锂离子电池隔膜材料研究进展

doi:10.11949/j.issn.0438-1157.20170985

摘要/Abstract

摘要：

近年来，锂离子电池技术发展迅速，隔膜作为电池中的核心材料之一，决定着锂离子电池的性能，因此隔膜材料及制备技术亟需被深入研究。目前，商业化的锂电池隔膜以聚烯烃隔膜为主，制备工艺正从干法向湿法过渡，但是近几年已经发展出了不同材料体系、不同制备工艺的隔膜。本文简要介绍了聚烯烃隔膜生产技术，重点综述了非织造隔膜材料、涂层以及新型隔膜制备技术的研究成果，并展望了锂电池隔膜的发展方向。

关键词: 锂离子电池, 隔膜, 聚合物, 涂层, 制备

Abstract:

In recent years, lithium-ion battery technology has developed rapidly. As one of the core materials in the battery, the separator determines the performance of lithium-ion battery, because its characteristics influence on the influence rate, cycle and safe performance for batteries. Therefore, we need further research in the fields of separator material and preparation technology. At the present, polyolefin separator is still the main production of the commercial lithium-ion battery separator, but the preparation process is transferring from dry process to wet process. In the field of research, different material systems have been developed, such as PET, PVDF, PMIA and so on. Firstly, the production technology of polyolefin separator briefly introduced. Then the results of nonwoven separator material, coating material research, and new separator preparation technology are mainly reviewed. Finally, the outlooks and future directions in this research field are given.

Key words: lithium ion battery, separator, polymers, coating, preparation

中图分类号:

TQ028.8

王振华, 彭代冲, 孙克宁. 锂离子电池隔膜材料研究进展[J]. 化工学报, 2018, 69(1): 282-294.

WANG Zhenhua, PENG Daichong, SUN Kening. Research progress of separator materials for lithium ion batteries[J]. CIESC Journal, 2018, 69(1): 282-294.

参考文献 68

[1]	LU W J, YUAN Z Z, ZHAO Y Y, et al. Porous membranes in secondary battery technologies[J]. Chem. Soc. Rev., 2017, 46(8):2199-2236.
[2]	WAKIHARA M. Recent developments in lithium ion batteries[J]. Materials Science and Engineering, 2001, 33(4):109-134.
[3]	郭炳焜, 徐徽, 王先友, 等. 锂离子电池[M]. 长沙:中南大学出版社, 2005:48-65. GUO B K, XUN H, WANG X Y, et al. Lihium Ion Battery[M]. Changsha:Central South University Press, 2005:48-65.
[4]	黄友桥, 管道安. 锂离子电池隔膜材料的研究进展[J]. 船电技术, 2011, 31(1):26-29. HUANG Y Q, GUAN D A. Recent development of the separator for lithium Ion battery[J]. Marine Electric & Electronic Technology, 2011, 31(1):26-29.
[5]	王畅, 吴大勇. 锂离子电池隔膜及技术进展[J]. 储能科学与技术, 2016, 5(2):120-128. WANG C, WU D Y. LIB separators and the recent technical progress[J]. Energy Storage Science and Technology, 2016, 5(2):120-128.
[6]	肖伟, 巩亚群, 王红, 等. 锂离子电池隔膜技术进展[J]. 储能科学与技术, 2016, 5(2):188-196. XIAO W, GONG Y Q, WANG H, et al. Research progress of separators for lithium-ion batteries[J]. Energy Storage Science and Technology, 2016, 5(2):188-196.
[7]	周黎明, 邱毓昌, 冯允平. SF6混合气体绝缘介质的研究与应用[J]. 华东电力, 1996, 5:21-23. ZHOU L M, QIU Y C, FENG Y P. Research and application of SF6 mixed gas insulating medium[J]. East China Electric Power, 1996, 5:21-23.
[8]	WANG Y R, YANG Y F, YANG Y B, et al. Enhanced electrochemical performance of unique morphological LiMnPO4/C cathodem material prepared by solvothermal method[J]. Solid State Communications, 2010, 150(1):81-85.
[9]	赵锦城, 杨固长, 刘效疆, 等. 锂离子电池隔膜的研究概述[J]. 材料导报, 2012, 26(20):187-192. ZHAO J C, YANG G C, LIU X J, et al. General description of research on separator for lithium ion battery[J]. Materials Review, 2012, 26(20):187-192.
[10]	芦长椿. 非织造布在电池隔膜上的应用[J]. 合成纤维, 2013, 42(8):7-31. LU C C. Application of nonwovens in the battery separator[J]. Synthetic Fiber in China, 2013, 42(8):7-31.
[11]	HUANG X. Performance evaluation of a non-woven lithium ion battery separator prepared through a paper-making progress[J]. Journal of Power Sources, 2014, 256(12):96-101.
[12]	ORENDORFF C J. The role of separators in lithium-ion cell safety[J]. Electrochemical Society Interface, 2012, 21(2):61-65.
[13]	HAO J, LEI G T, LI Z H, et al. A novel polyethylene terephthalate nonwoven separator based on electrospinning technique for lithium ion battery[J]. Journal of Membrane Science, 2012, 428:11-16.
[14]	MIAO Y, ZHU G N, HOU H, et al. Electrospun polyimide nanofiber-based nonwoven separators for lithium-ion batteries[J]. Journal of Power Sources, 2013, 226(6):82-86.
[15]	ZHANG H, ZHANG Y, XU T, et al. Poly(m-phenylene isophthalamide) separator for improving the heat resistance and power density of lithium-ion batteries[J]. Journal of Power Sources, 2016, 329:8-16.
[16]	SHI G, JU S, HUANG C F, et al. Tensile strength of surface treated PBO fiber[J]. Materials Science Forum, 2015, 815:662-668.
[17]	HAO X M, ZHU J, JIANG X, et al. Ultrastrong polyoxyzole nanofiber membranes for dendrite-proof and heat-resistant battery separators[J]. Nano Letters, 2016, 16:2981-2987.
[18]	LEE M J, HWANG J K, KIM J H, et al. Electrochemical performance of a thermally rearranged polybenzoxazole nanocomposite membrane as a separator for lithium-ion batteries at elevated temperature[J]. Journal of Power Sources, 2016, 305:259-266.
[19]	肖伟, 王绍亮, 赵丽娜, 等. 陶瓷复合锂离子电池隔膜研究进展[J]. 化工进展, 2015, 34(2):456-462. XIAO W, WANG S L, ZHAO L N, et al. Advance in ceramic-based composite separator for lithium-ion battery[J]. Chemical Industry and Engineering Progress, 2015, 34(2):456-462.
[20]	THACKERAY M M, WOLVERTON C, ISAACS C D. Electrical energy storage for transportation approaching the limits of, and going beyond, lithium-ion batteries[J]. Energy & Environmental Science, 2012, 5(1):7854-7863.
[21]	LIAO Y, SUN C, HU S, et al. Anti-thermal shrinkage nanoparticles/polymer and ionic liquid based gel polymer electrolyte for lithium ion battery[J]. Electrochimica Acta, 2013, 89(1):461-468.
[22]	LEE T, KIM W K, LEE Y, et al. Effect of Al2O3, coatings prepared by RF sputtering on polyethylene separators for high-power lithium ion batteries[J]. Macromolecular Research, 2014, 22(11):1190-1195.
[23]	KANG S M, RYOU M H, CHOI J W, et al. Mussel-and diatom-inspired silica coating on separators yields improved power and safety in Li-ion batteries[J]. Chemistry of Materials, 2012, 24(17):3481-3485.
[24]	JEONG H S, LEE S Y. Closely packed SiO2, nanoparticles/poly(vinylidene fluoride-hexafluoropropylene) layers-coated polyethylene separators for lithium-ion batteries[J]. Journal of Power Sources, 2011, 196(16):6716-6722.
[25]	PARK J H, CHO J H, PARK W, et al. Close-packed SiO2/poly(methyl methacrylate) binary nanoparticles-coated polyethylene separators for lithium-ion batteries[J]. Journal of Power Sources, 2010, 195(24):8306-8310.
[26]	KIM K M, LATIFATU M, LEE Y G, et al. Effect of ceramic filler-containing polymer hydrogel electrolytes coated on the polyolefin separator on the electrochemical properties of activated carbon supercapacitor[J]. Journal of Electroceramics, 2014, 32(2):146-153.
[27]	YANG C W, TONG H, LUO C P, et al. Boehmite particle coating modified microporous polyethylene membrane:a promising separator for lithium ion batteries[J]. Journal of Power Sources, 2017, 348:80-86.
[28]	JUNG H R, JU D H, LEE W J, et al. Electrospun hydrophilic fumed silica/polyacrylonitrile nanofiber-based composite electrolyte membranes[J]. Electrochimica Acta, 2009, 54(13):3630-3637.
[29]	IEON H K, YEON D Y, LEE T L, et al. A water-based Al2O3 ceramic coating for polyethylene-based microporous separators for lithium-ion batteries[J]. Journal of Power Sources, 2016, 315:161-168.
[30]	KIM S W, CHO K Y. Enhanced moisture repulsion of ceramic-coated separators from aqueous composite coating solution for lithium-ion batteries inspired by a plant leaf surface[J]. Journal of Materials Chemistry A, 2016, 4(14):5069-5074.
[31]	CHO J Y, JUNG Y C, LEE Y S, et al. High performance separator coated with amino-functionalized SiO2 particles for safety enhanced lithium-ion batteries[J]. Journal of Membrane Science, 2017, 535:151-157.
[32]	JEONG H S, CHOI E S, LEE S Y. Composition ratio-dependent structural evolution of SiO2/poly(vinylidene fluoride-hexafluoropropylene)-coated poly(ethylene terephthalate) nonwoven composite separators for lithium-ion batteries[J]. Electrochimica Acta, 2012, 86(1):317-322.
[33]	MAO X F, SHI L Y, ZHANG H J, et al. Polyethylene separator activated by hybrid coating improving Li+ ion transference number and ionic conductivity for Li-metal battery[J]. Journal of Power Sources, 2017, 342:816-824.
[34]	LEI P, WANG H, WU C, et al. Tannic-acid-coated polypropylene membrane as a separator for lithium-ion batteries[J]. ACS Appl. Mater. Interfaces, 2015, 7(29):16003-16010.
[35]	ZHANG P, CHEN L, SHI C, et al. Development and characterization of silica tube-coated separator for lithium ion batteries[J]. J. Power Sources, 2015, 284:10-15.
[36]	HU S Y, LIN S D, TU Y Y, et al. Novel aramid nanofiber-coated polypropylene separators for lithium ion batteries[J]. J. Mater. Chem. A, 2016, 9(4):3513-3526.
[37]	KIM Y K, LEE W Y, KIM K J, et al. Shutdown-functionalized nonwoven separator with improved thermal and electrochemical properties for lithium-ion batteries[J]. Journal of Power Sources, 2016, 305:225-232.
[38]	KIM J H, GU M, LEE D H, et al. Functionalized nanocellulose-integrated heterolayered nanomats toward smart battery separators[J]. Nano Letter, 2016, 16(9):5533-5541.
[39]	WU Y S, YANG C C, LUO S P, et al. PVDF-HFP/PET/PVDF-HFP composite membrane for lithium-ion power batteries[J]. International Journal of Hydrogen Energy, 2017, 42(10):6862-6875.
[40]	YANG Y, HUANG X P, CAO Z Y, et al. Thermally conductive separator with hierarchical nano/microstructures for improving thermal management of batteries[J]. Nano Energy, 2016, 22:301-309.
[41]	DAI J H, SHI C, LI C, et al. A rational design of separator with substantially enhanced thermal features for lithium-ion batteries by the polydopamine-ceramic composite modification of polyolefin membranes[J]. Energy Environ. Sci., 2016, 9(10):3252-3261.
[42]	LUO X Y, LIAO Y H, ZHU Y M, et al. Investigation of nano-CeO2 contents on the properties of polymer ceramic separator for high voltage lithium ion batteries[J]. Journal of Power Sources, 2016, 348:229-238.
[43]	LIU H, XU J, GUO B, et al. Effect of SiO2 content on performance of polypropylene separator for lithium-ion batteries[J]. J. Appl. Polym. Sci., 2014, 131(23):1-6.
[44]	STEPHAN A M, NAHM K S. Review on composite polymer electrolytes for lithium batteries[J]. Polymer, 2006, 47(16):5952-5964.
[45]	SMITH S A, WILLIAMS B P, JOO Y L. Effect of polymer and ceramic morphology on the material and electrochemical properties of electrospun PAN/polymer derived ceramic composite nanofiber membranes for lithium ion battery separators[J]. Journal of Membrane Science, 2017, 526:315-322.
[46]	ZHENG W Z, ZHU Y, NA B, et al. Hybrid silica membranes with a polymer nanofiber skeleton and their application as lithium-ion battery separators[J]. Composites Science and Technology, 2017, 144:178-184.
[47]	YANILMAZ M, LU Y, ZHU J D, et al. Silica/polyacrylonitrile hybrid nanofiber membrane separators via sol-gel and electrospinning techniques for lithium-ion batteries[J]. Journal of Power Sources, 2016, 313:205-212.
[48]	WANG M, CHEN X, WANG H, et al. Improved performances of lithium-ion batteries with a separator based on inorganic fibers[J]. J. Mater. Chem. A, 2017, 5(1):311-318.
[49]	LIU K, LIU W, QIU Y C, et al. Electrospun core-shell microfiber separator with thermal-triggered flame-retardant properties for lithium-ion batteries[J]. Science Advances, 2017, 3(1):1-8.
[50]	邹亚囡. 动力锂电池隔膜的改性研究进展[J]. 合成树脂及塑料, 2016, 33(6):87-90. ZHOU Y N. Research progress of modification for power lithium-ion battery membrane[J]. China Synthesis Resin and Plastic, 2016, 33(6):87-90.
[51]	刘会会, 柳邦威. 锂电池隔膜生产技术现状与研究进展[J]. 绝缘材料, 2014, 47(6):1-9. LIU H H, LIU B W. Production technology status and research progress of lithium battery separators[J]. Insulating Materials, 2014, 47(6):1-9.
[52]	HARVEY S B, ROBERT B I, MELVIN L D, et al. Microporous polymeric films[J]. Industrial Engineering Chemistry Research, 1974, 13(1):2-9.
[53]	周建军, 李林. 锂离子电池隔膜的国产化现状与发展趋势[J]. 新材料产业, 2008, (4):33-36. ZHOU J J, LI L. Localization status and development trend of lithium ion battery separator[J]. Advanced Materials Industry, 2008, (4):33-36.
[54]	IHM D W, NOH J G, KIM J Y. Effect of polymer blending and drawing conditions on properties of polyethylene separator prepared for Li-ion secondary battery[J]. Journal of Power Sources, 2002, 109(2):388-393.
[55]	蒋新龙, 蒋益花. 发展中的锂离子电池隔膜制备技术[J]. 浙江树人大学学报, 2009, 9(1):18-22. JIANG X L, JIANG Y H. Development of membrane preparation technology for lithium ion batteries[J]. Journal of Zhejiang Shuren University, 2009, 9(1):18-22.
[56]	WADSWORTH L C, 靳向煜. 纺丝直接成布与熔喷工艺[J]. 国外纺织技术, 1988, (7):38-41. WADSWORTH L C, JIN X Y. Direct spinning and spraying process of spinning[J]. Textile Technology Overseas, 1988, (7):38-41.
[57]	王翠平, 叶柳, 李爱侠, 等. 静电纺丝法制备纳米纤维及其应用进展[J]. 大学物理实验, 2016, 29(6):22-29. WANG C P, YE L, LI A X, et al. Progress in preparation and application of nano fibers by electrospinning[J]. Physical Experiment of College, 2016, 29(6):22-29.
[58]	FONG H, CHUN I, RENEKER D H. Beaded nanofibers formed during electrospinning[J]. Polymer, 1999, 40(16):4585-4592.
[59]	RENEKER D H, CHUN I. Nanometer diameter fibers of polymer, produced by electrospinning[J]. Nanotechnology, 1996, 7(3):216-223.
[60]	刘全兵, 毛国龙, 张健, 等. 锂离子电池隔膜研究与应用进展[J]. 电源技术, 2015, 139(4):838-848. LIU Q B, MAO G L, ZHANG J, et al. Research and application progress of lithium-ion batteries separator[J]. Chinese Journal of Power Sources, 2015, 139(4):838-848.
[61]	崔光磊, 张建军, 孔庆山, 等. 一种湿法抄纸工艺制备的聚芳砜酰胺基锂离子电池隔膜:103441228A[P]. 2013-12-11. CUI G L, ZHANG J J, KONG Q S, et al. Poly (arylene amide) lithium ion battery separator prepared by wet paper making process:103441228A[P]. 2013-12-11.
[62]	ZHANG J, YUE L, KONG Q, et al. Sustainable, heat-resistant and flame-retardant cellulose-based composite separator for high-performance lithium ion battery[J]. Science Reports, 2014, 4(1):3935.
[63]	ZHOU C, TAN D H, JANAKIRAMAN A P, et al. Modeling the melt blowing of viscoelastic materials[J]. Chemical Engineering Science, 2011, 66(18):4172-4183.
[64]	靳向煜, 吴海波. 熔喷纺丝过程中的非稳定现象分析[J]. 非织造布, 1999, 14(1):20-22. JIN X Y, WU H B. Analysis of unsteady phenomena in melt spinning process[J]. Nonwovens, 1999, 14(1):20-22.
[65]	邓荣坚, 刘勇, 丁玉梅, 等. 熔体静电纺丝技术替代熔喷技术的探索[J/OL]. 中国科技论文在线, 2009[2017-07-10]. http://www.paper.edu.cn/releasepaper/content/200903-1075. DENG R J, LIU Y, DING Y M, et al. Investigation on melt electrospinning technology substitutes for melt blowing technology[J/OL]. Sciencnpaper Online, 2009[2017-07-10]. http://www.paper.edu.cn/releasepaper/content/200903-1075.
[66]	ZHANG H, ZHANG H, LI X, et al. Ion exchange membranes for vanadium redox flow battery (VRB) applications[J]. Energy Environ. Sci., 2011, 4:1676-1679.
[67]	LEE H, YANILMAZ M, TOPRAKCI O, et al. A review of recent developments in membrane separators for rechargeable lithium-ion batteries[J]. Energy Environ. Sci., 2014, 7(12):3857-3886.
[68]	尹艳红, 毛新欣, 曹朝霞, 等. 相转化法制备陶瓷涂层改性锂离子电池隔膜[J]. 功能高分子学报, 2012, 25(2):172-177. YIN Y H, MAO X X, CAO Z X, et al. Modification of lithium ion battery separator with ceramic coating using phase inversion[J]. Journal of Functional Polymers, 2012, 25(2):172-177.