在LiCl-KCl-CeCl3熔盐中铝电极上欠电位沉积制备Al-Ce合金

在843K LiCl-KCl-CeCl3熔盐中活性铝电极上,研究了Ce(III)离子的电化学行为和欠电位沉积Al-Ce合金。对比循环伏安曲线发现,在Al电极上Ce(III)/Ce反应的氧化还原电势比在Mo惰性电极上更正;开路计时电位在金属铝和铈的沉积平台之间出现两个平台,这表明Ce(III)在Al活性电极上可以生成两种金属间化合物。以上结果在电化学机理上说明Ce(III)离子可以在Al电极上欠电位沉积形成金属间化合物。在该实验条件下通过恒电位电解,在Al电极上得到了Al-Ce合金,验证了理论分析的结果。经XRD表征,证实了形成AlCe和AlCe3两种合金;经SEM和EDS表征,证明了铈分布在Al电极表面厚度均一的合金镀层中（厚度28?m）。 关键词：LiCl-KCl熔盐;欠电位沉积;铝电极;Al-Ce合金     

LiF-MgF_2-BaF_2-KCl熔盐Mg~(2+)在钨电极上的电化学还原机理

采用循环伏安法、计时电流法、计时电位法研究以MgO为原料、LiF-MgF_2-BaF_2-KCl为电解质体系、温度为1173 K时镁离子在钨电极上的电化学还原过程。结果表明:镁离子在钨电极上的电化学还原是一步转移两个电子的过程,电极反应为Mg~(2+)+2e→Mg;镁在钨电极析出过程中出现成核极化现象,析出过程是受扩散控制的不可逆反应;1173 K时,Mg~(2+)在熔盐中的扩散系数D为1.28×10-5 cm2/s。     

电沉积制备La-Mg-Ni贮氢合金薄膜及其性能的研究

采用恒电流沉积方法在水溶液中沉积出LaMgNi4合金薄膜。利用循环伏安、模拟电池充放电循环、扫描电镜(SEM)以及X射线衍射(XRD)等方法研究了电沉积合金薄膜的电化学性能和表面形貌及结构。结果表明,该合金薄膜作为贮氢电极具有较好的电化学性能,其电化学活性高,活化性能好,首次充放电比容量达398mAh/g。     

在LiCl-KCl-CeCl_3熔盐中铝电极上欠电位沉积制备Al-Ce合金（英文）

在843 K LiCl-KCl-CeCl_3熔盐中活性铝电极上,研究了Ce(Ⅲ)离子的电化学行为和欠电位沉积Al-Ce合金。对比循环伏安曲线发现,在Al电极上Ce(Ⅲ)/Ce反应的氧化还原电势比在Mo惰性电极上更正;开路计时电位在金属铝和铈的沉积平台之间出现2个平台,这表明Ce(Ⅲ)在A1活性电极上可以生成两种金属间化合物。以上结果在电化学机理上说明Ce(Ⅲ)离子可以在Al电极上欠电位沉积形成金属间化合物。在该实验条件下通过恒电位电解,在Al电极上得到了Al-Ce合金,验证了电化学分析的结果。经XRD表征,证实形成了AlCe和AlCe_3两种合金,结合Al-Ce合金相图分析了只产生这两种合金的原因;结合开路电位计算了生成这两种合金的标准吉布斯自由能变值。经SEM和EDS表征,证明了铈在Al电极表面分布,并形成厚度均一约28μm的Al-Ce合金镀层。     

熔盐电解法制备铝-钪合金电解质体系电化学性质研究

熔盐体系的电化学性质对熔盐电解过程有很大影响,通过选用铝电解工业通用的冰晶石-氧化铝体系作为熔盐电解制取铝钪合金的基本电解质体系,采用循环伏安法、线性伏安法和稳态极化法对Sc3+在冰晶石熔盐体系中铝电极上的电化学还原过程及氧化钪在石墨电极上的分解电压进行研究.结果表明,Sc3+在熔盐中电解还原过程为一步获得三个电子的简单电荷传递过程.     

LiCl-KCl熔盐中共沉积直接电化学形成不同相Al-Y合金（英文）

在773 K的LiCl-KCl-AlCl_3-Y_2O_3熔盐体系中,采用循环伏安、方波伏安、开路计时电位和稳态极化研究了不同相的Al-Y合金的电化学制备过程。电化学研究表明钇在预先沉积的铝上欠电位沉积形成了2种铝钇金属间化合物。X射线衍射研究表明:这2种Al-Y金属间化合物为Al_2Y和α-Al_3Y。通过金相显微镜和电子扫描显微镜对合金样品进行了表征,结果显示钇元素主要分布于块状析出物上。通过调节熔盐中AlCl_3的含量可以获得不同相的Al-Y合金。     

锂离子在铝电极上的电极过程机理

利用线性扫描伏安法详细研究了锂离子在铝电极上的电极过程机理。锂在铝电极上的电极过程受锂在βＬｉＡｌ合金相中的扩散控制，扩散是通过空穴机制完成的。为电化学方法制备锂铝合金阳极提供了极限参考电压和电流，并计算了βＬｉＡｌ合金形成的活化能     

熔体旋淬Ml(NiCoMnAl)_5贮氢合金的微结构与电化学行为

研究了熔体旋淬和常规熔铸Ml(NiCoMnAl) 5贮氢合金的微结构和电化学行为。SEM和XRD分析表明 ,熔体旋淬合金由细小的柱状晶组成 ,它们的晶体结构与铸态一样 ,都为CaCu5型六方晶体结构。电化学测试表明 ,旋淬态合金电极初始容量较高 (>2 10mA·h/ g) ,经 1～ 2次循环就可达到最大放电容量。旋淬速度为 10m/s的合金电极的放电容量 (2 94mA·h/g)稍高于铸态合金电极的容量 ,所有旋淬态合金电极充放电循环稳定性皆优于铸态合金。在 6 0 0mA/ g电流质量密度下 ,旋淬速度为 10m/s的合金电极具有较好的高倍率充放电能力 ,但随着循环次数的增加 ,其容量稳定性稍次于旋淬速度为 2 5m/s和 40m/s的合金电极。     

Pb(Ⅱ)在LiCl-KCl-MgCl_2-PbCl_2熔盐体系中的电化学行为(英文)

在LiCl-KCl-PbCl2-MgCl2熔盐体系中借助循环伏安和计时电位技术对Pb(Ⅱ)的电化学行为以及Pb、Mg、Li的共沉积过程进行探讨,用不同的方法测算得到铅离子在熔盐中的扩散系数。循环伏安和计时电位的研究结果均表明,Li在先析出的Pb上发生欠电位沉积,生成液态的Li-Pb合金,而在熔盐中加入MgCl2后,会有相应的Mg-Li-Pb合金生成。用恒电流密度(6.21A/cm2)电解2h制备Mg-Li-Pb合金,并运用XRD对所得合金进行分析测试。结果表明,在Mg-Li-Pb合金中存在β-Li、PbLi3、Mg2Pb等合金相,并可以通过控制熔盐中PbCl2和MgCl2的浓度来改变合金相的组成。     

熔体旋淬Ml（NiCoMnAl）5贮氢合金的微结构与电化学行为

研究了熔体旋淬和常规熔铸Ml(NiCoMnAl)5贮氢合金的微结构和电化学行为。SEM和XRD分析表明,熔体旋淬合金由细小的柱状晶组成,它们的晶体结构与铸态一样,都为CaCu5型六方晶休结构。电化学测试表明,旋淬态合金电极初始容量较高（＞210mA.h/g)经1－2次循环就可达到最大放电容量。旋淬速度为10m/s的合金电极的放电容量（294mA.h/g)稍高于铸态合金电极的容量。所有旋淬态合金电极充放电循环稳定性皆优于铸态合金,在600mA/g电流质量密度下,旋流速度为10m/s的合金电极具有较好的高倍率充放电能力,但随着循环次数的增加,其容量稳定性稍次于旋淬速度为25m/s和40m/s的合金电极。     

Study of electrolyte effects on electrochemical synthesis and p-doping of poly(thienyl biphenyl) films

The electrochemical synthesis and charging–discharging process of a copolymer consisting of 3-octylthiophene (3-OT) and biphenyl units have been studied in different electrolytic media. The polymer material has been characterized by electrochemical and spectroscopic methods: cyclic voltammetry (CV), electrochemical quartz crystal microbalance (EQCM), chronopotentiometry, chronoamperometry and FTIR spectroscopy. The diffusion coefficients of different ions in poly(thienyl biphenyl) (PTB) films have been determined by chronoamperometry and compared with corresponding values in poly(3-octylthiophene) (POT) and poly(paraphenylene) (PPP). The best electrolytic conditions for synthesis of poly(thienyl biphenyl) concerning the copolymer structure was found to be in 0.1 M lithium hexafluoro arsenate (LiAsF₆) in acetonitrile. In this electrolyte solution, the content of phenylene segments compared to thienylene segments is highest resulting in a higher degree of cross-linking compared with films made in the presence of the other electrolyte salts studied.     

Electrochemical properties of the MmNi3.55Mn0.4Al0.3Co0.4Fe0.35 compound

In this paper, the electrochemical properties of the MmNi_3.55Mn_0.4Al_0.3Co_0.4Fe_0.35 alloy used as a negative electrode in Ni–MH accumulators, have been investigated by different electrochemical methods such as cyclic voltammetry, chronopotentiometry, chronoamperometry and electrochemical impedance spectroscopy. The experimental results indicate that the discharge capacity reaches a maximum value of 260 mAh g⁻¹ after 12 cycles and then decreases to about 200 mAh g⁻¹ after 70 cycles. The value of the mean diffusion coefficient D_H, determined by cyclic voltammetry, is about 3.44 × 10⁻⁹ cm² s⁻¹, whereas the charge transfer coefficient , determined by the same method, is about 0.5 which allows us to conclude that the electrochemical reaction is reversible. The hydrogen diffusion coefficients in this compound, corresponding to 10 and 100% of the charge state, determined by electrochemical impedance spectroscopy, are, respectively, equal to 4.15 × 10⁻⁹ cm² s⁻¹ ( phase) and 2.15 × 10⁻⁹ cm² s⁻¹ (β phase). These values are higher, for the phase and less, for the β phase, than the mean value determined by cyclic voltammetry. We assume that this is related to the number of interstitial sites susceptible to accept the hydrogen atom, which are more numerous in the phase than in the β phase. The chronoamperometry shows that the average size of the particles involved in the electrochemical reaction is about 12 μm.     

Electrochemical mechanism of electrolysis codeposition of Mg-Sr alloy in molten salt

The electrochemical process of Mg-Sr codeposition was studied in MgCl₂-SrCl₂-KCl melts containing different MgCl₂ concentrations at 700 °C by cyclic voltammetry, chronopotentiometry and chronoamperometry. The results show that the actual precipitation potential of Sr reduces by nearly 0.5 V because of the depolarization effects of Sr activity reduced by forming Mg-Sr alloy. The codeposition potential condition of Mg and Sr to form Mg-Sr alloy is as follows: When electrode potential is more negative than ?1.5 V, the magnesium will precipitate; when electrode potential is more negative than ?2.0 V, the magnesium and strontium will both deposit. The control step of codeposition process of Mg and Sr is not diffusion control step. The codeposition current condition of Mg and Sr to form Mg-Sr alloy by chronoptentiometry is as follows: cathode current densities are higher than 0.71, 1.57 and 2.83 A/cm² in MgCl₂-SrCl₂-KCl melts with MgCl₂ concentrations of 2%, 5% and 10% (mass fraction), respectively.     

1-乙基-3-甲基-咪唑四氟硼酸盐离子液体中镝电沉积行为

研究室温下Pt电极上Dy3+离子在1-乙基-3-甲基-咪唑四氟硼酸盐(EMIMBF4)离子液体中的电化学行为。循环伏安法结合计时电流法和计时电位法研究结果表明,Dy3+离子的电化学还原是不可逆过程,还原为一步完成,即Dy3++3e-→Dy。计时电流法结合恒电位电解研究表明,Dy3+离子的还原过程受扩散控制。测得浓度0.01mol/L的Dy3+离子在0.1mol/LLiCl-EMIMBF4离子液体中的传递系数、扩散系数分别为0.176和(4.87-5.04)×10-10cm2/s。SEM和XRD分析表明,金属镝颗粒直径为几百纳米。     

锡电极嵌锂过程的交流阻抗谱

采用交流阻抗谱研究锡电极的首次嵌锂和第二次嵌锂过程,对比锡纳米阵列电极、锡薄膜电极和锡箔3种不同材料微观结构对电极交流阻抗谱特征的影响。用等效电路模型分析交流阻抗谱,得到嵌锂过程电化学特征参数与电位关系。结果表明:锡纳米阵列电极与锡薄膜、锡箔电极具有不同交流阻抗谱特征,锡纳米阵列电极在中频区出现双电层阻抗;首次嵌锂时在1.6~0.8 V之间形成固体电解质膜(SEI);电极材料微观结构显著影响锡电极的SEI膜电阻、Warburg阻抗和锂离子扩散速率;锡纳米阵列电极上的SEI膜电阻和Warburg阻抗最小,锂离子扩散能力最强;锡纳米阵列电极上锂的扩散系数为4.4×10-15~1.4×10-11 cm2/s;锂扩散系数随电位变化显著。     

Electrochemical behaviors of Bi (Ⅲ) in dimethylsulfoxide

Cyclic voltammetry, chronoamperometry and chronopotentiometry were used to investigate the electrochemical behaviors of Bi(b!) in Bi(NO3)3-LiClO4-DMSO (dimethylsulfoxide) system on Pt and Cu electrodes. Experimental results indicated that the electroreducation of Bi(b!) to Bi(0) was irreversible on Pt and Cu electrodes. The diffusion coefficient and electron transfer coefficient of Bi(b!) in 0.01 mol     

Electrodeposition of Li and electrochemical formation of Mg–Li alloys from the eutectic LiCl–KCl

The electrochemical behavior of Li⁺ was studied at the inert and active electrodes in the molten LiCl–KCl eutectic. Transient electrochemical techniques, such as cyclic voltammetry, chronoamperometry and chronopotentiometry were used in order to explore the deposition mechanism of Li. The reduction process of Li⁺ is irreversible and the diffusion coefficient of Li⁺ at 723 K was determined as 6.68(±0.07) × 10⁻⁶ cm² s⁻¹. During the electrodeposition process of Li, the electrocrystallization played an important role. The chronoamperometric studies indicated that instantaneous nucleation existed during the electrodeposition process of Li metal. At a Mg electrode, the electroreduction of Li⁺ takes place at a less cathodic potential values than that at Mo electrode which indicated the formation of Mg–Li alloy. The Mg–Li alloy films with different crystal phase were obtained by potentiostatic electrolysis, and the samples were characterized by X-ray diffraction and scanning electron microscopy.     

Redox behavior of indium in molten chlorides

An electrochemical study on the redox behavior of indium in the eutectic LiCl-KCl system at 450 °C was carried out with the transient techniques of cyclic voltammetry and chronopotentiometry on an inert molybdenum electrode. The reduction of In(III) was found to be a two-step process involving In(III)/In(I) and In(I)/In couples at the potentials of about ?0.4 and ?0.8 V versus Ag/AgCl, respectively. The redox mechanism was further confirmed by the theoretical evaluation of the number of transferred electrons based on cyclic voltammetry and characterizations of the precipitates generated by the potentiostatic electrolysis. The diffusion coefficients of indium ions in the eutectic LiCl-KCl melt at 450 °C were estimated by cyclic voltammetry and chronopotentiometry. The results obtained through the two methods are in fair agreement, delivering an average diffusion coefficient of approximately 1.8×10^?5 cm²/s for In(III), and 1.4×10^?4 cm²/s for In(I).     

Electrodeposition of dixanthogen（TETD） on pyrite surface

The electrochemical reaction of xanthate on the surface of pyrite was studied using cyclic voltammogrametry, chronopotentiometry and rotating-disc electrode measurements.Experimental results demonstrate that the first step in the reaction is electrochemical adsorption of xanthate ion,and then the adsorbed ion associates with a xanthate ion from the solution and forms a dixanthogen on the pyrite electrode surface.The diffusion coefficient of butyl xanthate on pyrite electrode surface can be determined to be about 1.09×10- 6cm2/s.Using the galvanostatic technique,the kinetic parameters of oxidation of the butyl xanthate ion on the pyrite surface are calculated as Ja=200μA/cm2 ,β=0.203 and J0=27.1μA/cm2.