健那绿及其复合添加剂作用电解铜箔组织性能研究

刘家良; 李永乐; 廖洁娜; 张云朋; 刘俊; 黄剑; 齐亮; 杨红光; 齐素杰; 樊小伟

doi:10.16490/j.cnki.issn.1001-3660.2026.14.020

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表面技术 ›› 2026, Vol. 55 ›› Issue (14) : 224-233. DOI: 10.16490/j.cnki.issn.1001-3660.2026.14.020

功能表面及技术

健那绿及其复合添加剂作用电解铜箔组织性能研究

刘家良^1a,1b,2, 李永乐^1a,1b, 廖洁娜^1a,1b, 张云朋^1a,1b,2, 刘俊^1a,1b,2, 黄剑^1a,2, 齐亮^1c,2, 杨红光³, 齐素杰³, 樊小伟^1a,1b2,*

作者信息 +

Influence of Janus Green and Its Compound Additives on Microstructure and Properties of Electrolytic Copper Foil

LIU Jialiang^1a,1b,2, LI Yongle^1a,1b, LIAO Jiena^1a,1b, ZHANG Yunpeng^1a,1b,2, LIU Jun^1a,1b,2, HUANG Jian^1a,2, QI Liang^1c,2, YANG Hongguang³, QI Sujie³, FAN Xiaowei^1a,1b,2,*

Author information +

文章历史 +

摘要

目的电解铜箔作为锂离子电池负极集流体与印制线路板的导体材料,其力学性能和表面质量直接受电解液添加剂影响。方法开发了一种含健那绿复合添加剂体系,采用直流电沉积制备低轮廓锂电铜箔,提升抗拉强度,满足锂电池对高力学性能的需求。结果实验通过分子能级计算,结合LSV、SEM、CLSM、XRD、EBSD分析以及力学拉伸测试,研究健那绿（JGB）作用电沉积铜箔组织结构。添加Cl^-使单一JGB的去极化行为整体转变为协同作用的极化行为,初始沉积电位由-0.22 V负移至-0.25 V。由于JGB的分子轨道能级差ΔE仅1.14 eV,电子结构容易发生轨道相互作用,表现出更强的强配位与界面吸附能力,阻碍Cu²⁺还原,进而抑制铜快速沉积。加入1 mg/L的JGB时,铜箔表面粗糙度降低至1.25 μm,衍射峰呈晶面(220)择优取向的织构T_c为81.10%。添加硫脲（TU）,初始沉积电位进一步负移至-0.27 V,TU分子含—NH₂和C==S基团,发生Cu²⁺配位,与JGB产生电化学拮抗协同作用,增强阴极极化。TU的分子轨道能级差ΔE大至6.02 eV,主要表现在分子中具有孤对电子的硫原子上,优先吸附在铜沉积表面的高能活性位点,促使铜箔平整沉积,降低表面粗糙度。此外电结晶的晶体结构转变为致密的晶面(111)取向生长,并形成细晶强化机制。结论最终实现VMS+Cl^-+JGB+TU体系获得粗糙度1.17 μm、晶粒尺寸0.56 μm、抗拉强度607 MPa、延伸率2.10%的高性能铜箔。

Abstract

Copper foil is a conductor material for the negative electrode current collector of lithium batteries. Its mechanical properties and surface quality are directly affected by the additives in the electrolyte. A complex additive system containing Janus green is developed. Low-profile lithium battery copper foils are prepared by direct current electroplating, and the tensile strength is enhanced to meet the high mechanical property requirements of lithium batteries. The experiment studies the microstructure of copper foils electrodeposited with Janus green (JGB) through Molecular energy level calculation, LSV, SEM, CLSM, XRD, EBSD analysis and mechanical tensile tests. The depolarization of single JGB transforms into polarization with adding Cl^-, which is manifested by the initial deposition potential shifting from -0.22 V to -0.25 V negatively, and the overpotential increases by 0.03 V. Through density functional theory (DFT) calculation, the LUMO energy level of JGB is mainly distributed on the N atom and the N atom connected to the benzene ring, making these regions the preferred sites for electrophilic reactions. The HOMO energy level is concentrated on the N and C atoms coordinated with Cl^-, indicating that this area is the preferred site for nucleophilic reactions and is prone to preferential adsorption. Due to the small energy level difference ΔE (1.14 eV) of JGB, the electronic structure is more prone to orbital interaction, demonstrating a stronger ability for strong coordination and interface adsorption. It hinders the reduction of Cu²⁺ and thereby suppresses the rapid deposition of copper. Adding 1 mg/L of JGB reduces the surface roughness of the electrodeposition copper foils to as low as 1.25 μm, and the texture T_c with diffraction peaks showing a preferred orientation of the crystal plane (220) is 81.10%. Adding thiourea (TU), the initial deposition potential further shifts negatively to -0.27 V. The overpotential increases by 0.02 V, which is less than the influence of JGB. Because the energy level difference ΔE of TU is as large as 6.02 eV. Meanwhile, the LUMO energy levels of TU are uniformly distributed across the molecule, while the HOMO energy levels are mainly concentrated on the S atom. The sulfur atom in the thiourea molecule has lone pairs of electrons, which preferentially adsorb at the high-energy active sites on the copper deposition surface, inhibiting the rapid growth of the deposited grains. So the added thiourea (TU) molecule which containing —NH₂ and C==S groups, coordinates with Cu²⁺, and generates an electrochemical antagonistic synergistic effect with JGB, and both the additives enhance cathodic polarization. The result is promoting a smooth surface of the deposition, and reducing the roughness. Compared with the large grain size of 0.97 μm in the base solution (VMS) that only contains Cl^-, the electrocrystallization crystal structure of plating solution containing additives transforms into a dense crystal plane (111) with directional growth, and forms a fine-grained strengthening mechanism. Finally, the VMS+Cl^-+JGB+TU system is implemented to obtain high-performance copper foils, which include a roughness of 1.17 μm, a grain size of 0.56 μm, a tensile strength of 607 MPa, and an elongation of 2.1%.

导出引用

刘家良, 李永乐, 廖洁娜, 张云朋, 刘俊, 黄剑, 齐亮, 杨红光, 齐素杰, 樊小伟. 健那绿及其复合添加剂作用电解铜箔组织性能研究[J]. 表面技术. 2026, 55(14): 224-233

LIU Jialiang, LI Yongle, LIAO Jiena, ZHANG Yunpeng, LIU Jun, HUANG Jian, QI Liang, YANG Hongguang, QI Sujie, FAN Xiaowei. Influence of Janus Green and Its Compound Additives on Microstructure and Properties of Electrolytic Copper Foil[J]. Surface Technology. 2026, 55(14): 224-233

中图分类号： TB37

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