热处理工艺对静电纺丝制备PVDF/PMMA复合膜的力学性能的影响
|
摘要
利用热处理工艺对静电纺丝制备复合膜聚偏氟乙烯/聚甲基丙烯酸甲酯(PVDF/PMMA)进行改性,研究不同温度与不同压力对复合膜力学性能的影响,并与商用膜Celgard 2400在力学性能、离子电导率、循环性能方面进行对比。结果表明:在温度145℃,压强0.05 MPa时,PVDF/PMMA复合膜的拉伸强度为19.0 MPa,是未加压处理时其拉伸强度的10倍;PVDF/PMMA复合膜室温下的离子电导率为1.180mS/cm,比商用膜室温下的离子电导率高出187%;由PVDF/PMMA复合膜组装的纽扣电池在0.2C倍率下的放电比容量为140 (mA·h)/g,在1C倍率下的放电比容量为130(mA·h)/g,与商用膜同倍率下的放电比容量相同;在5C倍率下PVDF/PMMA复合膜的循环性能更优。
Polyvinylidene fluoride/polymethyl methacrylate(PVDF/PMMA)composite films prepared by electrospinning were mechanically modified by heat treatment process.The effects of temperature and pressure on the mechanical properties of the composite films were studied.The mechanical properties,ionic conductivities and cycling properties of the composite membranes were compared with those of commercial films Celgard 2400.The results show that the tensile strength of PVDF/PMMA composite film is 19.0 MPa after a treatment at 145℃and under a pressure of 0.05 MPa,which is 10 times higher than that of the composite film without pressure treatment;the ionic conductivity of PVDF/PMMA composite film at room temperature is 1.180 mS/cm,which is 187% higher than that of commercial film.The specific capacity of button cell assembled by PVDF/PMMA composite film is 140(mA·h)/g at 0.2 C ratio and 130(mA·h)/g at 1 Cratio,compared to commercial film at the same rate of discharge.The film presented better cycle performance at 5 Cratio.
Polyvinylidene fluoride/polymethyl methacrylate(PVDF/PMMA)composite films prepared by electrospinning were mechanically modified by heat treatment process.The effects of temperature and pressure on the mechanical properties of the composite films were studied.The mechanical properties,ionic conductivities and cycling properties of the composite membranes were compared with those of commercial films Celgard 2400.The results show that the tensile strength of PVDF/PMMA composite film is 19.0 MPa after a treatment at 145℃and under a pressure of 0.05 MPa,which is 10 times higher than that of the composite film without pressure treatment;the ionic conductivity of PVDF/PMMA composite film at room temperature is 1.180 mS/cm,which is 187% higher than that of commercial film.The specific capacity of button cell assembled by PVDF/PMMA composite film is 140(mA·h)/g at 0.2 C ratio and 130(mA·h)/g at 1 Cratio,compared to commercial film at the same rate of discharge.The film presented better cycle performance at 5 Cratio.
引文
[1]ANTON F.Process and apparatus for preparing artificial threads.US 1975504A[P].1934.
[2]MEGELSKI S,STEPHENS J S,BRUCE C,et al.Micro-and nanostructured surface morphology on electrospun polymer fibers[J].Macromolecules,2002,35(22):8456-8466.
[3]RENEKER D H,YARIN A L.Electrospinning jets and polymer nanofibers[J].Polymer,2008,49(10):2387-2425.
[4]师奇松,谢瑛鸾,戴晔,等.静电纺丝制备荧光导电双功能复合纳米纤维及其表征[J].功能高分子学报,2017,30(1):77-82.
[5]TAYLOR G.Disintegration of water drops in an electric field[J].Royal Society of London Proceedings,1964,280(1382):383-397.
[6]李霞,余厚咏,周颖,等.多次交替浸渍法构筑簇状ZnO的PAN复合纳米纤维膜及其光催化性能[J].功能高分子学报,2016,29(4):404-410.
[7]AHMED F E,LALIA B S,HASHAIKEH R.A review on electrospinning for membrane fabrication:Challenges and applications[J].Desalination,2015,356(1):15-30.
[8]YANG C,JIA Z,GUAN Z,et al.Polyvinylidene fluoride membrane by novel electrospinning system for separator of Li-ion batteries[J].Journal of Power Sources,2009,189(1):716-720.
[9]张传文,严玉蓉,区炜锋,等.静电纺丝法制备锂离子电池隔膜的研究进展[J].产业用纺织品,2009,27(1):1-6.
[10]于建香,刘太奇.静电纺丝法制备锂离子电池隔膜的研究进展[J].新技术新工艺,2012(5):61-64.
[11]漆东岳,刘延波,马营,等.PAN-PVDF复合增强静电纺锂离子电池隔膜[J].电源技术,2014(12):2231-2234.
[12]FAN Q,WHITTINGHAM M S.Electrospun manganese oxide nanofibers as anodes for lithium-ion batteries[J].Electrochemical and Solid-State Letters,2007,10(3):A48-A51.
[13]JI L,ZHANG X.Generation of activated carbon nanofibers from electrospun polyacrylonitrile-zinc chloride composites for use as anodes in lithium-ion batteries[J].Electrochemistry Communications,2009,11(3):684-687.
[14]漆东岳,刘延波,马营,等.PAN-PVDF复合增强静电纺锂离子电池隔膜[J].电源技术,2014,12:2231-2234.
[15]ZACCARIA M,FABIANI D,CANNUCCIARI G,et al.Effect of silica and tin oxide nanoparticles on properties of nanofibrous electrospun separators[J].Journal of the Electrochemical Society,2015,162(6):A915-A920.
[16]WU D,HUANG S,XU Z,et al.Polyethylene terephthalate/poly(vinylidene fluoride)composite separator for Li-ion battery[J].Journal of Physics:D.Applied Physics,2015,48(28):26-28.
[17]丁靖兰.静电纺丝法制备交联聚酰亚胺纤维膜及其作为锂电隔膜的应用研究[D].北京:北京化工大学,2014.
[18]LEE J,LEE C L,PARK K,et al.Synthesis of an Al2O3-coated polyimide nanofiber mat and its electrochemical characteristics as a separator for lithium ion batteries[J].Journal of Power Sources,2014,248(4):1211-1217.
[19]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(11):44-48.
[20]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(1/2):111-116.
[21]RAMAKRISHNA S,FUJIHARA K,TEO W E,et al.Electrospun nanofibers:solving global issues[J].Materials Today,2006,9(3):40-50.
[22]周明柱.PVDF/PMMA薄膜制备及改性研究[D].南京:南京工业大学,2013.
[23]WU X L,LIN J,WANG J Y,et al.Electrospun PVDF/PMMA/SiO2membrane separators for rechargeable lithium-ion batteries[J].Key Engineering Materials,2015,645/646(68):1201-1206.
[24]赵剑蒙.锂离子电池用PVDF/PMMA静电纺复合隔膜的制备与改性研究[D].上海:东华大学,2014.
[25]ZHAO J M,LIANG Y Z,CHENG S C,et al.Effect of thermal treatment on the physical properties of electrospun PVDF/PMMA composite membrane[J].Advanced Materials Research,2013,750/752(78):224-227.
[2]MEGELSKI S,STEPHENS J S,BRUCE C,et al.Micro-and nanostructured surface morphology on electrospun polymer fibers[J].Macromolecules,2002,35(22):8456-8466.
[3]RENEKER D H,YARIN A L.Electrospinning jets and polymer nanofibers[J].Polymer,2008,49(10):2387-2425.
[4]师奇松,谢瑛鸾,戴晔,等.静电纺丝制备荧光导电双功能复合纳米纤维及其表征[J].功能高分子学报,2017,30(1):77-82.
[5]TAYLOR G.Disintegration of water drops in an electric field[J].Royal Society of London Proceedings,1964,280(1382):383-397.
[6]李霞,余厚咏,周颖,等.多次交替浸渍法构筑簇状ZnO的PAN复合纳米纤维膜及其光催化性能[J].功能高分子学报,2016,29(4):404-410.
[7]AHMED F E,LALIA B S,HASHAIKEH R.A review on electrospinning for membrane fabrication:Challenges and applications[J].Desalination,2015,356(1):15-30.
[8]YANG C,JIA Z,GUAN Z,et al.Polyvinylidene fluoride membrane by novel electrospinning system for separator of Li-ion batteries[J].Journal of Power Sources,2009,189(1):716-720.
[9]张传文,严玉蓉,区炜锋,等.静电纺丝法制备锂离子电池隔膜的研究进展[J].产业用纺织品,2009,27(1):1-6.
[10]于建香,刘太奇.静电纺丝法制备锂离子电池隔膜的研究进展[J].新技术新工艺,2012(5):61-64.
[11]漆东岳,刘延波,马营,等.PAN-PVDF复合增强静电纺锂离子电池隔膜[J].电源技术,2014(12):2231-2234.
[12]FAN Q,WHITTINGHAM M S.Electrospun manganese oxide nanofibers as anodes for lithium-ion batteries[J].Electrochemical and Solid-State Letters,2007,10(3):A48-A51.
[13]JI L,ZHANG X.Generation of activated carbon nanofibers from electrospun polyacrylonitrile-zinc chloride composites for use as anodes in lithium-ion batteries[J].Electrochemistry Communications,2009,11(3):684-687.
[14]漆东岳,刘延波,马营,等.PAN-PVDF复合增强静电纺锂离子电池隔膜[J].电源技术,2014,12:2231-2234.
[15]ZACCARIA M,FABIANI D,CANNUCCIARI G,et al.Effect of silica and tin oxide nanoparticles on properties of nanofibrous electrospun separators[J].Journal of the Electrochemical Society,2015,162(6):A915-A920.
[16]WU D,HUANG S,XU Z,et al.Polyethylene terephthalate/poly(vinylidene fluoride)composite separator for Li-ion battery[J].Journal of Physics:D.Applied Physics,2015,48(28):26-28.
[17]丁靖兰.静电纺丝法制备交联聚酰亚胺纤维膜及其作为锂电隔膜的应用研究[D].北京:北京化工大学,2014.
[18]LEE J,LEE C L,PARK K,et al.Synthesis of an Al2O3-coated polyimide nanofiber mat and its electrochemical characteristics as a separator for lithium ion batteries[J].Journal of Power Sources,2014,248(4):1211-1217.
[19]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(11):44-48.
[20]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(1/2):111-116.
[21]RAMAKRISHNA S,FUJIHARA K,TEO W E,et al.Electrospun nanofibers:solving global issues[J].Materials Today,2006,9(3):40-50.
[22]周明柱.PVDF/PMMA薄膜制备及改性研究[D].南京:南京工业大学,2013.
[23]WU X L,LIN J,WANG J Y,et al.Electrospun PVDF/PMMA/SiO2membrane separators for rechargeable lithium-ion batteries[J].Key Engineering Materials,2015,645/646(68):1201-1206.
[24]赵剑蒙.锂离子电池用PVDF/PMMA静电纺复合隔膜的制备与改性研究[D].上海:东华大学,2014.
[25]ZHAO J M,LIANG Y Z,CHENG S C,et al.Effect of thermal treatment on the physical properties of electrospun PVDF/PMMA composite membrane[J].Advanced Materials Research,2013,750/752(78):224-227.