电沉积铜箔的微观组织结构——三维电结晶模式中的电结晶机理探讨

doi:10.13208/j.electrochem.210448

摘要/Abstract

摘要：

电沉积铜箔随着印刷线路板和锂离子电池的大量应用而越来越受到重视,产业规模仍在发展中。相对于电镀设备的制造和电沉积工艺的开发,但有关电沉积的机理方面的研究较少。本文总结了电沉积铜箔的制造过程并分析了不同电沉积铜技术中各电镀参数的差异,指出电沉积电流密度在铜箔形成过程中的重要作用。通过展示和比较不同电沉积铜箔的微观组织结构,讨论了电沉积中各影响因素对铜箔微观组织结构以及对其宏观机械性能的影响。从前人研究结果中发现电沉积条件和镀液组分对铜箔微观组织形貌及其宏观机械性能有重大影响,但电解铜箔的晶粒大小、织构等微观组织结构参数与其宏观机械性能间无法建立起有效的关联,这对以镀层的微观组织结构为桥梁来建立电沉积条件对铜箔宏观机械性能的理论框架带来极大的困扰。前人试图通过研究铜箔电沉积机理来解决这一难题。经典金属电沉积理论认为提高过电位能够增加瞬时成核数量并降低晶粒平均尺寸,但无法解释结晶中择优取向等问题。渡边辙发现电沉积与冶金的相似性,认为电沉积金属的微观组织结构与金属熔点相关,但其“微观结构控制”理论还存在一些缺陷,例如无法解释添加剂对晶粒的细化作用等。笔者建议可从价键及能带理论角度重塑电沉积机理与铜箔宏观性能间的关系,既通过建立铜箔电沉积过程中金属键形成与铜显微组织结构的理论联系,探讨其对铜箔宏观特性的影响。

关键词: 过电位, 电流密度, 铜晶粒, 铜箔织构, 物理性能

Abstract:

The manufacturing of electrolytic copper foil has attracted more and more attention with the extensive applications of printed circuit board and lithium battery. The industrial scale is still extending. Compared with the developments of electroplating equipment and electroplating process, there is limited research on the mechanism of electrodeposition. This paper summarizes the manufacturing process of electrodeposited copper foil and analyzes the differences of various electroplating parameters in different electrodeposited copper technologies, and points out the important role of electrodeposition current density in the formation of copper foil. By showing and comparing the microstructures of different electrodeposited copper foils, the influences of various factors in electrodeposition on the microstructures of copper foils and the corresponding macroscopic mechanical properties are discussed. From previous research results, it is found that the electrodeposition conditions and the composition of the plating solution have a significant impact on the microstructure and morphology of the copper foil, as well as the macroscopic mechanical properties. It is difficult to establish an effective relationship between the microstructures such as crystallite size and plane and the mechanical properties, which brings great challenge to the theoretical framework of the macro-mechanical properties of copper foils by using the microstructure of the coating as a bridge to establish electrodeposition conditions. Much effort has been tried to solve this problem by studying the mechanism of copper foil electrodeposition. The classical metal electrodeposition theory reveals that increasing the overpotential can increase the number of instantaneous nucleation and reduce the average grain size, however, it cannot explain the preferred orientation in crystallization. Watanabe found the similarity between electrodeposition and metallurgy, and believed that the microstructure of electrodeposited metal is related to the melting point of the metal, but this “microstructure control” theory still has some defects, such as the inability to explain the refining effect of additives on grains, etc. The author suggests that the relationship between the electrodeposition mechanism and the macroscopic properties of copper foil can be reshaped from the perspectives of valence bond and energy band theory. Influence of the macroscopic properties of copper foil can then be discussed.

Key words: over-potential, current density, electronic copper foil, microstructure, physical property

刘仁志, 谢平令, 王翀. 电沉积铜箔的微观组织结构——三维电结晶模式中的电结晶机理探讨[J]. 电化学（中英文）, 2022, 28(6): 2104481.

Ren-Zhi Liu, Ping-Ling Xie, Chong Wang. Microstructure of Electrodeposited Copper Foil: Discussion on the Mechanism Model of Three-Dimensional Electrocrystallization[J]. Journal of Electrochemistry, 2022, 28(6): 2104481.

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链接本文: https://electrochem.xmu.edu.cn/CN/10.13208/j.electrochem.210448

https://electrochem.xmu.edu.cn/CN/Y2022/V28/I6/2104481

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Main operational parameter	Electrodeposited copper foil	General acid copper electroplating
Concentration of inorganics Cu²⁺(g·L^-1)/H₂SO₄(g·L^-1) /Cl^-(mg·L^-1)	65 ~ 100 / 90 ~ 140 / 40	15 ~ 50 / 50 ~ 250 / 60
Additives	Natural reagent: collagen, gelatin, etc.	Artificial reagent: PEG,SPS,JGB, etc.
Temperature (^oC)	55 ~ 80	18 ~ 30
Current density (A·dm^-2)	35 ~ 130	1 ~ 3

Type	Reference	Average grain size	Dominant crystal plane orientation	Analysis
Acid electroplating copper	[44], [45]	15 ~ 40 nm; > 1 μm	Mostly (111) crystal plane	1. The copper foil with excellent mechanical pro- perties has no absolute co- rrelation with the orienta- tion of the dominant crys- tal plane. Different domin- minant crystal planes can obtain high tensile streng- th (> 400 MPa) and elong- ation (> 4.0%). 2. Small grain size (tens of nanometers) has high elongation (> 5.0%), but large grains can also ob- tain copper foil with high elongation.
Electronic circuit copper foil	[11], [33], [46]	0.57 ~ 0.97 μm	(220), (111)
Lithium battery copper foil	[47], [48], [11], [49], [50], [32]	35 nm ~ 14 μm	(200), (220), (111)

Crystal plane	Bright coating	Non-bright coating
Cu (111)	332	628
Cu (200)	223	473
Cu (220)	230	876