(华南理工大学 化学与化工学院 广东省燃料电池技术重点实验室，广州 510640)
摘 要: 采用线性电势扫描、循环伏安和计时电流研究50 ℃下Cl-、BSP、RPE单独存在或同时存在时，在含320 g/L CuSO4？5H2O、110 g/L H2SO4溶液中，Cu在铜电极上的电沉积过程，并通过SEM和XRD表征无添加剂和添加30 mg/L Cl-+5 mg/L BSP+5 mg/L RPE后得到的铜箔的形貌和结构。结果表明：Cl-、BSP在Cu的电沉积过程中起着去极化作用，RPE随着浓度的增大极化作用逐渐增强；BSP使成核数密度增大，但同时会降低铜离子的扩散系数，添加30 mg/L Cl-+5 mg/L BSP+5 mg/L RPE会增大表观传递系数和扩散系数，加快Cu的电沉积过程；在Cl-、RPE以及30 mg/L Cl-+5 mg/L BSP+5 mg/L RPE作用下，Cu的电沉积都是在开始时接近瞬时成核，随着时间延长，向连续成核靠近，最终偏离理论模型；而在BSP作用下，始终接近瞬时成核理论。添加30 mg/L Cl-+5 mg/L BSP+ 5 mg/L RPE可以在50 ℃高浓度酸铜溶液中快速电沉积得到光亮平整的电解铜箔，铜镀层呈现(111)晶面较大择优取向。
关键字: 电解铜箔；聚氧乙烯聚氧丙烯嵌段化合物；电沉积；添加剂；扩散系数
（School of Chemistry and Chemical Engineering, South China University of Technology,
Guangdong Key Laboratory of Fuel Cell Technology, Guangzhou 510640, China）
Abstract:The copper electrodepositions on copper electrode in the solutions containing 320 g/L CuSO4？5H2O and 110 g/L H2SO4 with Cl-, BSP, RPE alone or combination at 50 ℃ were studied by linear sweep voltammetry, cyclic voltammetry and chronoamperometry. The morphology and structure of electrolytic copper foil with additive free and 30 mg/L Cl-+5 mg/L BSP+5 mg/L RPE were characterized by SEM and XRD. The results show that Cl- and BSP have depolarization effect in the electrodeposition process, but the polarization effect of RPE increases with the increase of RPE concentration. BSP can increase the nuclear number density, but reduce the diffusion coefficient of Cu ion. 30 mg/L Cl-+5 mg/L BSP+5 mg/L RPE can increase the apparent transfer coefficient and diffusion coefficient, and speed up the copper electrodeposition process. At beginning, the electrodeposition process follows the instantaneous nucleation approximately, and then changes to the progressive nucleation with increasing time, but the process would deviate from the theoretical model after longer nucleation time with Cl-, RPE, 30 mg/L Cl-+5 mg/L BSP+5 mg/L RPE. It will always follow the instantaneous nucleation in the presence of BSP. Bright leveling electrolytic copper foil can be got at high speed with 30 mg/L Cl-+5 mg/L BSP+5 mg/L RPE at 50 ℃ in the concentrated acid copper sulfate solutions. The resulting copper coating has an orientation along (111) crystal plane.
Key words: electrolytic copper foil; polyxyethylene-polyoxypropylene glycals; electrodeposition; additive; diffusion coefficient
