Effect of Halide Ions on Electrodeposition Behavior and Morphology of Electrolytic Copper Powder

K. Ochi, M. Sekiguchi, S. Oue, Hiroaki Nakano
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Abstract

To investigate the e ff ect of halide ions on the electrodeposition behavior and morphology of copper powder, the polarization curves were measured and constant current electrolysis of 300A·m − 2 and 500A·m − 2 was conducted in an electrolytic solution of 0.079mol·dm − 3 of Cu 2+ and 0.5mol·dm − 3 of free H 2 SO 4 at 293K and 303K without stirring. In the deposition of copper powder, Cl − had a promoting e ff ect on the deposition of copper powder, while Br − and I − had a suppressing e ff ect. The current e ffi ciency for Cu deposition increased with the addition of Cl − and decreased with Br − . The addition of Cl − reduced the average particle size of the copper powder and grown dendrite – shaped branches and trunks, resulting in a lower tap density. On the other hand, when Br − was added, the average particle size and crystallite size of the copper powder became smaller, and the tap density also became smaller. With increasing Cl − concentration in solution, the current e ffi ciency for Cu deposition increased, that is, copper deposition was promoted even in the di ff usion rate – determining region of Cu 2+ ions, showing that the deposition of copper powder was a ff ected by the charge transfer process for Cu deposition. The change in morphology of Cu powder with halide ions is attributed to change of the charge transfer process. The deposition of Cu powder seems to proceed under a mixed rate – determining process of the di ff usion of Cu 2+ ions and charge transfer. [ doi:10.2320 / jinstmet.J2021008 ]
卤化物离子对电解铜粉电沉积行为及形貌的影响
为了研究卤化物离子对铜粉电沉积行为和形貌的影响,测量了极化曲线,并在0.079mol·dm−3 cu2 +和0.5mol·dm−3自由h2so4的电解溶液中,在293K和303K下,以300A·m−2和500A·m−2恒流电解,不搅拌。在铜粉沉积过程中,Cl−对铜粉的沉积有促进作用,而Br−和I−对铜粉的沉积有抑制作用。Cu沉积的电流效率随Cl−的加入而增加,随Br−的加入而降低。Cl−的加入降低了铜粉的平均粒径,形成了枝晶状的枝干,从而降低了铜粉的密度。另一方面,当添加Br−时,铜粉的平均粒径和晶粒尺寸变小,丝锥密度也变小。随着溶液中Cl−浓度的增加,Cu沉积的电流效率增加,即在cu2 +离子扩散速率决定区也促进了铜的沉积,说明铜粉的沉积受到Cu沉积电荷转移过程的影响。卤化物离子铜粉的形貌变化是由于电荷转移过程的改变引起的。铜粉的沉积过程似乎是在Cu 2+离子扩散和电荷转移的混合速率决定过程中进行的。[doi:10.2320 / jinstmet.]J2021008]
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