张柳燕,郝晓瑜,汪洋,杨英,古红涛,储松潮,武俊伟,郑军.锂电复合集流体用磁控溅射Cu籽晶层微观结构及性能调控[J].表面技术,2025,54(10):1-12.
ZHANG Liuyan,HAO Xiaoyu,WANG Yang,YANG Ying,GU Hongtao,CHU Songchao,WU Junwei,ZHEN Jun.Microstructure and Performance Regulation of Cu Seed Layer by Magnetron Sputtering for Composite Current Collector Used in Lithium Battery[J].Surface Technology,2025,54(10):1-12 |
| 锂电复合集流体用磁控溅射Cu籽晶层微观结构及性能调控 |
| Microstructure and Performance Regulation of Cu Seed Layer by Magnetron Sputtering for Composite Current Collector Used in Lithium Battery |
| 投稿时间：2025-01-22 修订日期：2025-04-27 |
| DOI：10.16490/j.cnki.issn.1001-3660.2025.10.001 |
| 中文关键词: 复合集流体 磁控溅射 Cu籽晶层 电学性能 结合力 |
| 英文关键词:composite current collectors magnetron sputtering Cu seed layer electrical properties adhesion |
| 基金项目:安徽省重点研究和开发计划(202304a05020084) |
| 作者 | 单位 |
| 张柳燕 | 安徽工业大学 先进金属材料绿色制备与表面技术教育部重点实验室 材料科学与工程学院，安徽 马鞍山 243002 |
| 郝晓瑜 | 安徽工业大学 先进金属材料绿色制备与表面技术教育部重点实验室 材料科学与工程学院，安徽 马鞍山 243002 |
| 汪洋 | 安徽工业大学 先进金属材料绿色制备与表面技术教育部重点实验室 材料科学与工程学院，安徽 马鞍山 243002 |
| 杨英 | 安徽工业大学 先进金属材料绿色制备与表面技术教育部重点实验室 材料科学与工程学院，安徽 马鞍山 243002 |
| 古红涛 | 安徽铜峰电子股份有限公司，安徽 铜陵 244000 |
| 储松潮 | 安徽铜峰电子股份有限公司，安徽 铜陵 244000 |
| 武俊伟 | 江苏英联复合集流体有限公司，江苏 扬州 225603 |
| 郑军 | 安徽工业大学 先进金属材料绿色制备与表面技术教育部重点实验室 材料科学与工程学院，安徽 马鞍山 243002 |
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| Author | Institution |
| ZHANG Liuyan | Key Laboratory of Green Fabrication and Surface Technology of Advanced Metal Materials,School of Materials Science and Engineering, Anhui University of Technology, Anhui Ma'anshan 243002, China |
| HAO Xiaoyu | Key Laboratory of Green Fabrication and Surface Technology of Advanced Metal Materials,School of Materials Science and Engineering, Anhui University of Technology, Anhui Ma'anshan 243002, China |
| WANG Yang | Key Laboratory of Green Fabrication and Surface Technology of Advanced Metal Materials,School of Materials Science and Engineering, Anhui University of Technology, Anhui Ma'anshan 243002, China |
| YANG Ying | Key Laboratory of Green Fabrication and Surface Technology of Advanced Metal Materials,School of Materials Science and Engineering, Anhui University of Technology, Anhui Ma'anshan 243002, China |
| GU Hongtao | Anhui Tongfeng Electronics Co., Ltd., Anhui Tongling 244000, China |
| CHU Songchao | Anhui Tongfeng Electronics Co., Ltd., Anhui Tongling 244000, China |
| WU Junwei | Jiangsu Yinglian Composite Collector Co., Ltd., Jiangsu Yangzhou 225603, China |
| ZHEN Jun | Key Laboratory of Green Fabrication and Surface Technology of Advanced Metal Materials,School of Materials Science and Engineering, Anhui University of Technology, Anhui Ma'anshan 243002, China |
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| 中文摘要: |
| 目的 解决锂电集流体用复合铜箔所面临的导电及界面结合问题。方法 采用磁控溅射技术在PP基体表面沉积纳米级Cu籽晶层，通过调控衬底温度、气体流量及溅射功率等工艺参数，制备出电阻率低、结合力好的Cu膜。采用场发射扫描电子显微镜对薄膜表面形貌进行表征，利用手持式四探针方阻仪测量薄膜方阻并计算电阻率，利用划格测试法对Cu膜结合力进行评级。结果 随着衬底温度的升高，薄膜晶粒尺寸增大，电阻率增加，膜基结合性能下降;随着气体流量的增加，薄膜沉积速率先上升后降低，电阻率先下降后上升，膜基结合力逐渐提高;随着溅射功率的增加，沉积速率增大，电阻率下降，薄膜附着力变差。综合考虑薄膜微观形貌、电学性能以及界面结合性能，优选出的Cu膜最佳沉积参数为:衬底温度为−15 ℃;气体流量(气压)为400 mL/min(0.24 Pa);溅射功率为1.5 kW;Cu膜厚度约为80 nm。在此工艺下制备的Cu膜微观结构致密，电学性能良好(9.72×10−8 Ω.m)，结合力评级为1级。结论 衬底温度、气体流量以及溅射功率均显著影响Cu膜的微观结构和性能。通过精细调控沉积工艺可以制备出综合性能优良的锂电复合集流体用Cu籽晶层。 |
| 英文摘要: |
| In this work, nanoscale Cu seed layers were deposited on PP substrates by DC magnetron sputtering technique, aiming to solve the conductivity and bonding issues of composite Cu foils applied in current collectors for lithium-ion batteries. Cu films with low resistivity and favorable adhesion performance were obtained by regulating process parameters such as substrate temperature, gas flow, sputtering power, etc. The surface morphology of Cu films was analyzed by field emission scanning electron microscope (FESEM). The four point probe meter was employed to test the film square resistance, and the resistivity was subsequently calculated. The adhesion strength was qualitatively assessed based on the cross-cut test method. With the increase of the substrate temperature, the grain sizes of the films increased, followed by the decrease of the film resistivity as well as adhesion strength. As the gas flow increased, the deposition rate initially increased and then decreased. Under low-pressure conditions, black spots appeared on the film surface. EDS analysis indicated that these black spots were not surface oxides, but rather the result of the film being too thin and incomplete island-to-island connectivity. The resistivity showed a trend of initially decreasing and then increasing, which was attributed to the presence of these microscopic defects that enhanced electron scattering within the film. Therefore, copper films deposited under low-pressure conditions typically exhibited higher resistivity, while the adhesion strength between the film and the substrate gradually improved. As the sputtering power (1, 1.5, 2, and 2.5 kW) increased, the deposition rate of the film significantly increased. The XRD results for the 2.5 kW showed only a weak Cu (111) diffraction peak, indicating that the Cu (111) plane with the lowest surface energy, preferentially grew during the early stages of film formation. At sputtering powers of 1 kW and 1.5 kW, micro-pores and cracks appeared on the surfaces of Cu films deposited on Si and PP substrates, respectively. By adjusting the deposition time for the 1 kW and 1.5 kW samples, the surface became smooth when the film thickness reached approximately 80 nm, and the observed micro-pores or cracks were attributed to insufficient film thickness. A comparison of the cross-hatch test results for Cu films of the same thickness but under different sputtering powers revealed that as the power increased, the adhesion strength between the film and the substrate decreased. Based on the microstructure, electrical and bonding properties of Cu seed layers, the optimal deposition parameters were found as follows:substrate temperature of −15 ℃, gas flow (pressure) of 400 mL/min (0.24 Pa), sputtering power of 1.5 kW, and Cu thickness of approximately 80 nm. Under the above deposition conditions, the Cu film exhibited a dense microstructure, and the resistivity was as low as 9.72×10−8 Ω.m. Besides, the bonding strength was rated as level 1. The microstructure and properties of Cu films were significantly affected by the substrate temperature, gas flow as well as sputtering power. Hence, the Cu seed layers for composite current collectors could be obtained by regulating deposition process with excellent performance. |
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