酸性镀铜工艺及镀层特性
(华南理工大学 化学与化工学院 广东省高等学校新能源技术重点实验室, 广州 510640)
摘 要: 锂离子电池用负极集流体铜箔材料目前主要采用电沉积法制备。为制备良好的电解铜箔，采用不同电镀工艺参数，在基于三乙醇胺(TEA)和乙二胺四乙酸二钠(EDTA·2Na)双络合体系的CuSO4/H2SO4溶液中进行镀铜工艺研究。通过线性扫描、循环伏安、SEM 和XRD手段对镀液性质、镀层微观形貌和结构进行测定和表征，并进行镀层质量重复性实验。结果表明：选择含P 0.1%的磷铜作为阳极，采取机械搅拌镀液的方式，在CuSO4·5H2O为300 g/L、H2SO4为90 g/L、Cl−为40~80 mg/L、TEA为3.5 g/L和EDTA·2Na为5 g/L中适量添加剂P的镀液中，以电流密度为490 mA/cm2，镀液温度为40~60 ℃，施镀5~10 min能得到良好镀层；添加剂明显降低循环伏安阴极峰电流，Cu2+的还原速度减慢；添加剂提高镀层表面的结晶细化程度，使晶体颗粒变小，致密性提高，镀层质量变好，整平作用明显，Cu镀层呈现(111)晶面择优取向；镀速可达19.4 mg/min，镀层质量有很好的重现性。
关键字: 电解铜箔；TEA；EDTA·2Na；镀速；槽电压；择优取向
coating properties based on system of TEA and EDTA·2Na
（Key Laboratory of New Energy Technology for Guangdong Universities, School of Chemistry and Chemical Engineering,
South China University of Technology, Guangzhou 510640, China）
Abstract:The copper foils for the anode current collectors of lithium-ion battery were prepared by electrodeposition. In order to obtain better electrodeposited copper foils, considering different electroplating technology parameters, the copper electrodepositing process based on the system of TEA and EDTA·2Na was studied in CuSO4/H2SO4 electrolytes. The morphology and structure of coating were characterized by SEM and XRD, and the property of electrolyte was tested by linear sweep voltammetry and cyclic voltammetry. The reproducibility of coating was also tested. The results show that a good coating can be got in the better condition that is as follows: 0.1% phosphor bronze as the anode, mechanical stirring, CuSO4·5H2O (300 g/L), H2SO4(90 g/L), Cl−(40−80 mg/L), TEA(3.5 g/L), EDTA·2Na (5 g/L), appropriate amount of additive P, current density (490 mA/cm2), bath temperature(40−60 ℃) and deposition time(5−10 min). The additives remarkably decrease the cathode peak current of cyclic voltammetry and slow down the reduction rate of copper ions. The additives can improve the crystallization refinement of the coating, reduce crystal particles and raise the compactness, owing to its significantly leveling effect. The copper coating has an orientation along (111) crystal plane. The deposition rate reaches up 19.4 mg/min, and the coating quality has good reproducibility.
Key words: electrodeposited copper foil; TEA; EDTA·2Na; deposition rate; bath voltage; preferred orientation
