大倍率高耐热聚醚酰亚胺-聚偏氟乙烯芯壳纳米纤维锂离子电池隔膜
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摘要
以高耐热、高强度的聚醚酰亚胺(PEI)为芯层材料,以电解液亲和性和界面稳定性优良的聚偏氟乙烯(PVDF)为壳层材料,构建了一种具有同轴结构的大倍率、高耐热PEI-PVDF纳米纤维锂离子电池隔膜。通过SEM、TEM、TGA、电化学工作站、电池测试系统对PEI-PVDF同轴隔膜的微观形貌和性能进行测试与表征。结果表明:PEI-PVDF同轴纤维具有清晰的芯壳结构,与商业隔膜相比,PEI-PVDF同轴隔膜具有优异的热稳定性,在180℃下处理2h,尺寸稳定并未发生热收缩;吸液率达到520%;电化学稳定性优异,电化学窗口达到5.0V;离子电导率达到2.3mS·cm-1;采用PEI-PVDF隔膜组装的锂离子电池在8C的放电流下放电比容量仍能达到107mAh·g-1,再回到0.2C时恢复到原始比容量的95.4%,且电池在1C电流下循环100次后容量保持率高达92.5%,PEI-PVDF隔膜表现出的大倍率、高耐热的特点说明该纤维膜是一种高功率、高安全的锂离子电池隔膜。
A new type nanofiber separator with coaxial structure for lithium ion battery was constructed through electrospinning method.Polyether imide(PEI)was adopted as the core layer material due to its high heat-resistance and high strength,and polyvinylidene fluoride(PVDF)with excellent electrolyte affinity and interfacial stability was adopted as the shell layer material.The structure and performances of PEI-PVDF coaxial separator were investigated by SEM,TEM,TGA,electrochemical workstation,and battery test system.The results show that PEI-PVDF coaxial fiber has a clear core-shell structure.Compared with the commercial separator,it has excellent thermal stability and does not shrink after treated at 180℃for 2 h.The liquid electrolyte absorption rate also increases greatly,and reaches up to 520%.The electrochemical stability window is up to 5.0 V.The ionic conductivity is2.3 mS·cm-1.The lithium ion battery assembled with PEI-PVDF coaxial separator still show the specific discharge capacity of 107 mAh·g-1 at discharge current density of 8 C.In the recovery at 0.2 Crate,the specific capacity retain 95.4% of its original specific capacity.The coulombic efficiency of the batteries is 92.5% after 100 cycles of charge and discharge.The characteristics of the high rate and high heat resistance of the PEI-PVDF separator show that it is a kind of high power,high safety separator for lithium ion battery.
A new type nanofiber separator with coaxial structure for lithium ion battery was constructed through electrospinning method.Polyether imide(PEI)was adopted as the core layer material due to its high heat-resistance and high strength,and polyvinylidene fluoride(PVDF)with excellent electrolyte affinity and interfacial stability was adopted as the shell layer material.The structure and performances of PEI-PVDF coaxial separator were investigated by SEM,TEM,TGA,electrochemical workstation,and battery test system.The results show that PEI-PVDF coaxial fiber has a clear core-shell structure.Compared with the commercial separator,it has excellent thermal stability and does not shrink after treated at 180℃for 2 h.The liquid electrolyte absorption rate also increases greatly,and reaches up to 520%.The electrochemical stability window is up to 5.0 V.The ionic conductivity is2.3 mS·cm-1.The lithium ion battery assembled with PEI-PVDF coaxial separator still show the specific discharge capacity of 107 mAh·g-1 at discharge current density of 8 C.In the recovery at 0.2 Crate,the specific capacity retain 95.4% of its original specific capacity.The coulombic efficiency of the batteries is 92.5% after 100 cycles of charge and discharge.The characteristics of the high rate and high heat resistance of the PEI-PVDF separator show that it is a kind of high power,high safety separator for lithium ion battery.
引文
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[2] JUNG J,LEE C,YU S,et al.Electrospun nanofibers as a platform for advanced secondary batteries:A comprehensive review[J].Journal of Materials Chemistry A,2016,4(3):703-750.
[3] XIANG Y Y,LI J S,LEI J H,et al.Advanced separators for lithium-ion and lithium-sulfur batteries:A review of recent progress[J].Chemsuschem,2016,9(21):3023-3039.
[4] WU D Z,SHI C,HUANG S H,et al.Electrospun nanofibers for sandwiched polyimide/poly(vinylidene fluoride)/polyimide separators with the thermal shutdown function[J].Electrochimica Acta,2015,176:727-734.
[5] KARUPPASAMY K,RHEE H W,REDDY P A,et al.Ionic liquid incorporated nanocomposite polymer electrolytes for rechargeable lithium ion battery:A way to achieve improved electrochemical and interfacial properties[J].Journal of Industrial and Engineering Chemistry,2016,40:168-176.
[6] WANG Z H,ZHANG J,YANG Y X,et al.Flexible carbon nanofiber/polyvinylidene fluoride composite membranes as interlayers in high-performance lithium-sulfur batteries[J].Journal of Power Sources,2016,329:305-313.
[7] LIU J Q,WU X F,HE J Y,et al.Preparation and performance of a novel gel polymer electrolyte based on poly(vinylidene fluoride)/graphene separator for lithium ion battery[J].Electrochimica Acta,2017,235:500-507.
[8] ZHANG S S.A review on the separators of liquid electrolyte li-ion batteries[J].Journal of Power Sources,2007,164(1):351-364.
[9] COSTA C M,SILVA M M,LANCEROS-MENDEZ S.Battery separators based on vinylidene fluoride(VDF)polymers and copolymers for lithium ion battery applications[J].RSC Advances,2013,3(29):11404-11417.
[10] DAS S,GHOSH A.Structure,ion transport,and relaxation dynamics of polyethylene oxide/poly(vinylidene fluoride cohexafluoropropylene)-lithium bis(trifluoromethane sulfonyl)imide blend polymer electrolyte embedded with ionic liquid[J].Journal of Applied Physics,2016,119(9):095101.
[11] NUNES J,COSTA C M,LANCEROS-MENDEZ S.Polymer composites and blends for battery separators:State of the art,challenges and future trends[J].Journal of Power Sources,2015,281:378-398.
[12] GOMES M C,CUNHA A,TRINDADE T,et al.The role of surface functionalization of silica nanoparticles for bioimaging[J].Journal of Innovative Optical Health Sciences,2016,9(4):DOI:10.1142/S1793545816300056.
[13] LEE Y,JEONG Y B,KIM D.Cycling performance of lithium-ion batteriesassembled with a hybrid composite membrane prepared by an electrospinning method[J].Journal of Power Sources,2013,195(18):6197-6201.
[14] XIONG M,TANG H,WANG Y,et al.Ethylcellulosecoated polyolefin separators for lithiumion batteries with improved safety performance[J].Carbohydrate Polymers,2014,101:1140-1146.
[15] HAO J,LEI G,LI Z,et al.A novel polyethylene terephthalate nonwoven separator based on electrospinning technique for lithium ion battery[J].Journal of Membrane Science,2013,428:11-16.
[16] LI F S,WU Y S,CHOU J,et al.A mechanically robust and highly ion conductive polymer blend coating for high power and long life lithium ion battery anodes[J].Advanced Materials,2015,27(1):130-137.
[17]巩桂芬,王磊,李泽.静电纺聚乙烯-乙烯醇磺酸锂/聚酰亚胺锂离子电池隔膜复合材料的电化学性能[J].复合材料学报,2018,35(10):2632-2639.GONG G F,WANG L,LI Z.Electrochemical properties of lithium ethylene-vinyl alcohol copolymer sulfate/polyimide Li-ion battery separator composite by electrospinning[J].Acta Materiae Compositae Sinica,2018,35(10):2632-2639(in Chinese).
[18] YANG C L,LI Z H,LI W J,et al.Batwing-like polymer membrane consisting of PMMA-grafted electrospun PVDFSiO2nanocomposite fibers for lithium-ion batteries[J].Journal of Membrane Science,2015,495(1):341-350.
[19]王欣,邓亮,刘勇,等.泰勒锥的形成及应用[J].计算机与应用化学,2011,28(11):1387-1392.WANG X,DENG L,LIU Y,et al.Formation and application of Taylor cone[J].Computer and Applied Chemistry,2011,28(11):1387-1392(in Chinese).
[20] ZHAO M,WANG J,CHONG C,et al.An electrospun lignin/polyacrylonitrile nonwoven composite separator with high porosity and thermal stability for lithium-ion batteries[J].RSC Advances,2015,5(122):101115-101120.
[21] LI W,WU Y,WANG J,et al.Hybrid gel polymer electrolyte fabricated by electrospinning technology for polymer lithium-ion battery[J].European Polymer Journal,2015,67:365-372.
[22]梁银峥.基于静电纺纤维的先进锂离子电池隔膜材料的研究[D].上海:东华大学,2011.LIANG Y Z.Research on the advanced lithium-ion battery diaphragm materials based on ESD fiber[D].Shanghai:Donghua University,2011(in Chinese).
[23] LU Y,LI Y,ZHANG S,et al.Parameter study and characterization for polyacrylonitrile nanofibers fabricated via centrifugal spinning process[J].European Polymer Journal,2013,49(12):3834-3845.
[24]巩桂芬,王磊,徐阿文.静电纺PMMA/EVOH-SO3Li锂离子电池隔膜复合材料的制备及性能[J].复合材料学报,2018,35(3):477-484.GONG G F,WANG L,XU A W.Preparation and properties of PMMA/EVOH-SO3Li Li-ion battery separator composite by electrospinning[J].Acta Materiae Compositae Sinica,2018,35(3):477-484(in Chinese).