting that increasing the temperature does promote intrinsic kinetics of fuel cell reactions.There are two sets of cathode apparent exchange current densities obtained, one set is for the low current density range, and the other is for the high current density range. The different values of cathode current densities in the two current density ranges can be attributed to the different states of the cathode Pt catalyst surface. In the low current density range, the cathode catalyst surface is a Pt/PtO, and in the high current density range, the catalyst surface becomes pure Pt.     

阴极极化对微生物在电极表面附着的影响

以天然海水作为电解质,利用荧光显微镜、扫描电镜等表征方法和开路电位、恒电位极化等电化学测试手段研究了生物膜附着与电极表面电位的相互影响。结果表明：（1）生物膜在电极表面的附着导致了开路电位正移;（2）阴极极化能有效抑制微生物附着,并且阴极氧还原反应是阴极极化抑制微生物附着的主要原因;（3）搅拌等能促进阴极反应、增大阴极极化电流密度的措施都会在一定程度上利于阴极极化对微生物附着的抑制作用。     

Electrochemical deposition and characterization of NiFe coatings as electrocatalytic materials for alkaline water electrolysis

In this study, nickel (Cu/Ni), iron (Cu/Fe) and nickel-iron (Cu/NiFe) composite coatings with various chemical compositions were electrochemically deposited on a copper electrode and characterized using cyclic voltammetry (CV), atomic absorption spectroscopy (AAS), scanning electron microscopy (SEM) and atomic force microscopy (AFM) techniques in view of their possible applications as electrocatalytic materials for the hydrogen evolution reaction (HER) in an alkaline medium. The electrocatalytic activity of the coatings for the HER was studied in 1 M KOH solution using cathodic current-potential curves and electrochemical impedance spectroscopy (EIS) techniques. The presence of nickel along with iron increases the electrocatalytic activity of the electrode for the HER when compared to nickel and iron coatings individually. The HER activity of the composite coatings depends on the chemical composition of the alloys. The Cu/NiFe-3 electrode (with a molar concentration ratio of Ni²⁺:Fe²⁺ of 4:6 in the plating bath) was found to be the best suitable cathode material for the HER in an alkaline medium under the experimental conditions studied. Furthermore, the electrocatalytic activity of the Cu/NiFe-3 electrode for the HER was tested for extended periods of time in order to evaluate the change in the electrocatalytic activity of the electrode with operation time. The HER was activation controlled and has not been changed after electrolysis. A constant current density of 100 mA cm⁻² was applied to the electrolysis system, and the corrosion behavior of the Cu/NiFe-3 electrode was investigated after different operation times using EIS and linear polarization resistance (LPR) techniques. For comparison, the corrosion behavior of a Cu/NiFe-3 electrode to which current was not applied was also investigated. The corrosion tests showed that the corrosion resistance of the Cu/NiFe-3 cathode changed when a cathodic current was applied to the electrolysis system.     

Electrochemical behaviour of nickel in nitric acid

The electrochemical investigations of nickel in a wide range of concentrations (1–14.6 M) of nitric acid were studied by potentiostatic, potentiodynamic and coulostatic method and by weight-loss measurements. The potentiostatic current-potential curves of nickel in nitric acid solutions can be classified into three categories, according to the proportion of the concentration of the acid. An increase of nitric acid concentration increases the influence of the cathodic reactions in the systems. The importance of cathodic reactions has been investigated by eliminating HNO₂ by additions of p-nitro aniline in the electrolyte. The coulostatic polarization has given distinct repassivation curves, indicating an intermediate state of nickel electrode between active and passive state. In the first part of repassivating process the potential value is more positive than the stationary potential of spontaneous passivation of nickel electrode in concentrated nitric acid. The return of the stationary potential of the passivity is a slow, time-dependent process. According to the experimental results and data given in the literature, it may be possible that in the beginning of the passivation process on nickel Ni(NO₃)₂ × 4 H₂O forms which changes to NiO₂ and than transforms slowly to NiO.     

Electrochemical behaviour of iron electrode in acidic acetonitrile solutions

Iron dissolution as well as hydrogen evolution was studied in HCl and HBr acetonitrile solutions in a concentration range between 2·8 × 10^?4 M. Halide concentration was changed by adding lithium halide to some of the previous solution. Measurements were performed at 0·0°C.Current efficiency for a two-electron transfer was about 100 per cent for both anodic and cathodic reactions.Corrosion and kinetic parameters were obtained from the polarization curves performed under different experimental conditions. Tafel slopes of 2·3 × 2 RT/F were found for both anodic and cathodic reactions.A reaction mechanism for the anodic reaction is postulated on the basis of anion adsorption. An inhibitory effect, probably due to solvent adsorption at the electrode, occurs as the acid concentration decreases, affecting both the anodic and cathodic polarization curves.     

Ceramic electrodes for an alkali metal thermo-electric converter (AMTEC)

TiN, TiC, TiC/TiN, and Mo electrodes for an Alkali Metal Thermo-Electric Converter (AMTEC) were prepared by ceramic processing and their cathodic polarization characteristics were studied at 600–800°C. The polarization characteristics for TiN and TIC electrodes were similar to those for the Mo electrode. Among three kinds of TiC electrodes with different morphologies, the electrode consisting of finer grains gave a higher power density (0.40 W cm^–2). The activation energies for the exchange current density were smaller for ceramic electrodes than for the Mo electrode. In the high current density region above about 1 A cm^–2, a limiting current region appeared. When the vacuum level of the low temperature region, which was controlled by introduction of argon, was below 10 Pa, the power density did not depend on the vacuum level but, above 10 Pa, the power density decreased with increase of argon pressure.     

高活性镍钴铁三元合金电极的制备及析氢性能研究

为进一步提高镍基电极的析氢性能,采用恒电位沉积法,通过改变镀液中各合金的质量浓度比、沉积电位、沉积时间等条件,制备出一种高活性的镍钴铁三元合金电极。通过测定电极在1 mol/L的NaOH溶液中的极化曲线,得到最佳的沉积工艺条件为:36.25 g/L NiSO_4·6H_2O,1.25 g/L NiCl_2·6H_2O,5 g/L CoSO_4·7H_2O,7.5 g/L FeSO_4·7H_2O,10 g/L H_3BO_3,0.5 g/L抗坏血酸,1 g/L十二烷基硫酸钠,pH=4.0,电沉积电位-1.45 V,电沉积时间300 s。阴极极化曲线测试结果表明在5 A/dm^2的条件下,镍钴铁三元合金电极的析氢过电位降低至121 mV,相比于纯镍电极过电位降低近50%,相比于镍钴电极过电位降低近35%。     

Die Kathodische reduktion von ozon an iridium in sauren elektrolyten

The cathodic reduction of ozone was studied at a smooth iridium electrode in acid electrolytes. The rest potentials deviate from the equilibrium values by ?500 to ?600 mV. They are determined by a mixed electrode system involving anodic oxygen evolution and cathodic reduction of ozone as half reactions.Tafel-lines with a slope between 120 and 160 mV (b-value) are obtained when steady state polarization measurements are carried out. Extrapolation of Tafel-lines to zero polarization and the determination of the charge transfer resistance give values for the pseudo-exchange current, which are in good agreement. A single electron transfer reaction is the rate determining step. Cathodic reaction orders of + 1 and zero are evaluated with respect to p_O3 and c_H+.

The charge transfer step does not involve H⁺-ions. In a succeeding chemical reaction an instable intermediate HO₃ is formed, the decomposition of which occurs in a fast reaction.Limiting currents are observed in a region of high cathodic polarization, which are diffusion controlled.     

Influence of CaF2 and AlF3 on the kinetics and mechanism of the Al electrode reaction in cryolite melts with various alumina contents

Electrochemical techniques were used to study the kinetics and mechanism of the aluminium electrode reaction in two cryolite-based melts containing cryolite with either 11 wt % AlF₃ or 5 wt % CaF₂ additions and variable alumina contents at 1000 °C. A three step electrode process was observed in both melts, comprising a preceding chemical reaction followed by two charge transfer steps. The exchange current density of the cathodic reaction was found to be dependent on the concentration of aluminium fluoride. By a combination of electrochemical impedance spectroscopy (EIS) and galvanostatic relaxation methods (GRM), the exchange current density of the first (slower) charge transfer step, the Warburg diffusion impedance, the double layer capacitance of the aluminium electrode and the rate of the preceding chemical step, were evaluated in the range of 2–8 wt % alumina. The role of the two additives, AlF₃ and CaF₂, was evaluated.     

Effects of antimony(III) on zinc electrodeposition from acidic sulfate electrolyte containing [BMIM]HSO<Subscript>4</Subscript>

The effect of antimony(III) on the cathodic current efficiency (CE), power consumption (PC), deposit morphology, and polarization behavior during electrodeposition of zinc from acidic sulfate solutions containing 1-butyl-3-methylimidazolium hydrogen sulfate-[BMIM]HSO₄ was investigated. The results indicated that the addition of Sb(III) alone decreased the CE, increased the PC, and deteriorated the quality of the zinc electrodeposits. However, the combined addition of Sb(III) and [BMIM]HSO₄ was found to be beneficial for zinc deposition and improved the surface morphology of the zinc electrodeposits. Maximum CE and minimum PC were obtained at the combined addition of 0.02 mg dm⁻³ Sb(III) and 5 mg dm⁻³ [BMIM]HSO₄. Depolarization of the cathode was noted in the presence of Sb(III) alone in the electrolyte whereas this effect was partly counteracted by the addition of [BMIM]HSO₄. Cathodic polarization curves were traced and analyzed to determine the electrokinetic parameters such as Tafel slope, transfer coefficient, and exchange current density so as to elucidate the nature of the electrode reactions. The data obtained from X-ray diffractogram revealed that the presence of Sb(III) did not change the structure of the electrodeposited zinc but affected the crystallographic orientation of the crystal planes.     

Flow influenced electrochemical corrosion of nickel aluminium bronze – Part I. Cathodic polarisation

The cathodic polarisation behaviour of CA 104 nickel aluminium bronze (NAB) has been examined in fully characterised seawaters (filtered and artificial) using the rotating disc electrode (RDE) and the rotating cylinder electrode (RCE). Linear sweep voltammetry and a potential step, current transient technique were used to examine the charge transfer and mass transfer controlled cathodic response as a function of both laminar and turbulent fluid flow. For freshly polished surfaces, the rate of irreversible charge transfer controlled oxygen reduction is controlled by the exchange of a single electron and hydrogen evolution is only significant at potentials more negative than approximately –1.0 V vs. the saturated calomel electrode (SCE).     

The effect of Cl(I)− ions on kinetics and mechanism of anodic dissolution and cathodic deposition of copper

The influence of Cl(I)^? ions on kinetics and mechanism of anodic dissolution and cathodic deposition of copper in acidic sulfate was investigated. For this investigation the galvanostatic single-pulse method has been used. The results indicate that Cl(I)^? ions change the exchange current density and transfer coefficients as determined from tafel analyses of the anodic and cathodic reactions.     

化学镀铜对LaMgNi3.7Co0.3储氢合金电化学性能的影响

在LaMgNi<,3.7>Co<,0.3>储氢合金粉末表面进行化学镀铜处理.覆铜后的合金粉末与镍粉混合后涂于泡沫镍上制成电极.当镀液中Cu<'2+>为1.2g/L,温度为30°C,pH为3.0,反应时间为2min时,合金电极在6 mol/L KOH电解液中的最大放电容量和循环稳定性能都有显著提高,合金电极的交换电流密度...     

In situ photoelectrochemistry and Raman spectroscopic characterization on the surface oxide film of nickel electrode in 30 wt.% KOH solution

The oxide films of nickel electrode formed in 30 wt.% KOH solution under potentiodynamic conditions were characterized by means of electrochemical, in situ PhotoElectrochemistry Measurement (PEM) and Confocal Microprobe Raman spectroscopic techniques. The results showed that a composite oxide film was produced on nickel electrode, in which aroused cathodic or anodic photocurrent depending upon polarization potentials. The cathodic photocurrent at −0.8 V was raised from the amorphous film containing nickel hydroxide and nickel monoxide, and mainly attributed to the formation of NiO through the separation of the cavity and electron when laser light irradiates nickel electrode. With the potential increasing to more positive values, Ni₃O₄ and high-valence nickel oxides with the structure of NiO₂ were formed successively. The composite film formed in positive potential aroused anodic photocurrent from 0.33 V. The anodic photocurrent was attributed the formation of oxygen through the cavity reaction with hydroxyl on solution interface. In addition, it is demonstrated that the reduction resultants of high-valence nickel oxides were amorphous, and the oxide film could not be reduced completely. A stable oxide film could be gradually formed on the surface of nickel electrode with the cycling and aging in 30 wt.% KOH solution.     

Zinc electrowinning from acidic sulphate solutions. Part III: Effects of quaternary ammonium bromides

The effects of the organic additives cetyltrimethylammonium bromide (CTABr) and tetrabutyl ammonium bromide (TBABr) on the electrowinning of zinc from acidic sulphate solutions were studied in the presence and absence of trace amounts of antimony(iii). The results indicated that CTABr has similar properties to the commonly used industrial additive glue with respect to current efficiency, power consumption, polarization behaviour, and the crystallographic orientation and surface morphology of the zinc deposits. TBABr was generally less useful with respect to all these properties. Voltammetric studies indicate that polarisation for zinc electrodeposition decreased in the order CTABr > glue > TBABr. The nature of the electrode reactions were investigated through measurements of exchange current densities, Tafel slopes and transfer coefficients.     

化学镀镍对LaMgNi3.7Co0.3储氢合金电化学性能的影响

在LaMgNi3.7Co0.3储氢合金粉末表面进行化学镀镍处理。镀覆镍的合金粉末与镍粉混合后涂于泡沫镍上制成电极。当镀液中Ni2+为40 g/L、温度为50°C、镀液pH为8.0、反应时间为30 min时,合金电极在6 mol/L KOH电解液中的最大放电容量和循环稳定性都有显著提高,合金电极的交换电流密度增大,极化电阻降低,其动力学性能增强。     

Effect of Pyridine and its Derivatives on the Electrodeposition of Nickel from Aqueous Sulfate solutions Part I: Current Efficiency, Surface Morphology and Crystal Orientation

The effects of pyridine and its derivatives on current efficiency, surface morphology and crystallographic orientations of electrodeposited nickel from acidic sulfate solutions were investigated. The results indicated that the presence of pyridine and picolines had no significant effect on current efficiency. The deposits obtained were smoother, more compact and uniform with picolines than with pyridine. A significant change in surface morphology of the electrodeposits was observed and picolines were found to be better additives than pyridine, 4-picoline being the best. X-ray diffraction revealed that the (200) plane was the most preferred plane and was not affected by the presence of any of these additives in the electrolyte.     

碳毡基体上电沉积Ni-Mo合金及其催化析氢性能

以碳毡为基体,采用瓦特型镀镍工艺电沉积镍,获得碳镍（C-Ni）电极,然后在离子液体体系中以C-Ni为基体电沉积Ni-Mo合金。采用扫描电镜和X射线衍射仪对合金电极的表面形貌和结构进行了表征,通过阴极极化曲线、交流阻抗等电化学测试研究了其析氢催化性能。实验结果表明,制得的Ni-Mo合金中Mo的质量百分含量约为5.12%,平均晶粒尺寸约为2.2 nm,为纳米晶结构;极化曲线测试表明,当电流密度为0.1 A·cm^-2时,Ni-Mo/C-Ni合金电极催化析氢电位较C-Ni电极正移108 mV,较碳毡正移557 mV,较水溶液中沉积的紫铜基Ni-Mo合金电极正移约50 mV;连续电解和断电流实验结果表明Ni-Mo/C-Ni合金电极具有良好的电化学稳定性,实用前景广阔。     

The use of channel flow cells for electrochemical kinetic studies in high temperature aqueous solutions

It has been shown that, for the case of one-step reactions of arbitrary order, the relationship between the average current density and the limiting current density on a working electrode mounted on the inner radius of an annular flow channel of arbitrary length obeys, with great accuracy, the same relations as does a reaction on a uniformly accessible surface. This allows us to combine the advantages of non-uniformly accessible surfaces (high sensitivity, and no need to use rotating contacts) with the advantages of uniformly accessible surface systems (simple treatment of experimental data). This feature can be very important when investigating systems at high temperatures and pressures, where RDEs are difficult to employ. Using this approach, and by employing previously measured polarization data, the kinetic parameters (exchange current density and anodic transfer coefficient) for the oxidation of hydrogen on platinized nickel in 0.1 M NaOH + 0.7 × 10⁻³ m H₂ at temperatures between 25 °C and 300 °C have been derived. The anodic transfer coefficient is found to be almost temperature independent with a value of 0.43. The exchange current density displays Arrhenius behavior with temperature, increasing from 1.9 × 10⁻⁴ A cm⁻² at 25 °C to 3.9 × 10⁻³ A cm⁻² at 300 °C.