聚酰亚胺纤维/溶解浆混合制备锂电池隔膜的研究
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摘要
为制备一种耐高温、强度大的锂电池隔膜,本研究以聚酰亚胺(PI)短切纤维和溶解浆为基材,采用湿法造纸技术制备PI/溶解浆隔膜,并对隔膜的物理性能进行了测定。结果表明,单独使用PI纤维制备的隔膜的抗张指数、孔隙率、孔径、吸液率分别为16. 7 N·m/g、2. 8%、82. 7μm、440%; PI纤维和溶解浆混抄,溶解浆用量为25%时,制备的PI/溶解浆隔膜的抗张指数、孔隙率、孔径、吸液率分别为17. 0 N·m/g、4. 3%、21. 2μm、594%,性能指标均高于前者。与PI纤维隔膜相比,添加溶解浆后的PI纤维表面有松散的絮状物,纤维之间不存在明显的间隙,溶解浆的存在使得纤维交织成多孔结构。传统的聚烯烃(PP)隔膜在加热至200℃时已经完全熔融收缩,而PI隔膜和PI/溶解浆隔膜加热至200℃时,尺寸未发生任何变化,因此PI隔膜和PI/溶解浆隔膜的热尺寸稳定性远优于传统的PP隔膜。
Traditional lithium ion battery separator are polyolefin-based membranes which have low heat resistance. Battery explosion often occurs due to the exothermic reactions during charge-discharge processes. In order to improve the safety level of lithium ion batteries,it is of necessity to prepare separators with high heat resistance and high mechanical strength. In this paper,novel lithium ion battery separators were prepared via a wet-laid papermaking technology from polyimide( PI) fibers and dissolving wood pulp. Results showed that the tensile index,porosity,pore size and electrolyte absorption of polyimide separators were 16. 7 N·m/g,2. 8%,82. 7 μm and 440%,respectively,while those of the separators prepared from mixing PI fibers and dissolving pulp( dissdving pulp dosage of 25%) were 17. 0 N·m/g,4. 3%,21. 2 μm,594%,respectively,which were better than those of the former. Dissolving pulp filled the gap between the polyimide fibers and reduced the pore size without affecting the porosity. Dissolving pulp also significantly improved the electrolyte absorption of separators due to its inherent porous and hydrophilic property. The polyolefin( PP) separator was completely melt-shrinked at 200℃ but the size of the PI separator and PI/dissolving pulp composite separator did not change. Therefore,the thermal dimensional stability of the PI separator and PI/dissolving pulp composite separator was much better than that of the conventional polyolefin separator.
Traditional lithium ion battery separator are polyolefin-based membranes which have low heat resistance. Battery explosion often occurs due to the exothermic reactions during charge-discharge processes. In order to improve the safety level of lithium ion batteries,it is of necessity to prepare separators with high heat resistance and high mechanical strength. In this paper,novel lithium ion battery separators were prepared via a wet-laid papermaking technology from polyimide( PI) fibers and dissolving wood pulp. Results showed that the tensile index,porosity,pore size and electrolyte absorption of polyimide separators were 16. 7 N·m/g,2. 8%,82. 7 μm and 440%,respectively,while those of the separators prepared from mixing PI fibers and dissolving pulp( dissdving pulp dosage of 25%) were 17. 0 N·m/g,4. 3%,21. 2 μm,594%,respectively,which were better than those of the former. Dissolving pulp filled the gap between the polyimide fibers and reduced the pore size without affecting the porosity. Dissolving pulp also significantly improved the electrolyte absorption of separators due to its inherent porous and hydrophilic property. The polyolefin( PP) separator was completely melt-shrinked at 200℃ but the size of the PI separator and PI/dissolving pulp composite separator did not change. Therefore,the thermal dimensional stability of the PI separator and PI/dissolving pulp composite separator was much better than that of the conventional polyolefin separator.
引文
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[10]Hu X.Study on the structure and properties of polyolefin fiber battery diaphragm paper[D].Ji’nan:Qilu University of Technology,2016.胡星.聚烯烃纤维电池隔膜纸结构及成纸性能的研究[D].济南:齐鲁工业大学,2016.
[11]UCHIDA I,ISHIKAWA H,MOHAMEDI M,et al.AC-impedance measurements during thermal runaway process in several lithium/polymer batteries[J].Journal of Power Sources,2003,119(6):821.
[12]Chen Y T,Zhang Q H.Progress in the Preparation and Application of Polyimide Fiber[J].Polymer Bulletin,2013(10):71.陈英韬,张清华.聚酰亚胺纤维的制备与应用研究进展[J].高分子通报,2013(10):71.
[13]LIU F,GUO H,YONG Z,et al.Enhanced Resistance to the Atomic Oxygen Exposure of POSS/Polyimide Composite Fibers with Surface Enrichment through Wet Spinning[J].European Polymer Journal,2018,105:115.
[14]LUONG N D,ULLA,KORHONEN,et al.Enhanced mechanical and electrical properties of polyimide film by graphene sheets via in situ polymerization[J].Polymer,2011,52(23):5237.
[15]Wang Y,Wang S,Wang Ai P.Preparation and properties of polyimide lithium diaphragm[J].Plastics Industry,2018(1):138.王岳,王爽,王爱萍.聚酰亚胺基锂电隔膜的制备及性能[J].塑料工业,2018(1):138.
[16]Chen Z P,Huang S X,Zhu H B,et al.Advances in the research of polyimide in the field of lithium battery diaphragm[J].Insulation,2018(4):1.陈志平,黄孙息,朱恒斌,等.聚酰亚胺在锂电池隔膜领域的研究进展[J].绝缘材料,2018(4):1.
[17]LV J,WANG Z J,LIU Y.Effects of Bacterial Cellulose and Coniferous Wood Pulp on Paper Properties[J].China Pulp&Paper,2012,31(1):19.吕瑾,王志杰,刘叶.细菌纤维素与针叶木浆配抄对纸张性质的影响[J].中国造纸,2012,31(1):19.
[18]LIU Y S,CHEN C X,LI J G,et al.The Quality Requirements of Dissolved Pulp and Its Production Technology[J].China Pulp&Paper,2016,35(2):56.刘一山,陈春霞,李建国,等.溶解浆的质量要求及其生产技术[J].中国造纸,2016,35(2):56.
[19]Chi T Y,He L,Chen Z M,et al.The application of cellulose in lithium ion battery diaphragm[J].Battery Industry,2014(4):206.迟婷玉,贺磊,陈宗明,等.纤维素在锂离子电池隔膜中的应用[J].电池工业,2014(4):206.
[20]Deng J Z.The Market and Process Technology of Dissolved Pulp[J].China Pulp&Paper,2012,31(4):58.邓继泽.溶解浆的市场及工艺技术[J].中国造纸,2012,31(4):58.
[21]TIAN C,HUANG Y,YANG X B,et al.Research Progress on the Reaction Properties of Dissolved Pulp[J].China Pulp&Paper,2015,34(1):61.田超,黄雁,杨小博,等.溶解浆的反应性能及相关研究进展[J].中国造纸,2015,34(1):61.
[22]ZHAO L,YUAN Z,KAPU N S,et al.Increasing efficiency of enzymatic hemicellulose removal from bamboo for production of highgrade dissolving pulp[J].Bioresource Technology,2017,223:40.
[2]Liu C N.Foreign lithium battery diaphragm industry dynamics[J].Chinese Journal of Power Sources,2013,37(6):919.刘春娜.国外锂电池隔膜产业动态[J].电源技术,2013,37(6):919.
[3]Xu Q.Preparation and properties of cellulose based lithium battery diaphragm[D].Qingdao:Qingdao University,2014.徐泉.纤维素基锂电池隔膜的制备与性能研究[D].青岛:青岛大学,2014.
[4]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(s2):187.赵锦成,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(s2):187.
[5]Zhang M Y,Niu H Q,Han En L,et al.Research and Application of Polyimide Fibers with High Strength and High Modulus[J].Insulating Materials,2016,49(8):12.张梦颖,牛鸿庆,韩恩林,等.高强高模聚酰亚胺纤维及其应用研究[J].绝缘材料,2016,49(8):12.
[6]Huang X.Separator technologies for lithium-ion batteries[J].Journal of Solid State Electro Chemistry,2011,15(4):649.
[7]Sun M L,Tang H L,Pan M.A Review on the Separators of Power Liion Batteries[J].Materials Review,2011,25(9):44.孙美玲,唐浩林,潘牧.动力锂离子电池隔膜的研究进展[J].材料导报,2011,25(9):44.
[8]Huang Y Q,Guan D An.Recent Development of the Separator for Lithium Ion Battery[J].Marine Electric&Electronic Technology,2011,31(1):26.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.
[9]Chen Y H,Tang Z Y,Lu X H,et al.Research of Explosion Mechanism of Lithium-Ion Battery[J].Progress In Chemistry,2006,18(6):140.陈玉红,唐致远,卢星河,等.锂离子电池爆炸机理研究[J].化学进展,2006,18(6):140.
[10]Hu X.Study on the structure and properties of polyolefin fiber battery diaphragm paper[D].Ji’nan:Qilu University of Technology,2016.胡星.聚烯烃纤维电池隔膜纸结构及成纸性能的研究[D].济南:齐鲁工业大学,2016.
[11]UCHIDA I,ISHIKAWA H,MOHAMEDI M,et al.AC-impedance measurements during thermal runaway process in several lithium/polymer batteries[J].Journal of Power Sources,2003,119(6):821.
[12]Chen Y T,Zhang Q H.Progress in the Preparation and Application of Polyimide Fiber[J].Polymer Bulletin,2013(10):71.陈英韬,张清华.聚酰亚胺纤维的制备与应用研究进展[J].高分子通报,2013(10):71.
[13]LIU F,GUO H,YONG Z,et al.Enhanced Resistance to the Atomic Oxygen Exposure of POSS/Polyimide Composite Fibers with Surface Enrichment through Wet Spinning[J].European Polymer Journal,2018,105:115.
[14]LUONG N D,ULLA,KORHONEN,et al.Enhanced mechanical and electrical properties of polyimide film by graphene sheets via in situ polymerization[J].Polymer,2011,52(23):5237.
[15]Wang Y,Wang S,Wang Ai P.Preparation and properties of polyimide lithium diaphragm[J].Plastics Industry,2018(1):138.王岳,王爽,王爱萍.聚酰亚胺基锂电隔膜的制备及性能[J].塑料工业,2018(1):138.
[16]Chen Z P,Huang S X,Zhu H B,et al.Advances in the research of polyimide in the field of lithium battery diaphragm[J].Insulation,2018(4):1.陈志平,黄孙息,朱恒斌,等.聚酰亚胺在锂电池隔膜领域的研究进展[J].绝缘材料,2018(4):1.
[17]LV J,WANG Z J,LIU Y.Effects of Bacterial Cellulose and Coniferous Wood Pulp on Paper Properties[J].China Pulp&Paper,2012,31(1):19.吕瑾,王志杰,刘叶.细菌纤维素与针叶木浆配抄对纸张性质的影响[J].中国造纸,2012,31(1):19.
[18]LIU Y S,CHEN C X,LI J G,et al.The Quality Requirements of Dissolved Pulp and Its Production Technology[J].China Pulp&Paper,2016,35(2):56.刘一山,陈春霞,李建国,等.溶解浆的质量要求及其生产技术[J].中国造纸,2016,35(2):56.
[19]Chi T Y,He L,Chen Z M,et al.The application of cellulose in lithium ion battery diaphragm[J].Battery Industry,2014(4):206.迟婷玉,贺磊,陈宗明,等.纤维素在锂离子电池隔膜中的应用[J].电池工业,2014(4):206.
[20]Deng J Z.The Market and Process Technology of Dissolved Pulp[J].China Pulp&Paper,2012,31(4):58.邓继泽.溶解浆的市场及工艺技术[J].中国造纸,2012,31(4):58.
[21]TIAN C,HUANG Y,YANG X B,et al.Research Progress on the Reaction Properties of Dissolved Pulp[J].China Pulp&Paper,2015,34(1):61.田超,黄雁,杨小博,等.溶解浆的反应性能及相关研究进展[J].中国造纸,2015,34(1):61.
[22]ZHAO L,YUAN Z,KAPU N S,et al.Increasing efficiency of enzymatic hemicellulose removal from bamboo for production of highgrade dissolving pulp[J].Bioresource Technology,2017,223:40.