聚乙烯-乙烯醇磺酸锂/聚偏氟乙烯-六氟丙烯锂离子电池隔膜的制备及性能
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摘要
以聚乙烯-乙烯醇的磺化物(EVOH-SO3Li)和聚偏氟乙烯-六氟丙烯(PVDF-HFP)为原料,利用高压静电纺丝技术纺制成高孔隙率、纤维粗细均匀的EVOH-SO3Li/PVDF-HFP复合隔膜材料。利用FTIR、SEM、万能拉伸试验仪、TGA、BMP3电化学工作站和电池检测系统对EVOH-SO3Li/PVDF-HFP隔膜进行测试分析。测试结果表明:EVOH-SO3Li/PVDF-HFP隔膜形成致密的三维网络结构,纤维粗细均匀,孔径均一,EVOH-SO3Li/PVDF-HFP隔膜的孔隙率和吸液率分别为85%和437%;与纯EVOH-SO3Li隔膜相比,EVOH-SO3Li/PVDF-HFP复合隔膜的拉伸强度最大值从2.17MPa提高至8.33MPa,起始热分解温度升高至310℃,并表现出良好的电化学性能和电池性能。其中电化学稳定窗口由5.6V增至5.8V,界面阻抗由425.51Ω降低至115.24Ω,离子电导率由1.592×10-3 S/cm提高至3.102×10-3 S/cm;采用EVOH-SO3Li/PVDF-HFP隔膜组装的锂离子电池在0.5C放电电流下循环100次后容量保持率为96.65%。
High-porosity and uniform-thickness composite separator was prepared by high-pressure electrospinning using polyethylene-vinyl alcohol sulfonate(EVOH-SO_3Li)and poly(vinylidene fluoride-hexafluoropropylene)(PVDF-HFP)as raw materials.The performance of the EVOH-SO_3Li/PVDF-HFP separator was characterized by FTIR,SEM,universal tensile tester,TGA,BMP3 electrochemical workstation and battery testing system.The test results show that the EVOH-SO_3Li/PVDF-HFP separator forms a dense three-dimensional network structure with uniform fiber thickness and uniform pore size.The porosity and liquid absorption rate of EVOH-SO_3Li/PVDFHFP separator are 85% and 437%,respectively.Compared with pure EVOH-SO_3Li separator,the maximum tensile strength of EVOH-SO_3Li/PVDF-HFP composite separator is increased from 2.17 MPa to 8.33 MPa.The initial thermal decomposition temperature also raises to 310℃.The excellent performance of electrochemical and battery is exhibited.The electrochemical stability window is increased from 5.6 Vto 5.8 V,the interfacial impedance is reduced from 425.51Ωto 115.24Ω,and the ionic conductivity is increased from 1.592×10-3 S/cm to 3.102×10-3 S/cm.Lithium-ion batteries assembled with EVOH-SO_3Li/PVDF-HFP separators have a capacity retention rate of 96.65% after 100 cycles at 0.5 Cdischarge current.
High-porosity and uniform-thickness composite separator was prepared by high-pressure electrospinning using polyethylene-vinyl alcohol sulfonate(EVOH-SO_3Li)and poly(vinylidene fluoride-hexafluoropropylene)(PVDF-HFP)as raw materials.The performance of the EVOH-SO_3Li/PVDF-HFP separator was characterized by FTIR,SEM,universal tensile tester,TGA,BMP3 electrochemical workstation and battery testing system.The test results show that the EVOH-SO_3Li/PVDF-HFP separator forms a dense three-dimensional network structure with uniform fiber thickness and uniform pore size.The porosity and liquid absorption rate of EVOH-SO_3Li/PVDFHFP separator are 85% and 437%,respectively.Compared with pure EVOH-SO_3Li separator,the maximum tensile strength of EVOH-SO_3Li/PVDF-HFP composite separator is increased from 2.17 MPa to 8.33 MPa.The initial thermal decomposition temperature also raises to 310℃.The excellent performance of electrochemical and battery is exhibited.The electrochemical stability window is increased from 5.6 Vto 5.8 V,the interfacial impedance is reduced from 425.51Ωto 115.24Ω,and the ionic conductivity is increased from 1.592×10-3 S/cm to 3.102×10-3 S/cm.Lithium-ion batteries assembled with EVOH-SO_3Li/PVDF-HFP separators have a capacity retention rate of 96.65% after 100 cycles at 0.5 Cdischarge current.
引文
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[17]巩桂芬,王磊,徐阿文.静电纺PMMA/EVOH-SO3Li复合锂离子电池隔膜的制备及性能[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).
[18]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 Liion battery separator composite by electrospinning[J].Acta Materiae Compositae Sinica,2018,35(10):2632-2639(in Chinese).
[19]SPASOVA M,MANOLOVA N,MARKOVA N,et al.Tuning the properties of PVDF or PVDF-HFP fibrous materials decorated with ZnO nanoparticles by applying electrospinning alone or in conjunction with electrospraying[J].Fibers and Polymers,2017,18(4):649-657.
[20]WANG C J,SHEN W Z,LU J,et al.Graphene oxide doped poly(vinylidene fluoride-co-hexafluoropropylene)gel electrode for lithium-ion battery[J].Ionics,2017,23(8):2045-2053.
[21]于宾,焦晓宁.P(VDF-HFP)/Al2O3复合锂离子电池隔膜的电化学性能[J].电源技术,2015,39(4):702-705.YU B,JIAO X N.Electrochemical characterization of P(VDF-HFP)/Al2O3 composite separator for lithium-ion battery[J].Chinese Journal of Power Sources,2015,39(4):702-705(in Chinese).
[2]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 Z H,PENG D C,SUN K N.Research progress of separator materials for lithium-ion batteries[J].Journal of Chemical Industry and Engineering,2018,69(1):282-294(in Chinese).
[3]闫金定.锂离子电池发展现状及其前景分析[J].航空学报,2014,35(10):2767-2775.YAN J D.Current status and development analysis of lithium-ion batteries[J].Acta Aeronautica et Astronautica Sinica,2014,35(10):2767-2775(in Chinese).
[4]LI Z D,ZHANG Y C,XIANG H F,et al.Trimethyl phosphite as an electrolyte additive for high-voltage lithium-ion batteries using lithium-rich layered oxide cathode[J].Journal of Power Sources,2013,240:471-475.
[5]HUANG X S.Separator technologies for lithium-ion batteries[J].Journal of Solid State Electrochemistry,2011,15(4):649-662.
[6]WANG Y R,YANG Y F,YANG Y B,et al.Enhanced electrochemical performance of unique morphological LiMnPO4/Ccathode material prepared by solvothermal method[J].Solid State Communications,2010,150(1-2):81-85.
[7]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.ZOU Y N.Research progress of modification for power lithium-ion battery membrane[J].China Synthetic Resin and Plastic,2016,33(6):87-90(in Chinese).
[8]夏清华.锂离子电池新型隔膜技术及市场概况[J].广东化工,2018,45(8):172-173.XIA Q H.Technology and market of lithium-ion battery separator[J].Guangdong Chemical Industry,2018,45(8):172-173(in Chinese).
[9]YANG C L,LI Z H,LI W J,et al.Batwing-like polymer membrane consisting of PMMA-grafted electrospun PVDF-SiO2nanocomposite fibers for lithium-ion batteries[J].Journal of Membrane Science,2015,495(1):341-350.
[10]DI N V,LAVINA S,GIFFIN G A,et al.Polymer electrolytes:Past and future[J].Electrochimica Acta,2011,57:4-13.
[11]CHEN J H,HU H J,LI S,et al.Evolution of mechanical properties of polypropylene separator in liquid electrolytes for lithium-ion batteries[J].Journal of Applied Polymer Science,2018,135(7):6-11.
[12]LIU S,ZHOU C,YU W.Phase separation and structure control in ultra-high molecular weight polyethylene microporous membrane[J].Journal of Membrane Science,2011,379(1-2):268-278.
[13]MIAO Y E,ZHU G N,HOU H Q,et al.Electrospun polyimide nanofiber-based nonwoven separators for lithium-ion batteries[J].Journal of Power Sources,2013,226:82-86.
[14]刘太奇,马福瑞,赵云腾.溶液聚偏氟乙烯静电纺纤维基超高分子量聚乙烯锂电池隔膜的制备[J].高分子材料科学与工程,2015,31(10):128-132.LIU T Q,MA F R,ZHAO Y T.Preparation of electrospun polyvinylidene fluoride fibers based UHMPWE lithium battery separator[J].Polymer Materials Science&Engineering,2015,31(10):128-132(in Chinese).
[15]ZHANG H,ZHOU M Y,LIN C E,et al.Progress in polymeric separators for lithium ion batteries[J].RSC Advance,2015,5(189):89848-89860.
[16]MATABOLA K P,MOUTLOALI R M.The influence of electrospinning parameters on the morphology and diameter of poly(vinyledene fluoride)nanofibers-effect of sodium chloride[J].Journal of Materials Science,2013,48(16):5475-5482.
[17]巩桂芬,王磊,徐阿文.静电纺PMMA/EVOH-SO3Li复合锂离子电池隔膜的制备及性能[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).
[18]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 Liion battery separator composite by electrospinning[J].Acta Materiae Compositae Sinica,2018,35(10):2632-2639(in Chinese).
[19]SPASOVA M,MANOLOVA N,MARKOVA N,et al.Tuning the properties of PVDF or PVDF-HFP fibrous materials decorated with ZnO nanoparticles by applying electrospinning alone or in conjunction with electrospraying[J].Fibers and Polymers,2017,18(4):649-657.
[20]WANG C J,SHEN W Z,LU J,et al.Graphene oxide doped poly(vinylidene fluoride-co-hexafluoropropylene)gel electrode for lithium-ion battery[J].Ionics,2017,23(8):2045-2053.
[21]于宾,焦晓宁.P(VDF-HFP)/Al2O3复合锂离子电池隔膜的电化学性能[J].电源技术,2015,39(4):702-705.YU B,JIAO X N.Electrochemical characterization of P(VDF-HFP)/Al2O3 composite separator for lithium-ion battery[J].Chinese Journal of Power Sources,2015,39(4):702-705(in Chinese).