高氢过电位Zn-In合金电沉积规律和性能的研究

用电化学方法研究了碱性锌锰电池铜集流体上电沉积Zn-In合金的方法,测量了Zn-In合金在7.0mol/L氢氧化钾溶液中的析氢性能以及合金中各组分的含量.结果表明,在硫酸盐体系中Zn-In合金电沉积为异常共沉积.在碱性体系中Zn-In合金具有较高的析氢过电位,可以用作碱锰电池的集流体镀层材料.     

稀土铈对镍-钴-磷合金电极的析氢催化性能的影响

采用自行研制的复合配合剂,用化学沉积法在酸性体系中制备了Ni-Co-P和Ni-Co-P稀土合金电极.研究了稀土元素铈对Ni-Co-P合金电极的析氢电催化活性和电化学稳定性的影响.通过电化学方法测定合金电极在7 mol/L KOH溶液中的阴极极化曲线、Tafel曲线和电化学稳定性曲线,结果表明,与Ni-Co-P合金电极相比,Ni-Co-P(RE)合金电极的析氢电位正移约90 mV,Ni-Co-P(RE)合金电极具有较优的析氢电催化活性和电化学稳定性.此外,还通过X射线衍射、扫描电镜和合金镀层成分分析,结果表明,稀土元素铈的加入使非晶态Ni-Co-P合金镀层晶粒细化,但稀土元素铈不与合金共沉积,只是起到改变镀层组织结构的作用.     

Ni-W-TiO2复合镀工艺及其镀层性能研究

为了进一步提高Ni-W合金镀层的析氢电催化活性,用电沉积方法制备了Ni-W-TiO2复合镀层,通过阴极极化曲线和交流阻抗等电化学技术研究了其在碱性溶液中的析氢电催化活性,并用扫描电镜观察了电极的表面形貌.结果表明,在Ni-W合金中掺入TiO2微粒可增大电极的比表面积,并改变Ni-W合金在碱性介质中的析氢反应机理.Ni-W-TiO2复合镀层有较高的析氢电催化活性,可用作电解水反应的活性电极.     

离子液体中电沉积钴铬合金析氢性能研究

为了研究电沉积合金材料的析氢性能,本文在离子液体中通过脉冲电沉积法在碳钢上制备钴铬合金,研究了离子液体中电沉积不同的钴盐浓度对析氢过电位的影响,并与离子液体中电沉积的Co电极和Cr电极,水溶液中电沉积的Co-Cr合金电极进行了对比分析。利用三电极体系测试沉积电极在碱性环境下的电化学性能,采用线性极化法、方波电位法、交流阻抗法、恒电流电解法等电化学测试方法,并结合XRD、SEM、EDS进行了形貌、物相与元素分析。实验结果表明：制备的Co-Cr合金是多晶的,其晶粒尺寸为12.3 nm;当电流密度为10和100 mA/cm²时,所对应的析氢过电位分别为-105和-408 mV;当塔菲尔斜率为-0.228 V/dec时,析氢电阻为2.45Ω,计算得到其微观表面积为647 cm²;合金中Cr的质量分数约为8.5%,Co的质量分数约78.5%。随着钴盐浓度的上升,电沉积的钴铬合金电极的析氢性能越来越好。在离子液体中,通过脉冲电沉积制备的Co-Cr合金电极具有出色的电化学析氢性能,析氢机理为析氢反应动力学中的Volmer-Heyrovsky反应机理,析氢性...     

Electrochemical properties of amorphous Ni-S-Co alloy in alkaline medium

用电沉积方法制备非晶态Ni-S-Co合金镀层, 研究了镀层的电化学性能. 结果表明,与非晶态Ni--S合金相比, Co的引入可提高镀层中S的含量.在析氢反应中非晶态Ni--S--Co合金电极具有很高的电化学活性,电流密度为150 mA×cm-2时其析氢过电位仅为70 mV,比非晶态Ni-S合金低20 mV.在长时间电解过程中S发生溶出反应有助于提高电极的表面粗糙程度, 是提高电极析氢活性的重要原因之一. 在析氢过程中,非晶态Ni--S--Co合金电极吸附大量的H原子, 使反应的活化能降低,这是其析氢活性高的主要原因. 非晶态Ni--S--Co合金镀层的析氢机理为电化学脱附机理,即一快速的Volmer反应(电化学步骤)和一较慢的Heyrovsky反应(电化学脱附步骤).     

非晶态Ni-S-Co合金的制备和电化学性能

用电沉积方法制备非晶态Ni-S-Co合金镀层,研究了镀层的电化学性能.结果表明,与非晶态Ni-S合金相比,Co的引入可提高镀层中S的含量.在析氢反应中非晶态Ni-S-Co合金电极具有很高的电化学活性,电流密度为150 mA·cm-2时其析氢过电位仅为70 mV,比非晶态Ni-S合金低20 mV.在长时间电解过程中S发生溶出反应有助于提高电极的表面粗糙程度,是提高电极析氢活性的重要原因之一.在析氢过程中,非晶态Ni-S-Co合金电极吸附大量的H原子,使反应的活化能降低,这是其析氢活性高的主要原因.非晶态Ni-S-Co合金镀层的析氢机理为电化学脱附机理,即-快速的Volmer反应(电化学步骤)和一较慢的Heyrovsky反应(电化学脱附步骤).     

AC/ Ni-Co 复合电极材料的制备及其催化析氢性能

采用复合电沉积法制备了AC(活性炭) / Ni-Co 复合电极。XRD 和SEM 测试结果表明, AC 微粒的复合未改变Ni-Co 合金电极的物相结构, 但使镀层的表面粗糙度和真实表面积增大。通过稳态阴极极化曲线和电化学交流阻抗技术考察了不同电极在1 mol·L-1 NaOH 溶液中的催化析氢性能, 结果表明, 镀液中AC 含量为3 g·L-1时所制备的AC/ Ni-Co 复合电极较Ni 电极和Ni-Co 合金电极具有更高的催化析氢活性, 电流密度为30 mA·cm-2时, 析氢反应极化电位分别比Ni 电极和Ni-Co 合金电极正移230 mV 和140 mV , 表观交换电流密度分别是Ni 电极和Ni-Co 合金电极的42 倍和9 倍, 复合电极催化析氢性能的提高主要归因于电极真实表面积的增大。      

Ni-S-Co涂层电极的制备及其电化学性能的研究

采用电沉积的方法以泡沫镍为基体制备出非晶Ni-S-Co合金电极.用电化学测试方法分析涂层的电化学行为.结果表明,较好的制备涂层电极条件为: CoSO4·7H2O掺杂浓度为10g/L,电流密度为50mA/cm2,温度为50℃,电沉积时间为40min,pH值为4.当电解电流密度为1200A/m2时,非晶Ni-S-Co合金电极的极化电位较非晶Ni-S合金电极低95mV,较Ni金属电极低405mV;根据Tafel曲线计算出Ni、非晶Ni-S以及非晶Ni-S-Co电极的表面活化能分别为49.5、40.3和38.6kJ/mol.Ni-S-Co电极具有更高的交换电流密度和更低的析氢活化能,因此具有更高的析氢催化活性.     

复合电沉积制备（Ni-Mo）-TiO2电极及其电催化析氢性能

为开发新型廉价高效的析氢材料,用恒电流复合电沉积方法制备了(Ni-Mo)-TiO2复合电极,讨论了TiO2悬浮量和电沉积时间对电极催化析氢性能的影响.用XRD和SEM对电极的晶体结构和表面形貌进行了表征,以稳态极化曲线对电极的催化析氢特性进行了评价.结果表明,(Ni-Mo)-TiO2电极是纳米TiO2粒子相和纳米晶Ni-Mo固溶体相构成的复合电极.电极具有较高的催化析氢活性.在25℃、0.5mol.dm-3H2SO4溶液中其表观交换电流密度是Ni-Mo合金电极的2.6倍,是Ni电极的60倍.在电流密度为100mA·cm-2时,电极电势相对于Ni-Mo电极正移了120mV,相对于Ni电极正移了542mV.催化活性的提高源于反应机理的改变,表观活化吉布斯自由能相对于Ni-Mo合金电极降低了24.48kJ·mol-1.     

FeCoNiMoCr高熵合金薄膜电极的电催化析氧性能

用磁控溅射法在Ti基底上沉积了FeCoNiMoCr高熵合金薄膜并制成电极,用SEM和EDS观察和分析了电极表面和横截面的形貌和元素分布,用表面轮廓测量仪测量了电极的表面粗糙度,用XRD分析了电极的物相和结构,使用电化学工作站表征了电极的电化学性能。结果表明,电极的表面粗糙、元素分布均匀,电极上的膜厚约为2.40 μm,薄膜呈非晶态。电极在碱性溶液中表现出良好的析氧性能和稳定性。在电流密度为10.0 mA/cm²条件下,过电位为360 mV、Tafel斜率为73.45 mV/dec。在过电位为360 mV的条件下连续使用24 h,电流密度没有明显的衰减。循环伏安实验和电化学阻抗分析的结果表明,FeCoNiMoCr高熵合金薄膜本征催化活性的提高使电极的电催化析氧性能优于贵金属RuO₂(过电位为409 mV,Tafel斜率为94.18 mV/dec)。     

电镀镍-钴合金对La-Mg-Ni基贮氢合金电化学性能的影响

为了改善La-Mg-Ni基贮氢合金的循环稳定性和综合电化学性能,研究了电镀镍-钴合金对La0.88Mg0.12Ni2.95Mn0.10Co0.55Al0.10贮氢合金粉末表面形貌和电极电化学性能的影响.FESEM表明,电镀处理后合金粉末表面沉积了球状的镍-钴合金颗粒.电化学性能测试表明,贮氢合金电极的放电容量、高倍率放电性能和循环稳定性均得到了显著改善.200周循环时合金电极的容量保持率从未处理合金电极的60%提高到镀覆镍-钴合金的80%,在放电电流密度1080mA/g下的高倍率放电性能提高了23%.线性极化曲线和电化学阻抗分析结果显示,包覆镍-钴合金后贮氢合金电极表面的电荷转移速率加快,电催化活性提高.     

Electrochemical reactions oh iron silicide surfaces in sulphuric acid

The electrochemical behaviour of pure FeSi₂ and FeSi electrodes has been examined in sulphuric acid solutions over a wide range of cathodic and anodic potentials. The potentiodynamic profiles exhibit a structureless hysteresis and thence shed no light on the possible pseudo-faradaic processes that might be involved.

Potentiostatic steady-state curves for the hydrogen evolution reaction (h.e.r.) show that the h.e.r. can be carried out at these electrodes at very high rates without affecting their electrochemical stability; for the sake of comparisons, the electroactivity of these electrodes is much less than that of smooth platinum but much higher than that of the commercially-available Ebonex electrodes made of ceramic titanium dioxide.

On the anodic side, oxide growth, rather than the evolution of oxygen, is the favoured process. Also, little activity is detected, at low electrode potentials (<3 V), for the anodic oxidation of HCOC⁻, CH₃COO⁻, CH₃OH, NH₂−NH₂ and Cl⁻. When the electrochemical reactions are forced at high rates through a galvanostatic arrangement, oxide growth to very high electrode potentials and dielectric breakdown are observed in all solutions except those containing chloride ions; in the latter case anodic evolution of chlorine is observed.     

化学镀Ni-Co-W-P及其析氢性能的研究

用化学镀方法制备出Ni-Co-W-P合金电极,测量了其在1 mol/L NaOH溶液中的阴极极化曲线并研究了其析氢电催化活性.试验表明,在相同的电流密度下,Ni-Co-P,Ni-W-P和Ni-Co-W-P合金电极的析氢过电位较Fe电极降低,其中Ni-Co-W-P的析氢过电位降低约230 mV,XRD试验显示其镀层为非晶态.并进一步测试了其在7 mol/L KOH中的连续电解曲线.结果表明:Ni-Co-W-P合金电极比Ni-Co-P,Ni-W-P合金电极具有更好的析氢电催化活性和电化学稳定性,有利于降低槽压,减少能耗.     

Distribution of sulphur and electrochemical properties of nickel sulphur coatings electrodeposited on the nickel foam as hydrogen evolution reaction cathodes

Nickel sulfur electrode was prepared on the nickel foam by electrodeposition method in a modified Watts bath into which thiourea, citric acid and a small amount of saccharin were added. The micrographs of various layers of nickel sulphur coatings were investigated by SEM. The distributions and mass contents of sulphur in nickel sulphur coatings were measured by EDX. The phase constitutions of the first layer of nickel sulphur coating were determined by XRD. The influence of current density on coating structures was studied. The hydrogen evolution potentials of various electrodes, including nickel sulphur coatings on foam and net nickel substrates, pure nickel foam and nickel net were measured. Results indicated that the distributions of sulphur contents in various layers are gradient and not homogeneous, the sizes of fine particles in various layers are not the same. XRD examinations show that the structure of the nickel sulphur coating is amorphous. With increase of current density the amorphous structures gradually increase and the crystal ones gradually decrease. In the range of sulphur contents from 18% to 18.8% the electrochemical activities of Ni–S coating electrodes are the highest. The hydrogen evolution reaction activity of amorphous Ni–S coatings on the nickel foam substrate is much higher than that on the nickel net substrate.     

退火处理对A2B7型La0.63(Pr0.1Nd0.1Y0.6Sm0.1Gd0.1)0.2Mg0.17Ni3.1Co0.3Al0.1储氢合金相结构和电化学性能的影响

利用高频感应熔炼法制备La0.63(Pr0.1Nd0.1Y0.6Sm0.1Gd0.1)0.2Mg0.17Ni3.1Co0.3Al0.1储氢合金,对铸态合金在900℃下退火热处理24h。结构分析表明,铸态合金微观组织由CaCu5型结构、Ce5Co19型结构及Ce2Ni7型结构三相组成,而退火合金则是单相Ce2Ni7型结构。铸态和退火合金电极均具有良好的活化性能,退火合金电极放电曲线更为平坦和宽阔。两种合金电极腐蚀电位基本一致,但铸态合金电极腐蚀电流更大。合金经过退火后其电极循环稳定性(S100=83.5%)明显优于铸态合金电极(S100=69%)。在100次电化学充放电循环内,低容量充电时,退火合金电极容量不衰减,合金电极容量衰减的充电容量临界点为活化最大放电容量(Cmax)的90%。铸态和退火合金电极动力学性能差别不大,铸态合金电极高倍率放电主要由氢在其体相中扩散控制,退火合金电极高倍率放电则主要由其表面电荷转移控制。     

碱液中镍电极的析氢机理

研究镍电极在碱液中的析氢机理对开发二次清洁能源有指导意义,过去对其研究不够.通过Tafel曲线和电化学阻抗谱对镍电极在KOH溶液中的析氢机理进行了研究.结果表明,过电位低于600 mV时,析氢服从复合脱附机理,反应历程为电化学步骤+复合脱附步骤;过电位高于600 mV时,析氢服从迟缓放电机理或电化学脱附机理,反应历程为电化学步骤+电化学脱附步骤.     

Effect of copper electroless coatings on the interaction between a molten Al–Si–Mg alloy and coated short carbon fibres

The role of electroless copper coatings applied on short carbon fibres on the interaction between an aluminium alloy (Al–Si–Mg) and coated fibres has been studied to get useful information for the fabrication of carbon fibre reinforced aluminium matrix composites by liquid or semi-liquid processing. The conditions used for electroless were optimized to obtain a uniform and continuous layer of copper. After characterization, uncoated and Cu coated carbon fibres were mixed with AA 6061 aluminium powders, compacted and heated at temperatures from 650 to 950 °C to study the reactivity and the resulting interface. To complete this study, differential thermal analysis (DTA) were carried out on compacted mixtures of aluminium alloy powders with Cu coated and uncoated carbon fibres, applying similar thermal cycles than for the composite manufacturing. The results show an important improving of reinforcement wetting by molten matrix when copper coatings are applied, jointly with a reduction of the alloying elements microsegregation in the matrix, unlike the composites manufactured with uncoated fibres. Additional microhardness and nanoindentation tests were carried out to study the effect of the copper incorporation from the coating to the matrix on the matrix response to the ageing hardening.     

Selective, electrochemically activated biofunctionalization of In2O3 nanowires using an air-stable surface modifier

Selective electrochemically activated biofunctionalization of In(2)O(3) nanowires (NWs) has been achieved, using monolayer coatings of p-dimethoxybenzene derivatives. Monolayer coatings of 4-(2,5-dimethoxyphenyl)butyl-phosphonic acid (DMP-PA) were deposited on planar indium-tin oxide (ITO) electrodes and In(2)O(3) NWs. The electrochemical behavior of the monolayer coating was first studied using ITO electrodes, as a model system for In(2)O(3) nanowires. When a potential of 950 mV vs a Ag/AgCl reference electrode is applied to an ITO electrode coated with DMP-PA in PBS buffer, the p-dimethoxyphenyl groups are converted to p-benzoquinone (BQ). The electrochemically formed benzoquinone groups react readily with alkyl thiol groups via a Michael addition. The reaction strategy optimized on ITO was applied to an In(2)O(3) NW mat sample coated with DMP-PA. Applying a potential of 950 mV to metal electrodes deposited on NWs converts the DMP-PA NW coating to BQ-PA, which reacts with a thiol-terminated 20-base oligonucleotide. These NWs showed strong fluorescence response after paring with the dye labeled compliment, demonstrating that the probe was bound to the NW surface and that it remained active toward hybridization with its compliment. The unactivated DMP-PA coated NWs showed no response, demonstrating the selective electrochemical functionalization of NWs and the potential of using them in multiplex sensing. We also compared the p-dimethoxybenzene derivative to the conventional hydroquinone analog. The results show that the former can largely enhance the selectivity during the functionalization of both ITO and In(2)O(3) NWs.     

铜导线表面热浸镀PbSn合金镀层的组织与性能

为了改善铜导线的可焊性和耐蚀性,采用热浸镀技术在铜导线表面制备Pb40Sn60和Pb37Sn63两种成分的低熔点合金镀层,利用扫描电镜(SEM)、能谱分析(EDS)、X射线衍射(XRD)等分析手段和电阻率检测实验、拉伸实验、中性盐雾实验等方法,系统研究其微观组织、相成分、电阻率、力学性能及耐蚀性。结果表明:Pb40Sn60和Pb37Sn63两种成分的合金镀层均由α相和β相两相组成,镀层的电阻率分别约为2.6832×10^-3,2.5929×10^-3Ω·m,均高于铜基体。铜导线热浸镀Pb40Sn60和Pb37Sn63两种成分合金镀层后的表面硬度分别为13.4,12.6HV0.2;抗拉强度分别为193,180 MPa;伸长率分别为35%和37%,与铜基体相比均降低。铜导线表面热浸镀PbSn合金镀层具有良好的导电性、力学性能及耐腐蚀性等综合性能。随着Pb含量的降低或Sn含量的增加,PbSn合金镀层中α相的相对量减少、β相的相对量增大,其电阻率、硬度和强度降低,塑性略有增大,耐蚀性增强。Pb40Sn60比Pb37Sn63合金镀层的腐蚀速率较高,分别为2.44×10^-2,3.65×10^-3 g·cm^-2·a^-1,耐腐蚀性较差。PbSn合金镀层中α相比β相的腐蚀程度更为严重,α相比β相的耐蚀性要差。