锂离子电池塑料-金属复合集流体的特性及制备研究进展

doi:10.19799/j.cnki.2095-4239.2023.0763

摘要/Abstract

摘要：

塑料-金属聚合物复合集流体（metallized plastic current collector，MPCC）通过减厚、减重可大幅提高电池的能量密度，且因聚合物自身绝缘、受热收缩、熔融等特性可提高电池的安全性，因此吸引了产业界研究者的诸多关注。了解聚合物基底和MPCC的特性及制备方法有利于高质量MPCC的研发，同时可促进高能量密度、高安全电池的发展，因此本文着重介绍了常用和亟待开发的聚合物的特性，阐明了目前市场生产的高质量PET、PP基复合集流体虽已应用于锂离子电池，但面临着各种挑战，例如PET的溶胀溶解反应，PP与金属层间的低黏结性等，并提出了相应的改进措施。此外，本文总结了聚合物表面沉积金属层的多种方法（磁控溅射、蒸镀、化学沉积和电镀等）的原理、优缺点和设备改良策略、注意事项，以期提高聚合物表面金属层的均匀性、一致性和导电率。最后，为提高MPCC在电池中的应用可行性，明确了MPCC未来研发的重点攻关问题，例如提高金属-聚合物界面黏结性，进一步提高电池安全性和导电率，并阐述了将来的发展趋势：功能化和精细化MPCC在电池中的应用。

关键词: 锂离子电池, 复合集流体, 塑料基膜, 金属涂层

Abstract:

Metallized plastic current collectors (MPCCs) have attracted considerable attention from industrial researchers as MPCCs can considerably increase the energy density of batteries by reducing the thickness and weight of devices. Furthermore, polymer properties, such as insulation, heat shrinkage, and melting considerably increase battery safety. Understanding the properties and preparation methods of polymer substrates and MPCCs is crucial for the development of high-quality MPCCs and the promotion of the development of high energy density and high-safety batteries. Therefore, this review focused on the properties of commonly used and potential polymers and clarified the advantages of high-quality polyethylene terephthalate (PET)-and polypropylene (PP)-based MPCCs applied to lithium-ion batteries as well as their fabrication and operational challenges, including the dissolution reaction of PET, low adhesion between PP, and metal layers. We have proposed measures to overcome these drawbacks. This paper summarizes the principles, advantages, disadvantages, and strategies (magnetron sputtering, evaporation, chemical deposition and electrochemical deposition, etc.) for depositing metal layers on polymer surfaces to improve the homogeneity, consistency, and electrical conductivity of the metal layers on polymer surfaces. Finally, to improve MPCC availability in batteries, the directions of developing MPCC, including improving the metal-polymer interfacial bonding, safety, and conductivity of batteries, as well as functionalizing and refining MPCC elaborated.

Key words: lithium-ion battery, composite current collector, plastic film, metal coating

中图分类号:

O 69

张稚国, 李华清, 王莉, 何向明. 锂离子电池塑料-金属复合集流体的特性及制备研究进展[J]. 储能科学与技术, 2024, 13(3): 749-758.

Zhiguo ZHANG, Huaqing LI, Li WANG, Xiangming HE. Characteristics and preparation of metallized plastic current collectors for lithium-ion batteries[J]. Energy Storage Science and Technology, 2024, 13(3): 749-758.

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材料名称	Cu	Cu MPCC	Al	Al MPCC	测试方法
厚度/μm	6	6	13	6	马尔测厚仪
面密度/(g/m²)	52	24	35	8.5	电子天平
抗拉强度(MD/TD)/MPa	400/380	260/250	205/200	210~230/150~210	拉力机
断裂拉伸率(MD/TD)/%	6.0/4.0	80/50	5.0/4.5	30~80/15~45	拉力机
表面达因系数	>38	38±2	>38	38±2	达因笔
方阻/mΩ	3	20±2	2.1	40±2	四探针
热收缩率(MD/TD)/%	/	0.2/0.01	/	0.15/0.01	烘箱(130 ℃/0.5 h)

材料	聚对苯二甲酸乙二醇酯(PET)	聚丙烯(PP)	聚酰亚胺(PI)
工作温度范围/℃	-60~120	-30~140	-269~280
抗拉强度/MPa	高, 250	低, 25~45	高, 200
断裂伸长率/%	90~150	200~400	>50
粗糙度	很高	低	高
热稳定性	良好	良好	良好
与金属间的界面作用力	良好	较差	良好
耐酸碱腐蚀性	差	良好	优秀
成本/(美元/吨)	1063	1120	高
质量密度/(g/cm³)	1.29~1.41	0.85~0.99	1.39~1.45
技术成熟程度	成熟	成熟	难度大
生产阶段	量产	小试	实验室研发
是否环保	是	是	是

材料	PE	PVC	PS	PC	PVDF
全称	Polyethylen	Polyvinyl chloride	Polystyrene	Polycarbonate	Polyvinylidene fluoride
工作温度范围/℃	-40~90	-40~90	-30~70	-45~135	-40~150
抗拉强度/MPa	低, 6	低, 50~80	低, 36~60	低, 69	低, 50~70
断裂伸长率/%	90~950	20~40	1.2~2.5	60~120	10~50
是否具有热稳定性	是	是	否	是	是
是否耐酸碱腐蚀	是	是	否	否	是
质量密度/(g/cm³)	0.94~0.96	1.38~1.58	1.05	1.18~1.22	1.77~1.80
是否环保	是	否	否	是	是

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