(華南理工大學(xué) 化學(xué)與化工學(xué)院 廣東省燃料電池技術(shù)重點(diǎn)實(shí)驗(yàn)室，廣州 510640)
摘 要: 采用線性電勢(shì)掃描、循環(huán)伏安和計(jì)時(shí)電流研究50 ℃下Cl-、BSP、RPE單獨(dú)存在或同時(shí)存在時(shí)，在含320 g/L CuSO4？5H2O、110 g/L H2SO4溶液中，Cu在銅電極上的電沉積過(guò)程，并通過(guò)SEM和XRD表征無(wú)添加劑和添加30 mg/L Cl-+5 mg/L BSP+5 mg/L RPE后得到的銅箔的形貌和結(jié)構(gòu)。結(jié)果表明：Cl-、BSP在Cu的電沉積過(guò)程中起著去極化作用，RPE隨著濃度的增大極化作用逐漸增強(qiáng)；BSP使成核數(shù)密度增大，但同時(shí)會(huì)降低銅離子的擴(kuò)散系數(shù)，添加30 mg/L Cl-+5 mg/L BSP+5 mg/L RPE會(huì)增大表觀傳遞系數(shù)和擴(kuò)散系數(shù)，加快Cu的電沉積過(guò)程；在Cl-、RPE以及30 mg/L Cl-+5 mg/L BSP+5 mg/L RPE作用下，Cu的電沉積都是在開(kāi)始時(shí)接近瞬時(shí)成核，隨著時(shí)間延長(zhǎng)，向連續(xù)成核靠近，最終偏離理論模型；而在BSP作用下，始終接近瞬時(shí)成核理論。添加30 mg/L Cl-+5 mg/L BSP+ 5 mg/L RPE可以在50 ℃高濃度酸銅溶液中快速電沉積得到光亮平整的電解銅箔，銅鍍層呈現(xiàn)(111)晶面較大擇優(yōu)取向。
關(guān)鍵字: 電解銅箔；聚氧乙烯聚氧丙烯嵌段化合物；電沉積；添加劑；擴(kuò)散系數(shù)
（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
