Investigation of electrochemical reactions on copper electrode in Cu4RbCl3I2 solid electrolyte

Investigations are carried out by potentiostatic method. It is found that at potentials ϕ less than 100 mV, a reaction rate of copper deposition is limited by the formation and the three-dimensional growth of copper nuclei and the rate of copper dissolution is limited by a two-dimensional growth of holes in the metal. The rate of nucleus growth was evaluated at 10⁻⁹...10⁻⁶ μm s⁻¹ depending on the potential. At ϕ>120 mV, the reaction rate is limited by charge transport at the exchange current density of 2.7 mA cm⁻² and the anodic transfer coefficient α_a≈ 0.45. The accumulation of a divalent copper phase on Cu/Cu₄RbCl₃I₂ interface at anodic polarization is explained by a parallel course of Cu⁺ − e → Cu²⁺ reaction.     

Highly Conducting and Flexible Radical Crystals

Together with high conductivity, high flexibility is an important property required for next generation organic electronic components. Both properties are difficult to achieve together especially when the components are crystalline because of the intrinsic high brittleness of organic molecular crystals. We report an organic radical crystal system that has both high flexibility and high conductivity. The crystal consists of 9,10‐bis(phenylethynyl)anthracene radical cation ( BPEA^.+ ) units, and shows flexibility under pressure with high conductivity in ambient condition exhibiting average conductivity of 2.68 S cm^?1 when normal linear shape, as well as 2.43 S cm^?1 when bent. The structural analysis reveals that both a short π–π distance (3.290 Å) between BPEA^.+ units that are aligned along the crystal length direction, and the presence of PF₆^? counter ions induce flexibility and high electrical conductivity.     

Temperature evolution for small particles formed during electrocrystallization

It is shown, by analyzing heat balance of a cluster formed during electrochemical crystallization, that the cluster temperature passes through maximum and can achieve the melting point in the crystallization initial stage. This allows preparing amorphous deposits.     

Electric fields in the rheology of disperse systems

In the present survey, the influence of electric fields on the structure and rheological properties of disperse systems as well as the effect of deformations on their electrical characteristics are discussed. The properties of these systems are considered in terms of the dielectric permittivity and electrification potential. The considerable thickness of the double electric layer around the disperse phase particles, which is characteristic of disperse systems with nonpolar hydrocarbon dispersion media, provides the possibility for strong electric fields to produce an electric nonuniformity on the surface of the disperse phase particles. The formation of hydrate layers on the particles creates the possibility of polarization of the disperse phase. In plastic disperse systems such as greases, a strong orientation effect is observed, which contributes to the creation of frozen flow patterns when the flow is suddenly stopped. The survey is concluded with a consideration of the process of formation of chain structures in the direction of the lines of force of the electric field whose orientation is normal to the direction of flow, which can lead to complete stoppage of the flow.     

Polynuclear crystal growth in electrocrystallization of silver: Determining the nucleus size via the nucleation theorem

We employ the nucleation theorem for a model-independent determination of the size of the two-dimensional (2D) Ag nucleus with the aid of experimental data for nucleation-mediated electrochemical crystal growth. The growth is investigated of a screw dislocation-free Ag(100) single crystal face in aqueous solution of AgNO₃ at 318 K. The data are for the stationary values of the overpotential during galvanostatic pulses with sufficiently high amplitudes to ensure polynuclear growth mechanism. It is found that the Gibbs-Thomson equation of the classical theory of 2D nucleation describes very well the experimentally obtained overpotential dependence of the size of the 2D Ag nucleus. Published in Russian in Elektrokhimiya, 2008, vol. 44, No. 6, pp. 698–703. The text was submitted by the authors in English.     

CuCl2硅溶胶和水溶液中铜的电化学行为研究

采用循环伏安法和计时安培法研究了CuCl2硅溶胶和水溶液中铜在玻碳电极上的电沉积和电结晶行为.结果表明在两种CuCl2电解质中,铜的电沉积分两个步骤完成,Cu2+还原为Cu+在硅溶胶中较水溶液中容易;采用吸附-成核模型解析电流-时间暂态曲线,并确定铜的电结晶机理为扩散控制下的连续成核三维生长(3DP),Cu2+在水溶液中的扩散系数较硅溶胶中的大,但相同电位下在硅溶胶中的饱和成核数密度高于水溶液中.     

氯离子对铜在玻碳电极上电结晶的影响

采用线性扫描伏安法和计时安培法研究了硫酸铜溶液中铜在玻碳电极上电结晶 的初期行为。在含与不含氯离子的0.05mol·L~(-1) cUso_4-0.5 mol·L~(-1) H_2SO_4电解液中,循环伏安实验结果表明铜在玻碳基体上的沉积没有经过UPD过 程;氯离子明显使Cu的沉积和氧化峰变得尖锐,促进Cu的沉积速度。计时安培实验 结果表明,Cu的电结晶按瞬时成核和三维生长方式进行。氯离子不改变Cu的结晶机 理,但在I～t曲线中,导致电流达最大(I_m)所需的时间t_m减小、晶核数密度和生 长速度增大,从而明显改变Cu沉积层的质量。当Cl~-浓度在10～20mg·L~(-1)范围 内,成核的晶核数密度达较大,即氯离子的最适宜添加量。     

Copper electrodeposition into ion-exchange materials

Electrodeposition of copper into spherical granules of ion-exchange materials KU-23 and KU-2 out of acid sulfate solutions is studied by a method of cyclic voltammetry. It is discovered that the discharge of copper ions in an ion-exchange matrix is characterized by a cathodic overvoltage that is higher than the overvoltage of the same process on a graphite substrate by 0.08 V, which is most probably connected with a limited mobility of ions localized at fixed groups [RSO ₃ ^? ]. The cyclic voltammogram exhibits an additional cathodic peak in the potential region corresponding to the reduction of single-charged copper ions that form as a result of their accumulation inside pores of the ion-exchange matrix during anodic dissolution of metal deposited previously. It is fixed microscopically that the process of deposition begins at the graphite substrate/ion-exchanger interface and passes into bulk upon the formation of an electron-conducting layer saturated with copper. Preliminary saturation of the ion-exchanger by copper deposited chemically facilitates uniform electrodeposition of copper over the entire volume of pores of the ion-exchange matrix.     

添加剂对锌电结晶行为的影响及参数的演化优化

用电位阶跃方法研究了氯化钾镀锌溶液中不同添加剂(OP-10,苄基苯基酮,NNO和CH-1光亮剂)存在时锌在玻碳电极上的电结晶行为;同时针对传统求解电结晶动力学参数方法的不足,设计出一种基于实数编码的遗传算法通过拟合恒电位暂态曲线,演化优化求得动力学参数(晶核密度数N~0和位置转移为晶核的速率常数A)和金属离子扩散系数D,并在些基础上对演化求得的参数进行了分析和讨论。结果表明,使用此遗传算法对整条曲线拟合优化出的参数更为合理,可用来解释添加剂对锌在玻碳电极上的电结晶的影响机理。