锂离子电池隔膜及技术进展

doi:10.3969/j.issn.2095-4239.2016.02.002

摘要/Abstract

摘要： 介绍了锂电池隔膜的功能及影响其性能的因素.总结了近十年来在锂电隔膜研发和技术领域的热点,即高安全性,新材料,陶瓷涂覆和提高润湿性等.分析了包括3C锂电池及动力锂电池等两类电池对隔膜性能的要求,指出了3C锂离子电池隔膜需要往厚度更薄,孔隙率更高,耐热温度更高,均匀性更好等方向发展,动力锂电池则着重于提高能量密度,扩大电化学稳定窗口,提升耐高电压特性.并从聚烯烃改性,聚烯烃-陶瓷复合隔膜,新材料体系,新工艺方法等方面介绍了隔膜领域的主要技术进展.最后,分析并展望了我国隔膜产业的现状,指出在提高产能的同时,应更加注重对技术及工艺的自主研发以保证产品质量.

关键词: 锂离子电池隔膜, 改性, 陶瓷涂覆, 新材料, 高安全性

Abstract: Lithium-ion-battery (LIB) separators and their properties which affect the LIB's performance were introduced. The hot spots, safety related properties, new materials, ceramic coating and high wettability in LIB separators research were summarized. The technical requirements for LIB separators by sorting the LIB into two types (3 C battery and power battery) are also discussed. It is noted that 3C LIB separators need to have thinner thickness, higher porosity, higher heat resistance and better uniformity, while power LIB focus on increasing the energy density, expanding the electrochemical stability, enhancing the resistance to high voltage. The main progress in LIB separators' research were reviewed from the following four aspects: polyolefin modification, polyolefin-ceramic composite separator, new material systems and new process methods. Finally, the authors analyzed the status of separator industry in China, and suggested that more attention should be paid to independent research on technology and processes to ensure the quality of products with increasing of the productivity.

Key words: LIB separator, modification, ceramic coating, new materials, high security

中图分类号:

TM912.9

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 Chang, WU Dayong. LIB separators and the recent technical progress[J]. Energy Storage Science and Technology, 2016, 5(2): 120-128.

参考文献

[1] KIM Y B，TRAN-PHU T，KIM M，et al. Facilitated ion diffusion in multiscale porous particles：Application in battery separators[J]. ACS Applied Materials & Interfaces，2015，7（8）：4511-4517.
[2] ETACHERI V，MAROM R，ELAZARI R，et al. Challenges in the development of advanced Li-ion batteries：A review[J]. Energy & Environmental Science，2011，4（9）：3243-3262.
[3] CAVALIERE S，SUBIANTO S，SAVYCH I，et al. Electrospinning：Designed architectures for energy conversion and storage devices[J]. Energy & Environmental Science，2011，4（12）：4761-4785.
[4] SCROSATI B，HASSOUN J，SUN Y K. Lithium-ion batteries：A look into the future[J]. Energy & Environmental Science，2011，4（9）：3287-3295.
[5] ARORA P，ZHANG Z. Battery separators[J]. Chemical Reviews，2004，104（10）：4419-4462.
[6] LEE H，YANILMAZ M，TOPRAKCI O，et al. A review of recent developments in membrane separators for rechargeable lithium-ion batteries[J]. Energy & Environmental Science，2014，7（12）：3857-3886.
[7] 操建华，于晓慧，吴大勇，等. 锂电隔膜研究及产业技术进展[J]. 中国科学B：化学，2014，44（7）：1125-1149.
CAO Jianhua，YU Xiaohui，WU Dayong，et al. Advances in research and industrial technology of lithium battery separator[J]. China Science B：Chemistry，2014，44（7）：1125-1149.
[8] 王辉. 锂离子电池隔膜的研究进展及发展方向[J]. 塑料制造，2015（6）：56-60.
WANG Hui. Research progress and development direction of lithium-ion battery separator[J]. Plastic Manufacturing，2015（6）：56-60.
[9] 中华人民共和国国家标准. 便携式电子产品用锂离子电池和电池组安全要求：GB 31241—2014[S].
National Standards of People's Republic of China. Lithium ion cells and batteries used in portable electronic equipments-safety requirements：GB 31241—2014[S].
[10] 王晓斌，黄美容，王松钊，吴耀根. 动力锂离子电池隔膜的性能要求及发展状况[J]. 塑料制造，2014（12）：59-64.
WANG Xiaobin，HUANG Meirong，WANG Songzhao，WU Yaogen. Development and performance requirements of power lithium-ion battery separator[J]. Plastic Manufacturing，2014（12）：59-64.
[11] 吴大勇，刘昌炎. 锂离子电池隔膜研究进展[J]. 新材料产业，2006（9）：48-53.
WU Dayong，LIU Changyan. Research progress of lithium-ion battery separator[J]. Advanced Materials Industry，2006（9）：48-53.
[12] （a）周建军，李林. 高β晶含量聚丙烯膜片的制备：ZL200610011884.6[P]. 2011-03-11；（b）周建军，李林，王磊. 非对称性的聚丙烯多孔膜及其制备方法：200710099005.4[P]. 2007-05-08.
（a）ZHOU Jianjun，LI Lin. Preparation of polypropylene with high β crystal content：ZL200610011884.6[P]. 2011-03-11；（b）ZHOU Jianjun，LI Lin，WANG Lei. Asymmetric porous polypropylene film and preparation method：200710099005.4[P]. 2007-05-08.
[13] BIERENBAUM H S，ISAACSON R B，DRUIN M L，et al. Microporous polymeric films[J]. Industrial & Engineering Chemistry Product Research and Development，1974，13（1）：2-9.
[14] KAMEI E，SHIMOMURA Y. Process of producing porous thermoplastic resin article：US4563317[P]. 1986-01-07.
[15] LLOYD D R，KIM S S，KINZER K E. Microporous membrane formation via thermally-induced phase separation. II. Liquid-liquid phase separation[J]. Journal of Membrane Science，1991，64（1）：1-11.
[16] KOTARO T，KOICHI K，TATSUYA T，et al. Microporous polyolefin membrane and method of producing same：US5051183[P]. 1991-09-24.
[17] NORIMITSU K，KOTARO T，KOICHI K，et al. Method of producing highly permeable microporous polyolefin membrane：US6153133[P]. 2000-11-28.
[18] PEKALA R W，KHAVARI M. Freestanding microporous separator including a gel-forming polymer：US6586138[P]. 2003-07-11.
[19] YU W C，HUX S E. Extrusion, bonding polyethylene, polypropylene：US5952120[P]. 1999-09-14.
[20] 陈志雄，吴耀根. 锂离子电池隔膜的市场与技术发展[J]. 国外塑料，2011，29（9）：57-59.
CHEN Zhixiong，WU Yaogen. Development of lithium-ion battery separator[J]. World Plastics，2011，29（9）：57-59.
[21] SONG K W，KIM C K. Coating with macroporous polyarylate via a nonsolvent induced phase separation process for enhancement of polyethylene separator thermal stability[J]. Journal of Membrane Science，2010，352（1）：239-246.
[22] RYOU M H，LEE Y M，PARK J K，et al. Mussel-inspired polydopamine-treated polyethylene separators for highpower Li-ion batteries[J]. Advanced Materials，2011，23（27）：3066-3070.
[23] KIM J Y，KIM S K，LEE S J，et al. Preparation of micro-porous gel polymer for lithium ion polymer battery[J]. Electrochimica Acta，2004，50（2）：363-366.
[24] 肖伟，王绍亮，赵丽娜，刘建国，严川伟. 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 Wei，WANG Shaoliang，ZHAO Lina，LIU Jianguo，YAN Chuanwei. Advance in ceramic-based composite separator for lithium-ion battery[J]. Chemial Industry and Engineering Progress，2015，34（2）：456-462.
[25] WEI H，MA J，LI B，et al. Enhanced cycle performance of lithium-sulfur batteries using a separator modified with a PVDF-C layer[J]. ACS Applied Materials & Interfaces，2014，6（22）：20276-20281.
[26] 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.
[27] LEE J R，WON J H，KIM J H，et al. Evaporation-induced self-assembled silica colloidal particle-assisted nanoporous structural evolution of poly(ethylene terephthalate) nonwoven composite separators for high-safety/high-rate lithium-ion batteries[J]. Journal of Power Sources，2012，216：42-47.
[28] YOO S H，KIM C K. Enhancement of the meltdown temperature of a lithium ion battery separator via a nanocomposite coating[J]. Industrial & Engineering Chemistry Research，2009，48（22）：9936-9941.
[29] 王洪，杨驰，谢文峰，余刚. 锂离子电池用陶瓷聚烯烃复合隔膜[J]. 应用化学，2014，31（7）：757-762.
WANG Hong，YANG Chi，XIE Wenfeng，YU Gang. A polyolefin/ceramic composite membrane for lithium ion batteries[J]. Applied Chemistry，2014，31（7）：757-762.
[30] JEONG H S，CHOI E S，LEE S Y. Composition ratio-dependent structural evolution of SiO2/poly(vinylidene fluoridehexafluoropropylene)-coated poly(ethylene terephthalate) nonwoven composite separators for lithium-ion batteries[J]. Electrochimica Acta，2012，86：317- 322.
[31] DJIAN D，ALLOIN F，MARTINET S，et al. Macroporous poly(vinylidene fluoride) membrane as a separator for lithium-ion batteries with high charge rate capacity[J]. Journal of Power Sources，2009，187（2）：575-580.
[32] TARASCON J M，GOZDZ A S，SCHMUTZ C，et al. Performance of Bellcore's plastic rechargeable Li-ion batteries[J]. Solid State Ionics，1996，86：49-54.
[33] LIU Y Q，LI X W，WEI X C，et al. Study on performance of PVDF piezoelectric film for the separator in Li-ion rechargeable cell[J]. Science China Technological Sciences，2013，56（11）：2646-2648.
[34] ZHOU L，WU N，CAO Q，et al. A novel electrospun PVDF/PMMA gel polymer electrolyte with in situ TiO2 for Li-ion batteries[J]. Solid State Ionics，2013，249：93-97.
[35] LI X，ZHANG M，HE J，et al. Effects of fluorinated SiO2 nanoparticles on the thermal and electrochemical properties of PP nonwoven/PVDF-HFP composite separator for Li-ion batteries[J]. Journal of Membrane Science，2014，455：368-374.
[36] WU D，SHI C，HUANG S，et al. Electrospun nanofibers for sandwiched polyimide/poly(vinylidene fluoride)/polyimide separators with the thermal shutdown function[J]. Electrochimica Acta，2015，176：727-734.
[37] CHEN W，LIU Y，MA Y，et al. Improved performance of lithium ion battery separator enabled by co-electrospinnig polyimide/poly (vinylidene fluoride-co-hexafluoropropylene) and the incorporation of TiO2-(2-hydroxyethyl methacrylate)[J]. Journal of Power Sources，2015，273：1127-1135.
[38] KOH M J，HWANG H Y，KIM D J，et al. Preparation and characterization of porous PVdF-HFP/clay nanocomposite membranes[J]. Journal of Materials Science & Technology，2010，26（7）：633-638.
[39] HWANG K，KWON B，BYUN H. Preparation of PVdF nanofiber membranes by electrospinning and their use as secondary battery separators[J]. Journal of Membrane Science，2011，378（1）：111-116.
[40] LI H，CHEN Y M，MA X T，et al. Gel polymer electrolytes based on active PVDF separator for lithium ion battery. I：Preparation and property of PVDF/poly (dimethylsiloxane) blending membrane[J]. Journal of Membrane Science，2011，379（1）：397-402.
[41] JEONG H S，KIM D W，JEONG Y U，et al. Effect of phase inversion on microporous structure development of Al2O3/poly (vinylidene fluoride-hexafluoropropylene)-based ceramic composite separators for lithium-ion batteries[J]. Journal of Power Sources，2010，195（18）：6116-6121.
[42] KURIBAYASHI I. Characterization of composite cellulosic separators for rechargeable lithium-ion batteries[J]. Journal of Power Sources，1996，63（1）：87-91.
[43] LIU H，HSIEH Y L. Ultrafine fibrous cellulose membranes from electrospinning of cellulose acetate[J]. Journal of Polymer Science Part B：Polymer Physics，2002，40（18）：2119-2129.
[44] CHIAPPONE A，NAIR J R，GERBALDI C，et al. Microfibrillated cellulose as reinforcement for Li-ion battery polymer electrolytes with excellent mechanical stability[J]. Journal of Power Sources，2011，196（23）：10280-10288.
[45] NYSTRO?M G，RAZAQ A，STR?MME M，et al. Ultrafast all-polymer paper-based batteries[J]. Nano letters，2009，9（10）：3635-3639.
[46] NYHOLM L，NYSTR?M G，MIHRANYAN A，et al. Toward flexible polymer and paper-based energy storage devices[J]. Advanced Materials，2011，23（33）：3751-3769.
[47] ZHANG J，LIU Z，KONG Q，et al. Renewable and superior thermal-resistant cellulose-based composite nonwoven as lithium-ion battery separator[J]. ACS Applied Materials & Interfaces，2012，5（1）：128-134.
[48] CHO T H，TANAKA M，OHNISHI H，et al. Composite nonwoven separator for lithium-ion battery：Development and characterization[J]. Journal of Power Sources，2010，195（13）：4272-4277.
[49] ORENDORFF C J. The role of separators in lithium-ion cell safety[J]. Electrochemical Society Interface，2012，21（2）：61-65.
[50] MIAO Y E，ZHU G N，HOU H，et al. Electrospun polyimide nanofiber-based nonwoven separators for lithium-ion batteries[J]. Journal of Power Sources，2013，226：82-86.
[51] JIANG W，LIU Z，KONG Q，et al. A high temperature operating nanofibrous polyimide separator in Li-ion battery[J]. Solid State Ionics，2013，232：44-48.
[52] DING J，KONG Y，YANG J. Preparation of polyimide/polyethylene terephthalate composite membrane for Li-ion battery by phase inversion[J]. Journal of the Electrochemical Society，2012，159（8）：A1198-A1202.
[53] WANG H，WANG T，YANG S，et al. Preparation of thermal stable porous polyimide membranes by phase inversion process for lithium-ion battery[J]. Polymer，2013，54（23）：6339-6348.
[54] 于晓慧，吴大勇，梁卫华，张艾. 一种高强度聚酰亚胺纳米纤维多孔膜及其制备方法和应用：ZL201310068925.5[P]. 2013-06-12.
YU Xiaohui，WU Dayong，LIANG Weihua，Zhang Ai. A high-strength polyimide nanofiber porous membrane and preparation method and application：ZL201310068925.5[P]. 2013-06-12.
[55] MOON S. The effect of polymer blending and extension conditions on the properties of separator prepared by wet process for Li ion secondary battery[J]. Polym. Korea，2002，26（1）：45.
[56] KANG G，WOO Y，KIM H，et al. Microporous polyolefin film and method for preparing the same：US application 13/733928 [P]. 2013-01-04.
[57] 吴大勇，王海燕，操建华. 经纬双向纺丝装置专利经纬双向静电纺丝制膜设备及设备的应用方法：ZL200910087706.5[P]. 2010-12-29.
WU Dayong，WANG Haiyan，CAO Jianhua. A equipment for preparing bidirectional electrospinning membrane and its application：ZL200910087706.5[P]. 2010-12-29.
[58] 王海燕，刘新厚，吴大勇. 静电纺丝及纳米纤维薄膜[J]. 物理化学学报，2007（s）：67-74.
WANG Haiyan，LIU Xinhou，WU Dayong. Electrospinning and nanofiber membrane[J]. Acta Physico-Chimica Sinica，2007（s）：67-74.
[59] KIM D W，SUN Y K. Electrochemical characterization of gel polymer electrolytes prepared with porous membranes[J]. Journal of Power Sources，2001，102（1）：41-45.
[60] LIU Z，JIANG W，KONG Q，et al. A core@ sheath nanofibrous separator for lithium ion batteries obtained by coaxial electrospinning[J]. Macromolecular Materials and Engineering，2013，298（7）：806-813.