Development status and progress of lithium ion battery separator

doi:10.16085/j.issn.1000-6613.2022-1183

Abstract

Abstract:

Separator is an important part of lithium ion battery, which significantly impact the safety and performance of the whole battery. At present, the pace of localization in China is accelerating, and there are obvious achievements and progress in the area of lithium-ion battery separators. The market share and production capacity in China are in the forefront of the world, but the high-end diaphragm market is still monopolized by foreign companies. Therefore, in order to further increase the localization rate of the high-end market, it is still necessary to strengthen the research on lithium-ion battery separators. This paper mainly expounds the main functions, types, performance differences, advantages and disadvantages of various battery separators, and the corresponding development status and progress. At the same time, the preparation process of lithium battery separators is described in detail. The types of diaphragms and different modification methods are summarized, including the differences in diaphragm performance caused by different modification methods, and the performances of several commercial separators and cellulose paper-based separators are compared. Finally, the future developments of lithium battery separator are summarized and prospected.

Key words: lithium ion battery separator, membrane modification, preparation process, multi-functional new diaphragm

摘要：

锂电池隔膜是锂离子电池的重要组成部分，对整个电池的安全及性能有显著影响。目前国内国产化步伐加快，在锂电池隔膜方面已有明显的成果进步，市场占有率和产能都位居世界前列，但高端隔膜市场却依旧被国外公司垄断，因此，为进一步提高高端化市场的国产化率，仍需加大锂电隔膜的研究力度。本文主要针对电池隔膜在电池中的主要作用、种类、性能差异及优缺点，详细阐述了相应的国内外研究和进展，同时还概括了锂电池隔膜的制备工艺方法等，包括湿法和干法制备工艺。对隔膜的种类以及不同的改性方法进行了概述，包括不同改性方法导致的隔膜性能上的差异，并以几种商业隔膜和纤维素纸基隔膜为例，进行了性能对比。最后对锂电池隔膜在工艺、新型锂电池隔膜发展以及研究方向等方面的未来发展趋势进行了总结展望。

关键词: 锂离子电池隔膜, 隔膜改性, 制备工艺, 多功能新型隔膜

CLC Number:

YU Jie, ZHANG Wenlong. Development status and progress of lithium ion battery separator[J]. Chemical Industry and Engineering Progress, 2023, 42(4): 1760-1768.

于捷, 张文龙. 锂离子电池隔膜的发展现状与进展[J]. 化工进展, 2023, 42(4): 1760-1768.

Figures/Tables 6

References 56

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项目	Celgard 2320	Celgard 2325	Celgard 2340	Celgard 2400	Celgard 2500	Celgard 2730
材料	PP/PE/PP	PP/PE/PP	PP/PE/PP	PP	PP	PE
厚度/µm	20	25	38	25	25	20
透气度/s·(100mL)^-1	530	575	775	620	200
孔径/nm	d=27	90×4	38×900	d=43	210×50
孔隙率/%	41	41	45	41	55	43
穿刺强度(钢针直1mm)/gf	360	375		450	>335
纵向拉伸强度/MPa		190	210
横向拉伸强度/MPa		13.5	13
参考文献	[27]	[28-29]	[28]	[27]	[27]	[30]

项目	Celgard 2320	Celgard 2325	Celgard 2340	Celgard 2400	Celgard 2500	Celgard 2730
材料	PP/PE/PP	PP/PE/PP	PP/PE/PP	PP	PP	PE
厚度/µm	20	25	38	25	25	20
透气度/s·(100mL)^-1	530	575	775	620	200
孔径/nm	d=27	90×4	38×900	d=43	210×50
孔隙率/%	41	41	45	41	55	43
穿刺强度(钢针直1mm)/gf	360	375		450	>335
纵向拉伸强度/MPa		190	210
横向拉伸强度/MPa		13.5	13
参考文献	[27]	[28-29]	[28]	[27]	[27]	[30]

项目	纤维素隔膜	CC隔膜	纤维素/PSA隔膜	MFC3隔膜	CCP-20	BC/Al₂O₃隔膜
材料	棉浆	刚毛藻纤维粉末	棉浆、芳砜纶浆粕	纤维素微纤丝、Al₂O₃粉末	漂白硫酸盐桉木浆、商业纤维素隔膜	细菌纤维素膜、九水合硝酸铝
厚度/µm	40	35	40	25	35	30
电解液吸收率/%	275		260		136.4	625
热收缩率/%	0(200℃)	0(150℃, 30min)	0(200℃, 30min)	<1(30~180℃)	0(100~150℃)	0(180℃, 30min)
孔隙率/%	70	46	66	54		74.7
离子电导率/mS·cm^-1	1.08	0.4	1.20	1.06	0.71	4.91
拉伸强度/MPa	15	61	17	12.2	49	140
参考文献	[39]	[40]	[41]	[42]	[43]	[44]

项目	纤维素隔膜	CC隔膜	纤维素/PSA隔膜	MFC3隔膜	CCP-20	BC/Al₂O₃隔膜
材料	棉浆	刚毛藻纤维粉末	棉浆、芳砜纶浆粕	纤维素微纤丝、Al₂O₃粉末	漂白硫酸盐桉木浆、商业纤维素隔膜	细菌纤维素膜、九水合硝酸铝
厚度/µm	40	35	40	25	35	30
电解液吸收率/%	275		260		136.4	625
热收缩率/%	0(200℃)	0(150℃, 30min)	0(200℃, 30min)	<1(30~180℃)	0(100~150℃)	0(180℃, 30min)
孔隙率/%	70	46	66	54		74.7
离子电导率/mS·cm^-1	1.08	0.4	1.20	1.06	0.71	4.91
拉伸强度/MPa	15	61	17	12.2	49	140
参考文献	[39]	[40]	[41]	[42]	[43]	[44]

指标名称	聚酰亚胺隔膜	PP/PE/PP三层隔膜
介电常数	3.4	2.2
介质损耗因数	10^-3	10^-2
透气性/mL·in^-2	>140	>140
孔隙率/%	90	42
溶解温度/℃	>500	175
纵向热收缩率/%	0 (350℃)	0.08 (85℃)
横向热收缩率/%	0 (350℃)	0.08 (85℃)
耐压值/kV·mm^-1	100～300	0.4
穿刺强度/gf	>2.5	>2.5