The role of iron in the prevention of nickel electrode deactivation in alkaline electrolysis

There is some uncertainty concerning the role of iron deposits on the surface of nickel electrodes with respect to electrode activity during alkaline water electrolysis. Iron deposits variously have been reported to enhance nickel electrode activity by providing additional surface area from electrolytic deposition of solution phase iron species or to depassivate nickel electrodes via a surface interaction effect. In this study, nickel electrodes were sputtered with a smooth iron layer to determine the effect of metallic iron on the electrode surface without significantly changing the electrode surface area. A permeation cell with 8 mol/L KOH at 70 °C was used to follow nickel electrode potentials during hydrogen evolution while the permeation current was used to detect changes in the electrode structure.Short term measurements reveal no difference in behavior of coated and non-coated electrodes. Longer term results showed that a metallic iron coating on nickel electrodes prevented deactivation of the electrodes. The deactivation effect was associated with an increased hydrogen flux through the electrodes indicative of an elevated hydrogen concentration at the electrode surface. This high surface concentration is concluded to be the result of nickel hydride phase formation at the surface of the nickel electrodes. The iron coating prevents this surface phase from forming and hence prevents deactivation of the electrode.     

The electrodeposition of Mn and Zn-Mn alloys from the room-temperature tri-1-butylmethylammonium bis((trifluoromethane)sulfonyl)imide ionic liquid

Zinc, manganese and zinc-manganese alloys were electrodeposited from the hydrophobic room-temperature ionic liquid, tri-1-butylmethylammonium bis((trifluoromethane)sulfonyl)imide. Zn(II) and Mn(II) species needed to produce these alloys were introduced into the ionic liquid by the anodic dissolution of the respective metallic electrodes. The diffusion coefficients of the dissolved Zn(II) and Mn(II) species are not constant, but decrease with the increasing concentrations of these ions, suggesting the formation of aggregated species at higher concentrations. Coatings containing Zn, Mn or Zn-Mn can be obtained by controlled-potential electrolysis. The current efficiencies of Mn electrodeposition in this ionic liquid approach 100%, which is a high improvement comparing to the results obtained in aqueous solution (20-70%). The Mn/Zn ratio of these alloys depended almost completely on Mn(II)/Zn(II) concentration ratio in the ionic liquid. The Zn-Mn alloy deposits obtained in this study were compact, adherent, and exhibited an amorphous structure. The surface morphology of these deposits depended on the Mn/Zn ratio. The addition of Mn up to about 50 a/o improves the corrosion resistance of Zn. However, the addition of Mn beyond this amount decreases the corrosion resistance of the Zn-Mn alloy.     

Zn-Ni合金电沉积过程中的渗氢行为

用电化学渗氢测试方法探讨了氯化物体系、硫酸盐-氯化物混合体系电沉积Zn-N i合金镀层过程中的渗氢行为。结果表明,氯化物体系比硫酸盐-氯化物混合体系渗氢电流小,用电镀过程中的氢覆盖率和镀层孔隙率对渗氢特点进行了解释。     

复合电沉积镍钼合金的Taguchi设计

镍钼合金镀层用于电极表面处理能提高其析氢催化性能。采用Ｔａｇｕｃｈｉ试验设计镍钼合金电镀工艺。阐述了Ｔａｇｕｃｈｉ设计方法的原理,通过正交试验优出一种镍钼合金电镀的最佳工艺,大大降低了镍钼合金镀层的析氢性能。     

钛合金化学镀Ni-P合金前处理工艺的研究

研究了浸蚀、浸锌等前处理过程对钛基体渗氢及化学镀Ni-P合金镀层与基体结合力的影响。结果表明,采用混酸浸蚀液,可以有效除去钛合金表面的钝化膜,控制基体中的渗氢量;二次浸锌得到的Ni-P合金镀层结合力较好,镀层均匀、紧密,镍晶粒尺寸较小。     

Study of the hydrogen absorption in Pd in alkaline solution

Hydrogen adsorption/absorption in palladium thin deposits on gold electrode, in 0.1 M NaOH solution, was studied. The contributions of adsorption and absorption to the total charge of hydrogen are separated from the total isotherms at different deposit thicknesses. The adsorbed hydrogen charge increases to a plateau of ∼73.5 μC cm⁻², which corresponds to the surface coverage ratio by adsorbed hydrogen of 0.36. The absorbed hydrogen charge agreed with that obtained from the permeation experiments at 50 μm Pd foil, at potentials between +100 and +300 mV vs. RHE. EIS was carried out at thin Pd deposits. The kinetics of hydrogen sorption is slower in alkaline solutions than in acids and the isotherms are shifted towards more negative potentials.     

Preparation of supported thin palladium-silver alloy membranes and their characteristics for hydrogen separation

Studies have been made on the characterization of composite membranes, consisting of a palladium-silver alloy film on the outer surface of an inorganic porous support, for hydrogen separation. The membranes were prepared in the manner of consecutive electroless-plating of palladium and silver, and then heat treatment in a stream of argon. As high temperatures above 1073 K were required to form a miscible palladium-silver alloy film, thermally durable porous alumina ceramic was selected as the support. The membranes thus prepared had a complete selectivity for hydrogen separation and they exhibited an extremely high rate of hydrogen permeation compared with commercial palladium-based membranes. For instance, permeation was about 30 times faster when 23 wt.% silver was melted to give a film thickness of 5.7 μm. The high rate of hydrogen permeation is a result of enhanced hydrogen solubility into the metal film as well as its reduced thickness.     

Surface alloy/GC电催化剂的制备与结构表征

以玻碳为载体 ,通过电化学方法在其表面沉积催化物质研制表面合金纳米电催化剂 (Surfacealloy/GC)。运用电化学循环伏安 (CV)和扫描电镜 (SEM)等技术进行结构和性能表征。结果表明 ,在Surfacealloy/GC上氢的析出电位负移至 - 0 40V(SCE) ,与Pt电极相比负移约 15 0mV ,具有较高的电还原应用价值。另外 ,Surfacealloy/GC的氧化电位正移至 0 64V ,其稳定性明显高于电有机合成中常用的Pb、Sb、Cu等金属电极。SEM研究结果表明 ,所研制的Surfacealloy/GC电催化剂是一种由粒度约为 70nm的纳米颗粒合金组成的薄膜     

化学镀铜对贮氢电极高倍率放电性能的影响

以A2B7型贮氢合金La1.5Mg0.5Ni6.5Co0.5为对象,用不同浓度硫酸溶液浸蚀合金粉末进行化学镀铜,系统研究了未包覆以及表面包覆Cu后对La1.5Mg0.5Ni6.5Co0.5合金电极动力学性能的影响,从动力学的角度对贮氢电极高倍率放电性能进行了分析. 结果表明,与未包覆Cu相比,包覆后合金电极的交换电流密度增大且随着H2SO4浓度的增加而增大. 其极限电流也逐渐增大,从H2SO4浓度为0.025 mol/L时的2166.01 mA/g增加到0.1 mol/L时的2681.93 mA/g. 合金电极中氢的扩散速率得到不同程度的提高. 表明化学镀铜能有效地提高贮氢合金电极吸、放氢过程的动力学性能. 其高倍率放电性能的改善是源于电极表面的电子迁移速率和氢在合金体相中扩散速率共同作用所引起的.     

梯度电流密度下电沉积制备铜-镍-钼合金电极及其性能研究

采用梯度电沉积法制备铜基Cu–Ni–Mo合金电极,电流密度参数为:10 mA/cm^2×5 min+30 mA/cm^2×40 min+50 mA/cm^2×5 min。通过扫描电子显微镜(SEM)、能谱仪(EDS)、X射线衍射仪(XRD)和X射线光电子能谱仪(XPS)分析了Cu–Ni–Mo合金镀层的表面形貌、元素组成、相结构和各元素的化学价态,并通过线性扫描伏安曲线(LSV)、电化学阻抗谱(EIS)和计时电流法对比了Cu–Ni和Cu–Ni–Mo合金电极在1 mol/L KOH溶液中的析氢性能和稳定性。结果表明,所得Cu–Ni–Mo合金镀层是呈花椰菜多孔形貌的非晶态结构。与Cu–Ni合金电极相比,Cu–Ni–Mo合金电极具有更大的比表面积,可为析氢反应提供更多活性位点,表现出更好的析氢性能,稳定性也更好。     

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。     

Pt、Rh及Pt-Rh合金电极上氢的吸附

The hydrogen adsorption on Pt-Rh alloys in sulfuric acid aqueous solutions was studied by the method of cathode pulses. Hydrogen adsorption on the electrode with all ratio of alloy components (ωRh = 0-100%) is well described by the Temkin logarithmic isotherm. The surface coverage by adsorbed hydrogen at the same potential is decreased with increasing content of rhodium in the system. A linear dependence of adsorption peak potential on the alloy compositions in the case of weakly bonded adsorbed hydrogen is established. Hydrogen adsorption heat as a function of surface coverage for Pt-Rh-electrodes was obtained. The shape of the current-potential curve and position of the weakly bonded hydrogen adsorption on the potential scale are all related to alloy compositions, thus can serve as the basis for the determination surface composition of allovs.     

电沉积Zn-Fe合金的渗氢行为研究

用双电解池测氢法研究氯化物镀液体系中电沉积Zn-Fe合金过程中的渗氢行为.结果表明:在所考察的工艺参数中,镀液pH值对渗氢电流的影响最大.用慢应变速率拉伸试验法(SSRT)考察了电镀Zn-Fe合金试样的氢脆特性,并用扫描电子显微镜(SEM)对断口的微观形貌进行了表征.所有Zn-Fe合金镀层的试样均显示出不同程度的氢脆敏感性.     

Promotion of the electrochemical hydrogenation of nitrobenzene at hydrogen storage alloys studied using a solid electrolyte method

The electrocatalytic properties of an AB₅-type hydrogen storage alloy towards the electrochemical hydrogenation of unsaturated organic compounds have been studied by a solid electrolyte method using electrochemical hydrogenation of nitrobenzene as a model reaction. Voltammetric studies reveal that the kinetics of the nitrobenzene electro-reduction on the hydrogen storage alloy electrode is similar to that on a Ni electrode. Aniline and p-aminophenol are produced as the reaction products. Compared to the Ni electrode, the production of aniline is considerably promoted on the hydrogen storage alloy electrode. Modifying the alloy surface with a thin layer of Cu enhances the reaction selectivity and current efficiency for aniline formation. Compared to a Cu electrode, the electrochemical hydrogenation of nitrobenzene to aniline is promoted on the Cu-modified alloy electrode. The hydrogenation promotion effect is attributed to the chemical reaction between nitrobenzene and metal hydrides that are electrochemically generated in situ. Hydrogen storage alloys therefore make it possible to intensify the electrochemical hydrogenation process of unsaturated organic compounds.     

Hydrogen permeation inhibition by thin layer Zn–Ni alloy electrodeposition

The inhibition of hydrogen permeation by zinc-nickel electrodeposited alloy was investigated using the Devanathan–Stachurski permeation technique. The hydrogen evolution and hydrogen permeation rates for the zinc–nickel alloy electrodeposits on iron are compared with the rates for bare iron, zinc electroplated on iron, and nickel electroplated on iron. Hydrogen evolution rates and hydrogen permeation rates were followed as functions of time at different applied potentials. The hydrogen permeation inhibition for thin zinc–nickel electroplates (20s at 10mAcm–2 and 10s at 20mAcm–2) averaged 80% and intermediate to that of nickel and zinc. This inhibition was considered to be mostly due to kinetic effects. Zinc–nickel electroplated for 20 and 40min. at 10mAcm–2 inhibited the hydrogen permeation greater than 95% as compared to bare iron. This inhibition was due to both kinetics and the barrier effect caused by the diffusion resistance of the membrane.     

Electrodeposition of Zn-Co alloys with pulse containing reverse current

The electrodeposition of Zn-Co alloy deposits was studied by means of pulse-plating technique. The surface morphologies of Zn-Co alloy deposits were examined using scanning electron microscopy (SEM), and an attendant energy dispersive X-ray analyser (EDA) was used to analyse the composition of Zn-Co alloy deposits. Results obtained showed that the average current density and reverse current density amongst all the variables investigated had very strong effects on the cobalt content in the Zn-Co alloy deposits. It is possible to electrodeposit Zn-Co alloy coatings with a very wide cobalt content range of 10-90 wt.% by modulating pulse parameters. Grain size, surface appearance and internal stress in the deposits were also improved significantly by introducing reverse current.     

添加元素对Zr1-xTix(NiCoMnV)2.1电极性能的影响

通过添加不同的导电剂和添加剂,制备了Zr1-xTix(NiCoMnV)2.1贮氢合金负极片,测试了不同负极片的放电容量. 结果表明：以镍粉为导电剂的Zr1-xTix(NiCoMnV)2.1负极片性能明显高于以碳黑为导电剂的负极片, 添加银粉的负极片初始容量能达到215 mA×h/g,平台K值大于90%.     

碳载Sb-Pb-Pt电催化纳米材料的制备与结构表征

:通过电化学方法在玻碳表面沉积催化物质研制Sb Pb Pt合金纳米材料。运用循环伏安(CV)、石英晶体微天平 (EQCM)、扫描隧道显微镜 (STM)和X 光电子能谱 (XPS)等技术对其进行表征。结果指出 ,碳载Sb Pb Pt电催化纳米材料的稳定性明显高于电有机合成中常用的Pb和Sb等电极。在酸性介质中碳载Sb Pb Pt电催化纳米材料电极上氢的析出电位负移至 - 0 45V ,有较高的电还原应用价值。通过EQCM技术对纳米薄膜合金电极的形成过程进行原位跟踪和STM观察 ,表明所研制的Sb Pb Pt纳米材料是由粒度均匀的纳米颗粒组成的合金薄膜。     

Electrochemical characteristics of hydrogen storage alloys modified by electroless nickel coatings

Multicomponent hydrogen storage alloy with the composition MmNi_3.31Mn_0.37Al_0.28CO_0.64 (Mm = misch metal consisting of 24.87% La, 52.56% Ce, 5.57% Pr, 16.86% Nd and 0.14% Sm) was used as a negative electrode material. To improve the performance of the negative electrode, the alloy particles were modified with various electroless Ni-P and Ni-B coatings. Electrochemical properties such as discharge capacity and high-rate dischargeability of the negative electrode were generally improved by the surface modifications. However, in the case of a Ni-P (10 wt % P) coating, the discharge capacity and high-rate dischargeability decreased with increasing thickness, due to the low hydrogen permeability and high electric resistivity of the coating. Consequently, both kinds of coating and their thickness are critical factors in determining the performance of such a negative electrode.     

A novel model equation for the permeation of hydrogen in mixture with carbon monoxide through Pd–Ag membranes

Hydrogen permeance decrease, owing to the covalent interaction of carbon monoxide with the Pd–Ag membrane surface, represents a considerable drawback, since this decreases the efficiency of the alloy membranes. This work proposes a novel Sieverts–Langmuir's model taking into account the mentioned adsorption. The proposed model equation, in order to take into account the fraction of the membrane surface not active for hydrogen permeation, introduces Langmuir's isotherm, which is the surface loading in the classical Sieverts’ permeation equation. The evaluation of the parameter and the Langmuir affinity constant involved in the proposed model was carried out using experimental data measured using a 60 μm thick Pd–Ag commercial membrane at 647 K (374 °C), up to a total pressure of 700 kPa. The presented model yields, in a parametric form, a quantitative assessment of hydrogen permeance decrease caused by the adsorption of gases on Pd–Ag membrane surfaces. Therefore, this novel Sieverts–Langmuir's equation models hydrogen permeation through Pd–Ag-based membranes in the presence of inhibitor gases such as CO. In addition, by ab initio evaluation of the and the Langmuir affinity constant, the proposed Sieverts–Langmuir's equation can identify a new membrane with better efficiency.