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Publication numberCN104393337 B
Publication typeGrant
Application numberCN 201410750614
Publication date22 Feb 2017
Filing date10 Dec 2014
Priority date10 Dec 2014
Also published asCN104393337A
Publication number201410750614.1, CN 104393337 B, CN 104393337B, CN 201410750614, CN-B-104393337, CN104393337 B, CN104393337B, CN201410750614, CN201410750614.1
Inventors张海源
Applicant天津力神电池股份有限公司
Export CitationBiBTeX, EndNote, RefMan
External Links: SIPO, Espacenet
一种多级结构的锂离子电池凝胶电解液及其制备方法 A lithium ion battery and a gel electrolyte prepared multi-stage structure translated from Chinese
CN 104393337 B
Abstract  translated from Chinese
本发明公开了一种多级结构的锂电子电池凝胶电解液及其制备方法。 The present invention discloses a multistage a gel electrolyte lithium ion battery and its preparation method of the structure. 本发明多级结构的锂电子电池凝胶电解液包括聚合物网络交联骨架和存在于网络骨架中的液态电解液,其中聚合物网络物理交联骨架,是由聚偏氟乙烯(PVDF)静电纺丝的纳米纤维构成,交联骨架吸附于基膜PE膜的两侧。 A gel electrolyte lithium ion battery of the present invention a plurality of stages comprises a crosslinked polymer network backbone and a liquid electrolyte present in the backbone network, wherein the network physically crosslinked polymer backbone, is polyvinylidene fluoride (PVDF) Electrostatic spun nanofibers, backbone crosslinking adsorbed on both sides of the base film PE film. 本发明制备方法按照以下步骤进行:1)配制静电纺丝溶液;2)静电纺丝制备一级骨架结构;3)聚合物涂覆制备二级骨架结构;3)高温原位聚合,制备PMMA凝胶聚合物三级骨架结构。 The method of the present invention is prepared according to the following steps: 1) preparing an electrostatic spinning solution; 2) Preparation of an electrostatic spinning skeletal structure; 3) Preparation of two polymer coated skeletal structure; 3) in situ polymerization temperature, condensate prepared PMMA three plastic polymer backbone structure. 本发明凝胶骨架为逐级结构分布,此多层次结构的高分子交联体系相较于常规凝胶体系有着机械强度高,保液能力强,网络结构孔隙率大,电导率高等优点,为新一代凝胶电解质的研究铺平了道路。 The present invention is a gel matrix structure stepwise distribution, polymer crosslinking system configuration of this multi-level system in comparison to conventional gel has high mechanical strength, liquid-retaining ability, the network structure of large porosity, conductivity advantages as Research on a new generation of gel electrolyte paved the way.
Claims(6)  translated from Chinese
1.一种多级结构的锂离子电池凝胶电解液,其特征是,其包括聚合物网络交联骨架和存在于网络骨架中的液态电解液,其中聚合物网络交联骨架为凝胶电解液的一级结构,是由聚偏氟乙烯静电纺丝的纳米纤维构成,交联骨架吸附于基膜PE膜的两侧;聚合物交联主体为聚偏氟乙烯与六氟丙烯共聚的重均分子量10-100万的高分子,其吸附于一级结构之间,作为凝胶电解液的二级结构;三级结构为以二级结构的聚偏氟乙烯与六氟丙烯共聚高分子交联网络为支点的聚甲基丙烯酸甲酯原位聚合高分子凝胶网络。 A gel electrolyte lithium ion battery 1. A multi-stage structure, characterized in that it comprises a crosslinked polymer network liquid electrolyte present in the backbone network and the backbone, wherein the backbone of the crosslinked polymer network gel electrolyte a liquid structure, is made of polyvinylidene fluoride electrospun nanofibers, scaffold adsorbed crosslinked PE film on both sides of the base film; crosslinked polymer is polyvinylidene fluoride body weight of ethylene copolymerized with hexafluoropropylene average molecular weight of 10-100 million for polymer adsorption between a structure, a secondary structure of a gel electrolyte; tertiary structure of the secondary structure of polyvinylidene fluoride and hexafluoropropylene Copolymers post linked network as a fulcrum in situ polymerization of poly (methyl methacrylate) polymer gel network.
2.一种如权利要求1所述的多级结构的锂离子电池凝胶电解液的制备方法,其特征是,按照以下步骤进行: (I)配制静电纺丝溶液: 将要进行静电纺丝的聚合物在温度为40〜80C下溶于相应的有机溶剂中,搅拌5.5-6.5小时使其混合均匀,制得聚合物静电纺丝溶液;聚合物在静电纺丝溶液中的体积浓度为10%〜30% ; ⑵静电纺丝制备一级骨架结构: 将步骤(I)配好的静电纺丝溶液装入温度为40〜80C的静电纺丝设备的储液装置中,储液装置的活塞与注射器栗相连,储液装置通过聚四氟乙烯管与喷丝头相连,调整静电纺丝溶液的供料速率为5〜300yL/min;静电纺丝设备的喷丝头与接地的收集器之间的距离为5〜25cm;环境温度为35〜80C;环境的空气流速为O〜8.5m3/h;将锂电池隔膜置于收集器上,开启高压电源,开启注射器栗,将静电纺丝溶液喷射流喷射到锂电池隔膜上,在隔膜上得 The method of preparation of a gel electrolyte lithium ion battery 2. A multi-level structure as claimed in claim 1, characterized in that, in accordance with the following steps: (the I) prepared electrospinning solution: to be subjected to electrostatic spinning polymer is dissolved at a temperature of 40~80 C under appropriate organic solvent, stirred for 5.5-6.5 hours for homogenization to prepare a polymer solution electrospinning; volume concentration of the polymer in the electrostatic spinning solution is 10% ~ 30%; prepared in a skeletal structure ⑵ electrostatic spinning: reservoir means in step (I) with a good electrostatic spinning solution temperature of 40~80 C was charged electrostatic spinning apparatus, the reservoir means connected to the piston and the syringe Li, the reservoir means connected to Teflon tubing via spinneret, adjusting the electrostatic spinning solution feed rate was 5~300yL / min; spinneret electrospinning apparatus with the ground the distance between the collector of 5~25cm; ambient temperature is 35~80 C; air flow rate environment for O~8.5m3 / h; the lithium battery separator was placed on the collector, high voltage power supply is turned on, injector Li is turned on, the electrostatic spinning solution is sprayed onto the jet lithium battery separator, the separator obtained in 到聚合物静电纺丝纳米纤维膜层,从而形成聚合物静电纺丝纳米纤维一级结构; ⑶聚合物涂覆制备二级骨架结构: 在上述含有聚合物静电纺丝纳米纤维的隔膜上涂覆分子量为50〜500万的高分子量聚偏氟乙烯与六氟丙烯共聚物,涂覆后烘干,得到穿插于聚合物纳米纤维间的聚偏氟乙烯与六氟丙烯共聚物二级骨架;所述涂覆用水性涂覆或用油性涂覆,水性涂覆溶剂选取水性溶剂去离子水;油性涂覆溶剂选取油性溶剂丙酮或二甲基甲酰胺,涂覆的混合浆料浓度为20%〜50%,涂覆的速度控制为0.5m/min〜15m/min,烘干的风速5000〜1800rpm,温度50C〜200 Γ; ⑷电池卷绕: 将含有纳米纤维及聚偏氟乙烯与六氟丙烯共聚物的隔膜清洗,干燥,抽真空储存,并卷绕于电池中; ⑶电解液预聚体注液: 在常规电解液中加入聚甲基丙烯酸甲酯PMMA的高分子预聚体,加入引发剂过氧化二 Electrospinning the polymer nanofiber membrane layer, thereby forming a nanofiber electrospinning a polymer structure; Preparation of polymer-coated ⑶ two backbone structures: the separator is coated on the polymer-containing nanofiber electrospinning a molecular weight of 50~500 million for the high molecular weight polyvinylidene fluoride and hexafluoropropylene copolymer, after coating and drying, to obtain interspersed between the polymer nanofibers polyvinylidene fluoride and hexafluoropropylene copolymer backbone two; the coating said aqueous coating or oil-based coating, an aqueous coating solvent is an aqueous solvent selected deionized water; oily coating solvent selection oily solvent such as acetone or dimethylformamide, mixing the coated slurry concentration of 20% 50%, the coating speed is controlled to 0.5m / min~15m / min, drying wind speed 5000~1800rpm, a temperature of 50 C~200 Γ; ⑷ battery wound: and nanofibers containing polyvinylidene fluoride and six hexafluoropropylene copolymer membrane washed, dried, evacuated stored and wound in the battery; ⑶ priming liquid electrolyte polymer: polymethyl methacrylate polymer is added in conventional electrolyte PMMA prepolymer, peroxide initiator was added 甲酰,交联剂三乙胺,与电解液常温搅拌12h后注入电池中; (6)高温原位聚合,制备PMMA凝胶聚合物三级骨架结构: 将注液后的电池在50 C〜150 C下静置,静置时间为5min〜12h,使其原位聚合,得到纳米纤维上聚偏氟乙烯与六氟丙烯共聚物二级骨架间穿插交联的PMMA三级聚合物交联网络结构。 Formyl, triethylamine crosslinking agent, injected into the cell with the electrolyte after 12h stirring at room temperature; (6) in situ polymerization temperature, the preparation of three PMMA gel polymer backbone structure: after the cell injection was 50 C and allowed to stand at ~150 C, standing time is 5min~12h, so that in situ polymerization to give a polymer PMMA three cross polyvinylidene fluoride and hexafluoropropylene copolymer backbone nanofibres between two interspersed crosslinked linked network structure.
3.根据权利要求2所述的多级结构的锂离子电池凝胶电解液的制备方法,其特征是,所述步骤(I)聚合物在静电纺丝溶液中的体积浓度为15%。 The method of preparing a gel electrolyte lithium ion battery multilevel structure according to claim 2, wherein said step (I) the volume concentration of the polymer in the electrostatic spinning solution is 15%.
4.根据权利要求2所述的多级结构的锂离子电池凝胶电解液的制备方法,其特征是,所述步骤⑵中调整静电纺丝溶液的供料速率为20〜150yL/min。 The method of preparing a gel electrolyte lithium ion battery multilevel structure according to claim 2, wherein said adjusting step ⑵ electrostatic spinning solution feed rate was 20~150yL / min.
5.根据权利要求2所述的多级结构的锂离子电池凝胶电解液的制备方法,其特征是,所述步骤(2)中静电纺丝设备的喷丝头与接地的收集器之间的距离为7〜20cm。 The method of preparing a gel electrolyte lithium ion battery multilevel structure according to claim 2, characterized in that, between the step of electrospinning spinneret device and the ground collector (2) the distance 7~20cm.
6.根据权利要求2所述的多级结构的锂离子电池凝胶电解液的制备方法,其特征是,所述步骤⑵中环境温度为40〜60C;环境的空气流速为0.5〜5m3/h。 The method of preparing a gel electrolyte lithium ion battery multilevel structure according to claim 2, wherein said step ⑵ ambient temperature is 40~60 C; air flow rate environment for 0.5~5m3 / h.
Description  translated from Chinese
一种多级结构的锂离子电池凝胶电解液及其制备方法 A lithium ion battery and a gel electrolyte prepared multi-stage structure

技术领域 FIELD

[0001] 本发明涉及多级结构的锂离子电池用聚合物凝胶电解液系统(包括凝胶电解液和隔膜支撑骨架),特别涉及包括PVDF静电纺丝纳米纤维、PVDF-HFP聚合物交联二级网络以及原位聚合的聚合物交联网络的凝胶电解液系统。 [0001] The present invention relates to a lithium ion polymer battery using a gel electrolyte system multi-stage structure (including a gel electrolyte and a separator support skeleton), and more particularly to an electrostatic nanofibers include PVDF, PVDF-HFP polymer crosslinked situ polymerization and secondary network crosslinked network polymer gel electrolyte systems.

背景技术 Background technique

[0002] 锂离子电池由于具有电压高、体积小、重量轻、能量密度高和循环寿命长等优点,已获得了市场的主导地位。 [0002] Since lithium ion battery has a high voltage, small size, light weight, high energy density and long cycle life, etc., it has gained market dominance.

[0003]目前,锂离子电池的电解液分为液态电解液和凝胶电解液。 [0003] Currently, lithium ion battery electrolyte into a gel electrolyte and a liquid electrolyte. 其中,液态电解液的特点是电化学性能稳定可靠,但却普遍存在安全性差、电池硬度不够易变形等问题。 Wherein the characteristics of liquid electrolyte is electrochemically stable and reliable performance, but the prevalence of poor security, battery deformation insufficient hardness and so on. 相比之下,凝胶电解液体系将流动态的溶剂分子固定在高分子凝胶骨架内,因不存在或较少存在游离态的溶剂而减小了电解液渗漏的风险,有效地降低了电池体系的燃烧性,进而提高了电池的安全性;同时,由于高分子骨架将整个电芯连成一个整体,因此有利于减少电芯变形和膨胀。 In contrast, a gel electrolyte flow system dynamically solvent molecules within the polymer gel matrix is fixed, due to the absence of a solvent or in the free state and there is less risk of electrolyte leakage is reduced, effectively reducing the combustion of the battery system, thereby improving the safety of the battery; the same time, since the entire polymer skeleton batteries together into a whole, and therefore helps to reduce distortion and cell expansion. 所以,凝胶电解液体系有着十分光明的应用前景。 Therefore, the gel electrolyte system has a very bright prospect.

[0004] 现有凝胶电解液一般是向液态电解液中添加可聚合单体制备而成的,所添加的可聚合单体可溶于液态电解液,生成的聚合物也可溶于液态电解液。 [0004] Usually a gel electrolyte is added prior to the liquid electrolyte may be polymerized from a monomer polymerizable monomer to be added is soluble in liquid electrolyte, the resulting polymer may also be dissolved in the electrolytic liquid liquid. 由于凝胶电解液前体中可聚合单体的浓度较低时,会不足以使液态电解液转换为凝胶电解液,因此往往需要添加较多的可聚合单体;但可聚合单体的浓度较高时,所生成的凝胶电解液中的聚合物浓度也较高,又会引发锂离子传导困难,以致出现锂离子电导率低、容易析锂等一系列电化学性能问题。 Since lower concentrations a gel electrolyte monomer precursor may be polymerized will be insufficient to convert liquid electrolyte is a gel electrolyte, it is often necessary to add more polymerizable monomers; however, a polymerizable monomer At higher concentrations, the concentration of the polymer gel electrolyte is also generated higher lithium ion conductivity will lead to difficulties, resulting in occurrence of low lithium ion conductivity, lithium is easy to analyze a series of electrochemical performance issues.

[0005] 有鉴于此,确有必要提供一种力学性能、电化学性能以及安全性全都良好的锂离子电池凝胶电解液。 [0005] needed, therefore, necessary to provide a mechanical properties, electrochemical performance and safety of lithium ion batteries are all excellent gel electrolyte.

发明内容 SUMMARY

[0006] 本发明的目的在于:提供一种力学性能、电化学性能以及安全性全都良好的锂离子电池凝胶电解液;本发明的另一个目的在于通过多级结构的设计得到一种保液量更强,结构更稳定的锂离子电池凝胶电解液。 [0006] The object of the present invention is: to provide a mechanical properties, electrochemical performance and safety of lithium ion batteries are all excellent gel electrolyte; a further object of the present invention is to obtain a multi-stage liquid retention structures by designing the amount of stronger, more stable structure of a gel electrolyte lithium ion batteries.

[0007] 为了实现上述目的,本发明的的技术方案如下: [0007] To achieve the above object, the technical solution of the present invention are as follows:

[0008] 本发明提供了一种多级结构的锂电子电池凝胶电解液,其包括聚合物网络交联骨架和存在于网络骨架中的液态电解液,其中聚合物网络交联骨架为凝胶电解液的一级结构,是由聚偏氟乙烯(PVDF)静电纺丝的纳米纤维构成,交联骨架吸附于基膜PE膜的两侧;聚合物交联主体为聚偏氟乙稀与六氟丙稀共聚(PVDF-HFP)的重均分子量10-100万的尚分子,其吸附于一级骨架之间,作为凝胶电解液的二级结构;三级骨架为以二级骨架的PVDF-HFP共聚高分子交联网络为支点的聚甲基丙烯酸甲酯(PMMA)原位聚合高分子凝胶网络,主要提供保持液态电液作用。 [0008] The present invention provides a multi-level structure of a gel electrolyte lithium ion battery, which comprises a crosslinked polymer network liquid electrolyte present in the backbone network and the backbone, wherein the backbone of the crosslinked polymer network gel a structure of the electrolytic solution, by polyvinylidene fluoride (PVDF) electrospun nanofibers, scaffold adsorbed crosslinked PE film on both sides of the base film; crosslinked polymer body is a polyvinylidene fluoride and six re-fluoro-propylene copolymer (PVDF-HFP) average molecular weight of 10-100 million for still molecules, the adsorption between a skeleton of a secondary structure of a gel electrolyte; two to three skeleton is a skeleton PVDF Copolymers -HFP crosslinked network as a fulcrum polymethyl methacrylate (PMMA) polymer gel in situ polymerization networks, mainly to provide a liquid holding electro-hydraulic action.

[0009] 本发明的优点是凝胶骨架的逐级结构分布,PE基膜之上静电纺丝纳米纤维的机械强度最高,主要提供体系强度和支撑,穿插于纳米纤维之间的PVDF-HFP聚合物为凝胶交联主体,起到提供部分体系强度和连接宏观一级结构和微观三级结构的过渡结构,三级结构PMMA原位聚合结构起到保持液态电解液中的小分子溶剂和锂离子盐的作用。 [0009] The advantage of the present invention, the skeleton structure of the gel is gradual distribution, the mechanical strength of the above base film PE electrospun nanofibers highest mainly provides strength and support system, interspersed between the PVDF-HFP nanofiber polymerization was crosslinked gel body, functions to provide strength and connection system part of the macro a transition structure and microstructure of the tertiary structure, tertiary structure PMMA situ polymeric structure serves to hold the solvent and small molecules in the liquid electrolyte lithium effect of ionic salt. 此多层次结构的高分子交联体系相较于常规凝胶体系有着机械强度高,保液能力强,网络结构孔隙率大,电导率高等优点,有着广阔的应用前景。 This multi-polymer crosslinking system hierarchy compared to conventional gel systems with high mechanical strength, liquid-retaining ability, the network structure of large porosity, conductivity advantages, has broad application prospects.

[0010] 多级结构的锂电子电池凝胶电解液的制备方法,包括以下的步骤: Preparation [0010] The method of a gel electrolyte lithium ion battery of the plurality of stages, comprising the steps of:

[0011] (I)配制静电纺丝溶液: [0011] (I) prepared electrospinning solution:

[0012] 将要进行静电纺丝的聚合物在温度为40〜80C (优选50C)下溶于相应的有机溶剂中,搅拌(一般为6小时左右)使其混合均匀,制得聚合物静电纺丝溶液;聚合物在静电纺丝溶液中的体积浓度为10%〜30%,优选体积浓度为15% ; [0012] The electrospun polymer to be dissolved at a temperature of 40~80 C (preferably 50 C) under appropriate organic solvent, with stirring (typically about 6 hours) to mix homogeneously, to prepare polymerization was electrospinning solution; volume concentration of the polymer in the electrostatic spinning solution is 10% ~ 30%, preferably a volume concentration of 15%;

[0013] (2)静电纺丝制备一级骨架结构: [0013] (2) Preparation of an electrostatic spinning skeletal structure:

[0014] 将步骤⑴配好的静电纺丝溶液装入温度为40〜80C的静电纺丝设备的储液装置中,储液装置的活塞与注射器栗相连,储液装置通过聚四氟乙烯管与喷丝头相连,调整静电纺丝溶液的供料速率为5〜300yL/min,优选为20〜150yL/min;静电纺丝设备的喷丝头与接地的收集器之间的距离为5〜25cm,优选为7〜20cm;环境温度为35〜80C,优选为40〜60C;环境的空气流速为O〜8.5m3/h,优选为0.5〜5m3/h;将锂电池隔膜置于收集器上,开启高压电源(静电压为I〜60kV,适宜值为15〜20kV),开启注射器栗,将静电纺丝溶液喷射流喷射到锂电池隔膜上,在隔膜上得到聚合物静电纺丝纳米纤维膜层,从而形成聚合物静电纺丝纳米纤维一级结构; [0014] Step ⑴ electrostatic spinning solution was charged with a good temperature of the liquid receive means electrospinning apparatus 40~80 C, the syringe plunger is connected to the accumulator means Li, the reservoir means via PTFE vinyl tube is connected to a spinneret electrospinning solution to adjust the feed rate of 5~300yL / min, preferably 20~150yL / min; the distance between the spinneret electrospinning apparatus for the collector and ground 5~25cm, preferably 7~20cm; ambient temperature is 35~80 C, preferably 40~60 C; air flow rate environment for O~8.5m3 / h, preferably 0.5~5m3 / h; lithium batteries diaphragm disposed on the collector, high voltage power supply is turned on (the static voltage I~60kV, a suitable value 15~20kV), open syringe Li, electrostatic spinning solution was sprayed onto the jet lithium battery separator, to obtain a polymer in the membrane electrospinning nanofiber membrane layer, thereby forming a nanofiber electrospinning a polymer structure;

[0015] (3)聚合物涂覆制备二级骨架结构: [0015] (3) Preparation of polymer-coated two backbone structures:

[0016] 在上述含有聚合物静电纺丝纳米纤维的隔膜上涂覆分子量为50〜500万的高分子量PVDF-HFP共聚物,涂覆后烘干,得到穿插于聚合物纳米纤维间的PVDF-HFP共聚物二级骨架;涂覆可用水性涂覆,其中溶剂可选取水性溶剂如去离子水;涂覆也可用油性涂覆,其中溶剂可选取油性溶剂如丙酮,二甲基甲酰胺(DMF);涂覆的混合浆料浓度为20%〜50%(PVDF-HFP的百分比),涂覆的速度控制位0.5m/min〜15m/min,烘干的风速5000〜1800rpm,温度50C 〜200C; [0016] In the diaphragm-containing polymer coated nanofiber electrospinning molecular weight of 50~500 million for the high molecular weight PVDF-HFP copolymer, after coating and drying, to obtain interspersed between the polymer nanofibers PVDF- two HFP copolymer backbone; coated with an aqueous coating, wherein the solvent is selected from water solvents such as deionized water; oily coating may also be applied, wherein the solvent is an oily solvent may be selected such as acetone, dimethylformamide (DMF) ; mixed coating slurry concentration of 20% ~ 50% (the percentage of PVDF-HFP), speed control bits coated 0.5m / min~15m / min, drying wind speed 5000~1800rpm, a temperature of 50 C ~ 200 C;

[0017] ⑷电池卷绕。 [0017] ⑷ battery winding.

[0018] 将含有纳米纤维及PVDF-HFP的隔膜清洗,干燥,抽真空储存,并卷绕于电池中; [0018] The separator containing nanofibers and washing PVDF-HFP, dried, evacuated stored and wound in the battery;

[0019] (5)电解液预聚体注液: [0019] (5) a prepolymer electrolyte injection:

[0020] 在常规电解液中加入聚甲基丙烯酸甲酯PMMA的高分子预聚体,加入引发剂过氧化二苯甲酰(BPO),交联剂三乙胺,与电解液常温搅拌12h后注入电池中; After [0020] Poly (methyl methacrylate) PMMA were added in a conventional polymer electrolyte prepolymer was added dibenzoyl peroxide initiator (the BPO), triethylamine crosslinking agent, and electrolyte solution stirred 12h at room temperature injected into the cell;

[0021] (6)高温原位聚合,制备PMMA凝胶聚合物三级骨架结构: [0021] (6) high-temperature in situ polymerization, preparing three PMMA gel polymer backbone structure:

[0022] 将注液后的电池进行高温下静置,使其原位聚合,得到纳米纤维上PVDF-HFP 二级骨架间穿插交联的PMMA三级聚合物交联网络结构;其中,锂离子电池静置温度为50C〜150C,静置时间为5min〜12h。 [0022] The injection was carried out after the battery was allowed to stand at a high temperature, so that in situ polymerization to give a polymer PMMA three crosslinked network structure on the PVDF-HFP nanofiber interspersed between two crosslinked backbone; wherein the lithium ion battery temperature is allowed to stand 50 C~150 C, standing time is 5min~12h.

[0023] 交联网络结构在不同尺度范围内分级展开,可以大大的提高聚合物交联网络结构的保液性和机械稳定性,从而提高锂离子电池安全性能和循环性能。 [0023] The hierarchical structure of the crosslinked network deployed in different scales, can greatly improve the liquid retention and the mechanical stability of the crosslinked polymer network structure, thereby improving battery safety performance, and cycle performance of a lithium ion.

[0024]与现有技术相比,本发明的含有多级结构的锂离子电池凝胶电解液有如下的优占.V. [0024] Compared with the prior art, a gel electrolyte containing a lithium ion battery of the present invention, a multi-stage structure has the following advantages accounted .V.

[0025]由于其结构的多层次性,各级结构在不同的尺度范围内对凝胶电解液有支撑作用,大尺度下纳米纤维作为支撑主体,微观尺度下PMMA聚合物三维交联网络作为保持电液的主体,使得本发明制备的凝胶电池相较于传统凝胶电池,其保液能力更强,凝胶电液的机械强度更高,凝胶电池的安全性能更好,静电纺丝纳米纤维膜层孔隙率较高,使得凝胶电解液整体的电导性能提高,循环性能也有较大的提升,为未来新一代的凝胶电池开拓了新的方向。 [0025] Because of the multilevel nature of its structure, a supporting effect on the stages of a gel electrolyte in different scales, large-scale nanofiber as a supporting body, PMMA polymer three dimensional crosslinked network held at a micro-scale electric body fluid, such gels prepared by the present invention is a battery compared to conventional gel battery, more liquid-retention capacity, high mechanical strength of the gel electrolyte solution, gel better safety performance of the battery, electrospinning nanofiber layer high porosity, conductive properties of such a gel electrolyte improve overall cycle performance is also greatly improved, open up a new direction for future generations of gel batteries.

附图说明 BRIEF DESCRIPTION

[0026]图1,凝胶电解液多级结构示意图; [0026] FIG. 1, a schematic view of multi-level structure of a gel electrolyte;

[0027] 图2,凝胶电解液一级结构,PVDF纳米纤维网络结构扫描电子显微镜(SEM)图; [0027] FIG 2, a structure of a gel electrolyte, PVDF nanofiber network structure of a scanning electron microscope (SEM) FIG;

[0028] 图3,凝胶电解液二级结构及三级结构,PVDF纳米纤维网络之间超高分子量PVDF-HFP与PMMA聚合物交联网络SEM图; [0028] FIG. 3, a gel electrolyte secondary structure and tertiary structure, between the nanofiber network ultrahigh molecular weight PVDF PVDF-HFP and PMMA polymer crosslinked network SEM image;

[0029] 图4,凝胶电解液二级结构及三级结构,PVDF纳米纤维表面吸附的聚合物交联网络SEM 图; [0029] FIG. 4, a gel electrolyte secondary structure and tertiary structure, PVDF nanofiber surface adsorbed crosslinked polymer network SEM image;

[0030] 图5,聚合物静电纺丝过程示意图。 [0030] FIG. 5, a schematic diagram of the polymer during electrospinning.

具体实施方式 detailed description

[0031] 本发明锂电子电池凝胶电解液结构如图1所示,其包括聚合物网络交联骨架和存在于网络骨架中的液态电解液,其中聚合物网络物理交联骨架为凝胶电解液的一级结构1,是由聚偏氟乙烯(PVDF)静电纺丝的纳米纤维构成,交联骨架吸附于基膜PE膜4的两侧;聚合物交联主体为PVDF-HFP共聚的重均分子量10-100万的高分子,其吸附于一级骨架之间,作为凝胶聚合物二级结构2;三级骨架3为以二级骨架的PVDF-HFP共聚高分子交联网络为支点的聚甲基丙烯酸甲酯PMMA原位聚合高分子凝胶网络,主要提供保持液态电液作用。 [0031] The lithium ion battery of the present invention, a gel electrolyte shown in Figure 1, which comprises a crosslinked polymer network backbone and the network backbone is present in the liquid electrolyte, wherein the polymer backbone network is physically crosslinked gel electrolyte a structure of a liquid, is polyvinylidene fluoride (PVDF) electrospun nanofibers, scaffold adsorbed crosslinked PE film on both sides of the base film 4; crosslinked polymer is PVDF-HFP copolymer body weight average molecular weight of 10-100 million for polymer adsorption between a skeleton, as the gel polymer secondary structure 2; 3 at three backbone copolymer PVDF-HFP polymer crosslinked network skeleton is two fulcrum poly (methyl methacrylate) PMMA in situ polymerization of polymer gel networks, mainly to provide electro-hydraulic action remains liquid.

[0032] 实施例1 [0032] Example 1

[0033] I).配制静电纺丝溶液。 [0033] I). Electrospinning solution is prepared. 将要进行静电纺丝的聚合物(聚偏氟乙烯)在50C下溶于N,N-二甲基甲酰胺中,搅拌6h使其混合均匀,制得聚合物静电纺丝溶液,其中聚合物在静电纺丝溶液中的体积浓度为15% (g/mL)。 To be subjected to electrostatic spinning of polymer (polyvinylidene fluoride) in N at 50 C, N- dimethylformamide was stirred 6h for homogenization to prepare a polymer solution electrospinning, wherein the polymerization volume concentration was electrospinning solution is 15% (g / mL).

[0034] (2)静电纺丝制备一级骨架结构: [0034] (2) Preparation of an electrostatic spinning skeletal structure:

[0035] 过程如图5所示,将步骤I)配好的静电纺丝溶液装入温度为50C的静电纺丝设备的储液装置中,储液装置的活塞与注射器栗相连,储液装置通过聚四氟乙烯管与喷丝头相连,喷丝头固定,金属平板上放置无纺布作为收集器。 [0035] The process shown in Figure 5, in step I) with a good charged electrostatic spinning solution temperature of the liquid receive means electrospinning apparatus at 50 C, the syringe plunger is connected to the accumulator means Li, Chu fluid means through a Teflon tube connected to the spinneret, the spinneret is fixed, the nonwoven fabric is placed on a metal plate as a collector. 调节喷丝头与收集板之间的距离为15cm;纺丝的环境温度为50C,包括储液装置中静电纺丝溶液的温度和收集板的温度均为50C,环境中的空气流速控制在0.5〜0.8m3/h;开启高压电源,调节电压至15kV,静电纺丝溶液的供料速率为60yL/min,开启注射器栗,将静电纺丝溶液喷射流喷射到锂电池隔膜上,在隔膜上得到聚合物静电纺丝纳米纤维膜层,从而在形成聚合物静电纺丝纳米纤维一级结构。 Adjustment between the spinneret and the collector plate distance of 15cm; spinning temperature is 50 C, including the temperature of the reservoir and the collecting plate means in the electrostatic spinning solution are 50 C, ambient air in the flow rate control 0.5~0.8m3 / h; high voltage power supply is turned on, to adjust the voltage 15kV, the feed rate of the electrostatic spinning solution was 60yL / min, injector Li is turned on, the electrostatic spinning solution was sprayed onto the jet lithium battery separator, electrospinning nanofibers obtained polymer film layer on the membrane, thereby forming a nanofiber electrospinning a polymer structure. 纤维平均直径为500nm,聚合物静电纺丝纳米纤维膜层厚度为40μπι (聚合物静电纺丝纳米纤维膜层的SEM图见图2)。 Average fiber diameter was 500nm, the polymer nanofibers electrospun film thickness of 40μπι (electrospun polymer nanofiber membrane layer SEM shown in Figure 2).

[0036] (3)聚合物涂覆制备二级骨架结构: [0036] (3) Preparation of polymer-coated two backbone structures:

[0037] 在含有聚合物静电纺丝纳米纤维隔膜上涂覆分子量约为50w的高分子量PVDF-HFP共聚物(产品购于阿克玛公司,型号为LBG),涂覆后烘干,得到穿插于聚合物纳米纤维间的PVDF-HFP共聚物二级骨架。 [0037] In electrospinning a polymer containing fiber membranes coated on the nano molecular weight of about 50w high molecular weight PVDF-HFP copolymer (product commercially available from Arkema, the LBG model), after coating and drying, to give interspersed nano polymer PVDF-HFP copolymer backbone between the two fibers. 涂覆使用油性涂覆,其中溶剂选取油性溶剂丙酮。 Oily coating using a coating, wherein the oily solvent is selected solvent such as acetone. 涂覆的混合浆料浓度为20%,涂覆的速度控制位lm/min,烘干的风速5000rpm,温度90C。 Mixing the coated slurry concentration of 20%, the coating speed control bit lm / min, 5000 rpm for drying wind speed, temperature of 90 C.

[0038] ⑷电池卷绕。 [0038] ⑷ battery winding.

[0039] 将含有纳米纤维及PVDF-HFP的隔膜使用乙醇清洗,干燥,抽真空储存,并卷绕于电池中。 [0039] and containing PVDF-HFP nanofiber membrane washed with ethanol, dried, vacuum reservoir, and wound in the battery.

[0040] (5)电解液预聚体注液: [0040] (5) a prepolymer electrolyte injection:

[0041] 调配电解液碳酸乙烯酯(EC),碳酸二甲酯(DEC),碳酸甲乙酯(EMC)配比为1:1:1,六氟磷酸锂的摩尔浓度为1.0mol/L。 [0041] formulations as ethylene carbonate (EC), dimethyl carbonate (DEC), ethylmethyl carbonate (EMC) ratio of 1: 1: 1, the molar concentration of lithium hexafluoro phosphate was 1.0mol / L. 在电解液中加入聚甲基丙烯酸甲酯PMMA的高分子预聚体,加入引发剂BPO,交联剂三乙胺,其中电液中PMMA的百分含量为10%,BPO的百分含量为0.1%,三乙胺的百分含量为1%与电解液常温搅拌12h后注入电池中。 Polymethyl methacrylate PMMA was added in an electrolyte polymer prepolymer, addition of BPO initiator, a crosslinking agent, triethylamine, wherein the percentage of electrically PMMA was 10%, the percentage content of BPO 0.1%, the percentage of 1% triethylamine was injected into the cell after 12h stirring at room temperature with the electrolyte.

[0042] ⑶高温原位聚合,制备PMMA凝胶聚合物三级骨架结构: [0042] ⑶ situ polymerization temperature, the preparation of three PMMA gel polymer backbone structure:

[0043] 将注液后的电池进行高温下静置,使其原位聚合,得到纳米纤维上PVDF-HFP 二级骨架间穿插交联的PMMA三级聚合物交联网络结构。 [0043] The injection was carried out after the battery was allowed to stand at a high temperature, so that in situ polymerization to give a polymer PMMA three crosslinked network structure on the PVDF-HFP nanofiber interspersed between two skeleton crosslinked. 其中,锂离子电池静置温度为80C,静置时间为24h。 Wherein the temperature of the lithium ion battery is allowed to stand 80 C, resting time was 24h.

[0044] 凝胶电解液二级结构及三级结构,PVDF纳米纤维网络之间超高分子量PVDF-HFP与PMMA聚合物交联网络SEM图见图3。 [0044] The gel electrolyte secondary structure and tertiary structure, between the nanofiber network ultrahigh molecular weight PVDF PVDF-HFP and PMMA SEM crosslinked polymer network is shown in Figure 3. 凝胶电解液二级结构及三级结构,PVDF纳米纤维表面吸附的聚合物交联网络SM图见图4。 A gel electrolyte secondary structure and tertiary structure, PVDF nanofiber surface adsorbed crosslinked polymer network is shown in Figure 4 SM.

[0045] 实施例2 [0045] Example 2

[0046] I).配制静电纺丝溶液。 [0046] I). Electrospinning solution is prepared. 将要进行静电纺丝的聚合物(聚偏氟乙烯)在50C下溶于N,N-二甲基甲酰胺中,搅拌6h使其混合均匀,制得聚合物静电纺丝溶液,其中聚合物在静电纺丝溶液中的体积浓度为15% (g/mL)。 To be subjected to electrostatic spinning of polymer (polyvinylidene fluoride) in N at 50 C, N- dimethylformamide was stirred 6h for homogenization to prepare a polymer solution electrospinning, wherein the polymerization volume concentration was electrospinning solution is 15% (g / mL).

[0047] (2)静电纺丝制备一级骨架结构: [0047] (2) Preparation of an electrostatic spinning skeletal structure:

[0048] 将步骤I)配好的静电纺丝溶液装入温度为50C的静电纺丝设备的储液装置中,储液装置的活塞与注射器栗相连,储液装置通过聚四氟乙烯管与喷丝头相连,喷丝头固定,金属平板上放置无纺布作为收集器。 [0048] The step I) with a good charged electrostatic spinning solution temperature of the liquid receive means electrospinning apparatus at 50 C, the syringe plunger is connected to the accumulator means Li, a reservoir by means of polytetrafluoroethylene and the nozzle is connected to the head tube of the spinneret is fixed, the nonwoven fabric is placed on a metal plate as a collector. 调节喷丝头与收集板之间的距离为15cm;纺丝的环境温度为50C,包括储液装置中静电纺丝溶液的温度和收集板的温度均为50C,环境中的空气流速控制在0.5〜0.8m3/h;开启高压电源,调节电压至15kV,静电纺丝溶液的供料速率为60yL/min,开启注射器栗,将静电纺丝溶液喷射流喷射到锂电池隔膜上,在隔膜上得到聚合物静电纺丝纳米纤维膜层,从而在形成聚合物静电纺丝纳米纤维一级结构。 Adjustment between the spinneret and the collector plate distance of 15cm; spinning temperature is 50 C, including the temperature of the reservoir and the collecting plate means in the electrostatic spinning solution are 50 C, ambient air in the flow rate control 0.5~0.8m3 / h; high voltage power supply is turned on, to adjust the voltage 15kV, the feed rate of the electrostatic spinning solution was 60yL / min, injector Li is turned on, the electrostatic spinning solution was sprayed onto the jet lithium battery separator, electrospinning nanofibers obtained polymer film layer on the membrane, thereby forming a nanofiber electrospinning a polymer structure. 纤维平均直径为500nm,聚合物静电纺丝纳米纤维膜层厚度为40μπι (聚合物静电纺丝纳米纤维膜层的SEM图见图2) ο Average fiber diameter was 500nm, the polymer nanofibers electrospun film thickness of 40μπι (electrospun polymer nanofiber membrane layer SEM shown in Figure 2) ο

[0049] ⑶聚合物涂覆制备二级骨架结构: [0049] Preparation of polymer-coated ⑶ two backbone structures:

[0050] 在含有聚合物纳米纤维隔膜上涂覆分子量约为45w的高分子量PVDF-HFP共聚物(产品购于苏威公司,型号21216,其中HFP共聚比例较高),涂覆后烘干,得到穿插于聚合物纳米纤维间的PVDF-HFP共聚物二级骨架。 [0050] In the membrane comprising a polymeric coating nanofibers approximate molecular weight of the high molecular weight 45w of PVDF-HFP copolymer (available from Solvay product, model 21216, wherein high HFP copolymerization ratio), after coating and drying, resulting PVDF-HFP copolymer interspersed in the backbone between the two polymer nanofibers. 涂覆使用油性涂覆,其中溶剂选取油性溶剂丙酮。 Oily coating using a coating, wherein the oily solvent is selected solvent such as acetone. 涂覆的混合浆料浓度为20%,涂覆的速度控制位lm/min,烘干的风速5000rpm,温度90C。 Mixing the coated slurry concentration of 20%, the coating speed control bit lm / min, 5000 rpm for drying wind speed, temperature of 90 C.

[0051] ⑷电池卷绕。 [0051] ⑷ battery winding.

[0052] 将含有纳米纤维及PVDF-HFP的隔膜使用乙醇清洗,干燥,抽真空储存,并卷绕于电池中。 [0052] and containing PVDF-HFP nanofiber membrane washed with ethanol, dried, vacuum reservoir, and wound in the battery.

[0053] (5)电解液预聚体注液: [0053] (5) a prepolymer electrolyte injection:

[0054] 调配电解液碳酸乙烯酯(EC),碳酸二甲酯(DEC),碳酸甲乙酯(EMC)配比为1:1:1,六氟磷酸锂的摩尔浓度为1.0mol/L。 [0054] formulations as ethylene carbonate (EC), dimethyl carbonate (DEC), ethylmethyl carbonate (EMC) ratio of 1: 1: 1, the molar concentration of lithium hexafluoro phosphate was 1.0mol / L. 在电解液中加入聚甲基丙烯酸甲酯PMMA的高分子预聚体,加入引发剂BPO,交联剂三乙胺,其中电液中PMMA的百分含量为10%,BPO的百分含量为0.1%,三乙胺的百分含量为1%与电解液常温搅拌12h后注入电池中。 Polymethyl methacrylate PMMA was added in an electrolyte polymer prepolymer, addition of BPO initiator, a crosslinking agent, triethylamine, wherein the percentage of electrically PMMA was 10%, the percentage content of BPO 0.1%, the percentage of 1% triethylamine was injected into the cell after 12h stirring at room temperature with the electrolyte.

[0055] (6)高温原位聚合,制备PMMA凝胶聚合物三级骨架结构: [0055] (6) high-temperature in situ polymerization, preparing three PMMA gel polymer backbone structure:

[0056] 将注液后的电池进行高温下静置,使其原位聚合,得到纳米纤维上PVDF-HFP 二级骨架间穿插交联的PMMA三级聚合物交联网络结构。 [0056] The injection was carried out after the battery was allowed to stand at a high temperature, so that in situ polymerization to give a polymer PMMA three crosslinked network structure on the PVDF-HFP nanofiber interspersed between two skeleton crosslinked. 其中,锂离子电池静置温度为80C,静置时间为24h。 Wherein the temperature of the lithium ion battery is allowed to stand 80 C, resting time was 24h.

[0057] 实施例3 [0057] Example 3

[0058] I).配制静电纺丝溶液。 [0058] I). Electrospinning solution is prepared. 将要进行静电纺丝的聚合物(聚偏氟乙烯)在50C下溶于N,N-二甲基甲酰胺中,搅拌6h使其混合均匀,制得聚合物静电纺丝溶液,其中聚合物在静电纺丝溶液中的体积浓度为15% (g/mL)。 To be subjected to electrostatic spinning of polymer (polyvinylidene fluoride) in N at 50 C, N- dimethylformamide was stirred 6h for homogenization to prepare a polymer solution electrospinning, wherein the polymerization volume concentration was electrospinning solution is 15% (g / mL).

[0059] (2)静电纺丝制备一级骨架结构: [0059] (2) Preparation of an electrostatic spinning skeletal structure:

[0060] 将步骤I)配好的静电纺丝溶液装入温度为50C的静电纺丝设备的储液装置中,储液装置的活塞与注射器栗相连,储液装置通过聚四氟乙烯管与喷丝头相连,喷丝头固定,金属平板上放置无纺布作为收集器。 [0060] The step I) with a good charged electrostatic spinning solution temperature of the liquid receive means electrospinning apparatus at 50 C, the syringe plunger is connected to the accumulator means Li, a reservoir by means of polytetrafluoroethylene and the nozzle is connected to the head tube of the spinneret is fixed, the nonwoven fabric is placed on a metal plate as a collector. 调节喷丝头与收集板之间的距离为15cm;纺丝的环境温度为50C,包括储液装置中静电纺丝溶液的温度和收集板的温度均为50C,环境中的空气流速控制在0.5〜0.8m3/h;开启高压电源,调节电压至15kV,静电纺丝溶液的供料速率为60yL/min,开启注射器栗,将静电纺丝溶液喷射流喷射到锂电池隔膜上,在隔膜上得到聚合物静电纺丝纳米纤维膜层,从而在形成聚合物静电纺丝纳米纤维一级结构。 Adjustment between the spinneret and the collector plate distance of 15cm; spinning temperature is 50 C, including the temperature of the reservoir and the collecting plate means in the electrostatic spinning solution are 50 C, ambient air in the flow rate control 0.5~0.8m3 / h; high voltage power supply is turned on, to adjust the voltage 15kV, the feed rate of the electrostatic spinning solution was 60yL / min, injector Li is turned on, the electrostatic spinning solution was sprayed onto the jet lithium battery separator, electrospinning nanofibers obtained polymer film layer on the membrane, thereby forming a nanofiber electrospinning a polymer structure. 纤维平均直径为500nm,聚合物静电纺丝纳米纤维膜层厚度为40μπι (聚合物静电纺丝纳米纤维膜层的SEM图见图2) ο Average fiber diameter was 500nm, the polymer nanofibers electrospun film thickness of 40μπι (electrospun polymer nanofiber membrane layer SEM shown in Figure 2) ο

[0061] (3)聚合物涂覆制备二级骨架结构: [0061] (3) Preparation of polymer-coated two backbone structures:

[0062] 在含有聚合物纳米纤维隔膜上涂覆分子量约为50w的高分子量PVDF-HFP共聚物(产品购于阿克玛公司,型号为8500,此为阿克玛公司专门为凝胶电解液开发的一款含氟高分子胶黏剂),涂覆后烘干,得到穿插于聚合物纳米纤维间的PVDF-HFP共聚物二级骨架。 [0062] In a gel electrolyte containing a polymer nano-fiber membranes coated on the molecular weight of about 50w high molecular weight PVDF-HFP copolymer (product commercially available from Arkema, Model 8500, which is dedicated to Arkema the development of a fluorine polymer adhesive), after coating and drying, to obtain a PVDF-HFP copolymer interspersed backbone between two polymer nanofibers. 涂覆使用油性涂覆,其中溶剂选取油性溶剂丙酮。 Oily coating using a coating, wherein the oily solvent is selected solvent such as acetone. 涂覆的混合浆料浓度为20%,涂覆的速度控制位lm/min,烘干的风速5000rpm,温度90C。 Mixing the coated slurry concentration of 20%, the coating speed control bit lm / min, 5000 rpm for drying wind speed, temperature of 90 C.

[0063] ⑷电池卷绕。 [0063] ⑷ battery winding.

[0064] 将含有纳米纤维及PVDF-HFP的隔膜使用乙醇清洗,干燥,抽真空储存,并卷绕于电池中。 [0064] and containing PVDF-HFP nanofiber membrane washed with ethanol, dried, vacuum reservoir, and wound in the battery.

[0065] (5)电解液预聚体注液: [0065] (5) a prepolymer electrolyte injection:

[0066] 调配电解液碳酸乙烯酯(EC),碳酸二甲酯(DEC),碳酸甲乙酯(EMC)配比为1:1:1,六氟磷酸锂的摩尔浓度为1.0mol/L。 [0066] formulations as ethylene carbonate (EC), dimethyl carbonate (DEC), ethylmethyl carbonate (EMC) ratio of 1: 1: 1, the molar concentration of lithium hexafluoro phosphate was 1.0mol / L. 在电解液中加入聚甲基丙烯酸甲酯PMMA的高分子预聚体,加入引发剂BPO,交联剂三乙胺,其中电液中PMMA的百分含量为10%,BPO的百分含量为0.1%,三乙胺的百分含量为1%与电解液常温搅拌12h后注入电池中。 Polymethyl methacrylate PMMA was added in an electrolyte polymer prepolymer, addition of BPO initiator, a crosslinking agent, triethylamine, wherein the percentage of electrically PMMA was 10%, the percentage content of BPO 0.1%, the percentage of 1% triethylamine was injected into the cell after 12h stirring at room temperature with the electrolyte.

[0067] (6)高温原位聚合,制备PMMA凝胶聚合物三级骨架结构: [0067] (6) high-temperature in situ polymerization, preparing three PMMA gel polymer backbone structure:

[0068] 将注液后的电池进行高温下静置,使其原位聚合,得到纳米纤维上PVDF-HFP 二级骨架间穿插交联的PMMA三级聚合物交联网络结构。 [0068] The injection was carried out after the battery was allowed to stand at a high temperature, so that in situ polymerization to give a polymer PMMA three crosslinked network structure on the PVDF-HFP nanofiber interspersed between two skeleton crosslinked. 其中,锂离子电池静置温度为80C,静置时间为24h。 Wherein the temperature of the lithium ion battery is allowed to stand 80 C, resting time was 24h.

[0069] 实施例4 [0069] Example 4

[0070] I).配制静电纺丝溶液。 [0070] I). Electrospinning solution is prepared. 将要进行静电纺丝的聚合物(聚偏氟乙烯)在70C下溶于二甲基乙酰胺DMAc中,搅拌6h使其混合均匀,制得聚合物静电纺丝溶液,其中聚合物在静电纺丝溶液中的体积浓度为15% (g/mL)。 To be subjected to electrostatic spinning of polymer (polyvinylidene fluoride) dissolved in dimethylacetamide DMAc at 70 C, it was stirred for 6h mixed to prepare a polymer solution electrospinning, wherein the polymer in the electrostatic the volume concentration of the spinning solution was 15% (g / mL).

[0071] (2)静电纺丝制备一级骨架结构: [0071] (2) Preparation of an electrostatic spinning skeletal structure:

[0072] 将步骤I)配好的静电纺丝溶液装入温度为50C的静电纺丝设备的储液装置中,储液装置的活塞与注射器栗相连,储液装置通过聚四氟乙烯管与喷丝头相连,喷丝头固定,金属平板上放置无纺布作为收集器。 [0072] The step I) with a good charged electrostatic spinning solution temperature of the liquid receive means electrospinning apparatus at 50 C, the syringe plunger is connected to the accumulator means Li, a reservoir by means of polytetrafluoroethylene and the nozzle is connected to the head tube of the spinneret is fixed, the nonwoven fabric is placed on a metal plate as a collector. 调节喷丝头与收集板之间的距离为15cm;纺丝的环境温度为50C,包括储液装置中静电纺丝溶液的温度和收集板的温度均为50C,环境中的空气流速控制在0.5〜0.8m3/h;开启高压电源,调节电压至15kV,静电纺丝溶液的供料速率为60yL/min,开启注射器栗,将静电纺丝溶液喷射流喷射到锂电池隔膜上,在隔膜上得到聚合物静电纺丝纳米纤维膜层,从而在形成聚合物静电纺丝纳米纤维一级结构。 Adjustment between the spinneret and the collector plate distance of 15cm; spinning temperature is 50 C, including the temperature of the reservoir and the collecting plate means in the electrostatic spinning solution are 50 C, ambient air in the flow rate control 0.5~0.8m3 / h; high voltage power supply is turned on, to adjust the voltage 15kV, the feed rate of the electrostatic spinning solution was 60yL / min, injector Li is turned on, the electrostatic spinning solution was sprayed onto the jet lithium battery separator, electrospinning nanofibers obtained polymer film layer on the membrane, thereby forming a nanofiber electrospinning a polymer structure. 纤维平均直径为500nm,聚合物静电纺丝纳米纤维膜层厚度为40μπι (聚合物静电纺丝纳米纤维膜层的SEM图见图2) ο Average fiber diameter was 500nm, the polymer nanofibers electrospun film thickness of 40μπι (electrospun polymer nanofiber membrane layer SEM shown in Figure 2) ο

[0073] (3)聚合物涂覆制备二级骨架结构: [0073] (3) Preparation of polymer-coated two backbone structures:

[0074] 在含有聚合物纳米纤维隔膜上涂覆分子量约为50w的高分子量PVDF-HFP共聚物(产品购于阿克玛公司,型号为LBG),涂覆后烘干,得到穿插于聚合物纳米纤维间的PVDF-HFP共聚物二级骨架。 [0074] In the nano-fiber membranes containing the polymer coated molecular weight of about 50w high molecular weight PVDF-HFP copolymer (product commercially available from Arkema, the LBG model), after coating and drying, to obtain a polymer interspersed PVDF-HFP copolymer backbone between two nanofibers. 涂覆使用油性涂覆,其中溶剂选取油性溶剂丙酮。 Oily coating using a coating, wherein the oily solvent is selected solvent such as acetone. 涂覆的混合浆料浓度为20%,涂覆的速度控制位lm/min,烘干的风速5000rpm,温度90C。 Mixing the coated slurry concentration of 20%, the coating speed control bit lm / min, 5000 rpm for drying wind speed, temperature of 90 C.

[0075] ⑷电池卷绕。 [0075] ⑷ battery winding.

[0076] 将含有纳米纤维及PVDF-HFP的隔膜使用乙醇清洗,干燥,抽真空储存,并卷绕于电池中。 [0076] and containing PVDF-HFP nanofiber membrane washed with ethanol, dried, vacuum reservoir, and wound in the battery.

[0077] (5)电解液预聚体注液: [0077] (5) a prepolymer electrolyte injection:

[0078] 调配电解液碳酸乙烯酯(EC),碳酸二甲酯(DEC),碳酸甲乙酯(EMC)配比为1:1:1,六氟磷酸锂的摩尔浓度为1.0mol/L。 [0078] formulations as ethylene carbonate (EC), dimethyl carbonate (DEC), ethylmethyl carbonate (EMC) ratio of 1: 1: 1, the molar concentration of lithium hexafluoro phosphate was 1.0mol / L. 在电解液中加入聚丙烯酸PAA的高分子预聚体,加入引发剂BPO,交联剂三乙胺,其中电液中PAA的百分含量为1 %,BPO的百分含量为0.1 %,三乙胺的百分含量为1%与电解液常温搅拌12h后注入电池中。 Add polyacrylic acid PAA polymer electrolyte in the prepolymer, addition of BPO initiator, a crosslinking agent, triethylamine, wherein liquid electrically PAA percentage was 1%, the percentage of 0.1% BPO, tris ethylamine percentage of 1% after 12h with the electrolyte injected into the cell at room temperature with stirring.

[0079] ⑶高温原位聚合,制备PAA凝胶聚合物三级骨架结构: [0079] ⑶ situ polymerization temperature to prepare PAA gel polymer backbone three structures:

[0080] 将注液后的电池进行高温下静置,使其原位聚合,得到纳米纤维上PVDF-HFP 二级骨架间穿插交联的PAA三级聚合物交联网络结构。 [0080] The injection was carried out after the battery was allowed to stand at a high temperature, so that in situ polymerization to give three polymer PAA crosslinked network structure on the PVDF-HFP nanofiber interspersed between two skeleton crosslinked. 其中,锂离子电池静置温度为80C,静置时间为24h。 Wherein the temperature of the lithium ion battery is allowed to stand 80 C, resting time was 24h.

[0081] 实施例5 [0081] Example 5

[0082] I).配制静电纺丝溶液。 [0082] I). Electrospinning solution is prepared. 将要进行静电纺丝的聚合物(聚偏氟乙烯)在55C下溶于丙酮中,搅拌6h使其混合均匀,制得聚合物静电纺丝溶液,其中聚合物在静电纺丝溶液中的体积浓度为15% (g/mL)。 To be subjected to electrostatic spinning of polymer (polyvinylidene fluoride) at 55 C for dissolved in acetone and stirred for homogenization 6h, electrospinning a polymer solution was prepared, wherein the polymer solution in electrospinning volume concentration of 15% (g / mL).

[0083] (2)静电纺丝制备一级骨架结构: [0083] (2) Preparation of an electrostatic spinning skeletal structure:

[0084] 将步骤I)配好的静电纺丝溶液装入温度为50C的静电纺丝设备的储液装置中,储液装置的活塞与注射器栗相连,储液装置通过聚四氟乙烯管与喷丝头相连,喷丝头固定,金属平板上放置无纺布作为收集器。 [0084] The step I) with a good charged electrostatic spinning solution temperature of the liquid receive means electrospinning apparatus at 50 C, the syringe plunger is connected to the accumulator means Li, a reservoir by means of polytetrafluoroethylene and the nozzle is connected to the head tube of the spinneret is fixed, the nonwoven fabric is placed on a metal plate as a collector. 调节喷丝头与收集板之间的距离为15cm;纺丝的环境温度为50C,包括储液装置中静电纺丝溶液的温度和收集板的温度均为50C,环境中的空气流速控制在0.5〜0.8m3/h;开启高压电源,调节电压至15kV,静电纺丝溶液的供料速率为60yL/min,开启注射器栗,将静电纺丝溶液喷射流喷射到锂电池隔膜上,在隔膜上得到聚合物静电纺丝纳米纤维膜层,从而在形成聚合物静电纺丝纳米纤维一级结构。 Adjustment between the spinneret and the collector plate distance of 15cm; spinning temperature is 50 C, including the temperature of the reservoir and the collecting plate means in the electrostatic spinning solution are 50 C, ambient air in the flow rate control 0.5~0.8m3 / h; high voltage power supply is turned on, to adjust the voltage 15kV, the feed rate of the electrostatic spinning solution was 60yL / min, injector Li is turned on, the electrostatic spinning solution was sprayed onto the jet lithium battery separator, electrospinning nanofibers obtained polymer film layer on the membrane, thereby forming a nanofiber electrospinning a polymer structure. 纤维平均直径为500nm,聚合物静电纺丝纳米纤维膜层厚度为40μπι (聚合物静电纺丝纳米纤维膜层的SEM图见图2) ο Average fiber diameter was 500nm, the polymer nanofibers electrospun film thickness of 40μπι (electrospun polymer nanofiber membrane layer SEM shown in Figure 2) ο

[0085] (3)聚合物涂覆制备二级骨架结构: [0085] (3) Preparation of polymer-coated two backbone structures:

[0086] 在含有聚合物纳米纤维隔膜上涂覆分子量约为50w的高分子量PVDF-HFP共聚物(产品购于阿克玛公司,型号为LBG),涂覆后烘干,得到穿插于聚合物纳米纤维间的PVDF-HFP共聚物二级骨架。 [0086] In the nano-fiber membranes containing the polymer coated molecular weight of about 50w high molecular weight PVDF-HFP copolymer (product commercially available from Arkema, the LBG model), after coating and drying, to obtain a polymer interspersed PVDF-HFP copolymer backbone between two nanofibers. 涂覆使用油性涂覆,其中溶剂选取油性溶剂丙酮。 Oily coating using a coating, wherein the oily solvent is selected solvent such as acetone. 涂覆的混合浆料浓度为20%,涂覆的速度控制位lm/min,烘干的风速5000rpm,温度90C。 Mixing the coated slurry concentration of 20%, the coating speed control bit lm / min, 5000 rpm for drying wind speed, temperature of 90 C.

[0087] ⑷电池卷绕。 [0087] ⑷ battery winding.

[0088] 将含有纳米纤维及PVDF-HFP的隔膜使用乙醇清洗,干燥,抽真空储存,并卷绕于电池中。 [0088] and containing PVDF-HFP nanofiber membrane washed with ethanol, dried, vacuum reservoir, and wound in the battery.

[0089] (5)电解液预聚体注液: [0089] (5) a prepolymer electrolyte injection:

[0090] 调配电解液碳酸乙烯酯(EC),碳酸二甲酯(DEC),碳酸甲乙酯(EMC)配比为1:1:1,六氟磷酸锂的摩尔浓度为1.0mol/L。 [0090] formulations as ethylene carbonate (EC), dimethyl carbonate (DEC), ethylmethyl carbonate (EMC) ratio of 1: 1: 1, the molar concentration of lithium hexafluoro phosphate was 1.0mol / L. 在电解液中加入均苯三甲酰氯高分子预聚体,加入交联剂哌嗪,催化剂三乙胺,其中电液中均苯三甲酰氯的百分含量为10%,哌嗪的百分含量为10%,三乙胺的百分含量为1%,与电解液常温搅拌12h后注入电池中。 In the electrolytic solution was added trimesoyl chloride polymer prepolymer, crosslinking agent is added piperazine, triethylamine catalyst, wherein the average percentage of power fluid trimesoyl chloride 10%, the percentage of piperazine is 10%, the percentage of 1% triethylamine. after stirring for 12h at room temperature with an electrolyte injected into the cell.

[0091] ⑶高温原位聚合,制备聚酰胺凝胶聚合物三级骨架结构: [0091] ⑶ situ polymerization temperature, the preparation of three polymer backbone polyacrylamide gel structure:

[0092] 将注液后的电池进行高温下静置,使其原位聚合,得到纳米纤维上PVDF-HFP 二级骨架间穿插交联的聚酰胺三级聚合物交联网络结构。 [0092] The injection was carried out after the battery was allowed to stand at a high temperature, so that in situ polymerization to give a polyamide polymer crosslinked network structure three on PVDF-HFP nanofiber interspersed between two skeleton crosslinked. 其中,锂离子电池静置温度为80C,静置时间为24h。 Wherein the temperature of the lithium ion battery is allowed to stand 80 C, resting time was 24h.

[0093] 实施例6 [0093] Example 6

[0094] I).配制静电纺丝溶液。 [0094] I). Electrospinning solution is prepared. 将要进行静电纺丝的聚合物(聚偏氟乙烯)在60C下溶于丙酮与DMF (N,N-二甲基甲酰胺)比例为7:3的混合溶剂中,搅拌6h使其混合均匀,制得聚合物静电纺丝溶液,其中聚合物在静电纺丝溶液中的体积浓度为15% (g/mL)。 To be subjected to electrostatic spinning of polymer (polyvinylidene fluoride) was dissolved in acetone and DMF at 60 C (N, N- dimethylformamide) ratio of 7: 3 mixed solvent, and stirred to mix 6h homogenisation electrospinning a polymer solution, wherein the volume concentration of the polymer in the electrostatic spinning solution was 15% (g / mL).

[0095] (2)静电纺丝制备一级骨架结构: [0095] (2) Preparation of an electrostatic spinning skeletal structure:

[0096] 将步骤I)配好的静电纺丝溶液装入温度为50C的静电纺丝设备的储液装置中,储液装置的活塞与注射器栗相连,储液装置通过聚四氟乙烯管与喷丝头相连,喷丝头固定,金属平板上放置无纺布作为收集器。 [0096] The step I) with a good charged electrostatic spinning solution temperature of the liquid receive means electrospinning apparatus at 50 C, the syringe plunger is connected to the accumulator means Li, a reservoir by means of polytetrafluoroethylene and the nozzle is connected to the head tube of the spinneret is fixed, the nonwoven fabric is placed on a metal plate as a collector. 调节喷丝头与收集板之间的距离为15cm;纺丝的环境温度为50C,包括储液装置中静电纺丝溶液的温度和收集板的温度均为50C,环境中的空气流速控制在0.5〜0.8m3/h;开启高压电源,调节电压至15kV,静电纺丝溶液的供料速率为60yL/min,开启注射器栗,将静电纺丝溶液喷射流喷射到锂电池隔膜上,在隔膜上得到聚合物静电纺丝纳米纤维膜层,从而在形成聚合物静电纺丝纳米纤维一级结构。 Adjustment between the spinneret and the collector plate distance of 15cm; spinning temperature is 50 C, including the temperature of the reservoir and the collecting plate means in the electrostatic spinning solution are 50 C, ambient air in the flow rate control 0.5~0.8m3 / h; high voltage power supply is turned on, to adjust the voltage 15kV, the feed rate of the electrostatic spinning solution was 60yL / min, injector Li is turned on, the electrostatic spinning solution was sprayed onto the jet lithium battery separator, electrospinning nanofibers obtained polymer film layer on the membrane, thereby forming a nanofiber electrospinning a polymer structure. 纤维平均直径为500nm,聚合物静电纺丝纳米纤维膜层厚度为40μπι (聚合物静电纺丝纳米纤维膜层的SEM图见图2) ο Average fiber diameter was 500nm, the polymer nanofibers electrospun film thickness of 40μπι (electrospun polymer nanofiber membrane layer SEM shown in Figure 2) ο

[0097] (3)聚合物涂覆制备二级骨架结构: [0097] (3) Preparation of polymer-coated two backbone structures:

[0098] 在含有聚合物纳米纤维隔膜上涂覆分子量约为50w的高分子量PVDF-HFP共聚物(产品购于阿克玛公司,型号为LBG),涂覆后烘干,得到穿插于聚合物纳米纤维间的PVDF-HFP共聚物二级骨架。 [0098] In the nano-fiber membranes containing the polymer coated molecular weight of about 50w high molecular weight PVDF-HFP copolymer (product commercially available from Arkema, the LBG model), after coating and drying, to obtain a polymer interspersed PVDF-HFP copolymer backbone between two nanofibers. 涂覆使用油性涂覆,其中溶剂选取油性溶剂丙酮。 Oily coating using a coating, wherein the oily solvent is selected solvent such as acetone. 涂覆的混合浆料浓度为20%,涂覆的速度控制位lm/min,烘干的风速5000rpm,温度90C。 Mixing the coated slurry concentration of 20%, the coating speed control bit lm / min, 5000 rpm for drying wind speed, temperature of 90 C.

[0099] ⑷电池卷绕。 [0099] ⑷ battery winding.

[0100] 将含有纳米纤维及PVDF-HFP的隔膜使用乙醇清洗,干燥,抽真空储存,并卷绕于电池中。 [0100] and containing PVDF-HFP nanofiber membrane washed with ethanol, dried, vacuum reservoir, and wound in the battery.

[0101] (5)电解液预聚体注液: [0101] (5) a prepolymer electrolyte injection:

[0102] 调配电解液碳酸丙烯酯(PC),碳酸二甲酯(DEC),碳酸甲乙酯(EMC)配比为1:1:1,六氟磷酸锂的摩尔浓度为1.0mol/L。 [0102] propylene carbonate electrolyte formulations (PC), dimethyl carbonate (DEC), ethylmethyl carbonate (EMC) ratio of 1: 1: 1, the molar concentration of lithium hexafluoro phosphate was 1.0mol / L. 在电解液中加入聚甲基丙烯酸甲酯PMMA的高分子预聚体,加入引发剂BPO,交联剂三乙胺,其中电液中PMMA的百分含量为10%,BPO的百分含量为 Polymethyl methacrylate PMMA was added in an electrolyte polymer prepolymer, addition of BPO initiator, a crosslinking agent, triethylamine, wherein the percentage of electrically PMMA was 10%, the percentage content of BPO

0.1%,三乙胺的百分含量为1%与电解液常温搅拌12h后注入电池中。 0.1%, the percentage of 1% triethylamine was injected into the cell after 12h stirring at room temperature with the electrolyte.

[0103] ⑶高温原位聚合,制备PMMA凝胶聚合物三级骨架结构: [0103] ⑶ situ polymerization temperature, the preparation of three PMMA gel polymer backbone structure:

[0104] 将注液后的电池进行高温下静置,使其原位聚合,得到纳米纤维上PVDF-HFP 二级骨架间穿插交联的PMMA三级聚合物交联网络结构。 [0104] The injection was carried out after the battery was allowed to stand at a high temperature, so that in situ polymerization to give a polymer PMMA three crosslinked network structure on the PVDF-HFP nanofiber interspersed between two skeleton crosslinked. 其中,锂离子电池静置温度为80C,静置时间为24h。 Wherein the temperature of the lithium ion battery is allowed to stand 80 C, resting time was 24h.

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Classifications
International ClassificationH01M10/058, H01M10/056
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