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Study on Charge Transfer Reactions in Electrodeposition

电沉积中电荷转移反应的研究

基本信息

批准号：
15560021
负责人：
SAITOU Masatoshi
金额：
$ 2.43万
依托单位：
University of the Ryukyus
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2003
资助国家：
日本
起止时间：
2003 至 2004
项目状态：
已结题

项目摘要

(1)Charge transfer reactions in the Helmholtz layer in electrodepositionElectrochemical impedance spectroscopy measurements under a small alternating current density were performed to make investigations into electrochemical reactions on (110) single-crystalline nickel surfaces in nickel sulfamate electrolyte. The reaction impedance shows a power law of the ac modulation frequency and two exponents for the reaction resistance and reaction capacitance are found to agree with the values predicted by a homogeneous charge-transfer reaction model. In addition, the Nyquist diagrams exhibit the absence of inductive loops. A condition for the existence of inductive loops derived in this study suggests that the electrocrystallization of Ni^<2+> ions may take place in the slow reaction step Ni^<2+>+e^-→Ni^+_<abs> and in the fast reaction step Ni^+_<abs>+e^-→Ni.(2)Transient process in the Helmholtz layer in electrodepositionA method is described for the study of the kinetics of electrode reaction … More s on the basis of analytical solutions of three transient electrochemical processes comprising the diffusion of ions, charge-transfer reactions and a charging process of an electrochemical double-layer. Multi-pulse currents are applied to a working electrode and the potentials are recorded. The measured potential-time curves agree with those predicted by the analytical solution. The kinetic constant, exchange current density and double-layer capacitance are determined from the measured potential-time curves using the analytical solution.(3)Surface nucleation and growth in electrodepositionVoltage-time curves in surface growth on single crystalline nickel electrodes in nickel sulfamate have been measured under a fixed current density with a nanosecond rise-time. The transient voltage-time curves in a two-electrode system exhibit three continuous regions that correspond to the reduction of nickel ions by two-step electrochemical reactions, the crystallization process such as nucleation and growth, and steady state surface growth. The measured voltage-time curves are well consistent with the calculation results predicted by phenomenological equations proposed in this study. Less

(1)电沉积亥姆霍兹层中的电荷转移反应为了研究氨基磺酸镍电解液中(110)单晶镍表面的电化学反应，进行了小交流密度下的电化学阻抗谱测量。反应阻抗显示了交流调制频率的幂律，并且发现反应电阻和反应电容的两个指数与均相电荷转移反应模型预测的值一致。此外，奈奎斯特图显示不存在感应环路。本研究推导的感应环存在的条件表明，Ni^<2+>离子的电结晶可能发生在慢反应步骤Ni^<2+>+e^-→Ni^+_<abs>和快反应步骤Ni^+_<abs>+e^-→Ni。 (2)电沉积中亥姆霍兹层的瞬态过程描述了一种研究电极反应动力学基于三个瞬态电化学过程的分析解决方案，包括离子扩散、电荷转移反应和电化学双层的充电过程。将多脉冲电流施加到工作电极并记录电势。测量的电位-时间曲线与解析解预测的一致。使用解析溶液从测量的电位-时间曲线确定动力学常数、交换电流密度和双层电容。(3)电沉积中的表面成核和生长在氨基磺酸镍中的单晶镍电极上在纳秒上升时间的固定电流密度下测量了表面生长的电压-时间曲线。双电极系统中的瞬态电压-时间曲线呈现出三个连续区域，分别对应于两步电化学反应镍离子的还原、成核和生长等结晶过程以及稳态表面生长。测量的电压-时间曲线与本研究提出的唯象方程预测的计算结果非常一致。较少的