CN104766938B - A kind of compound lithium ion battery separator and preparation method thereof - Google Patents

A kind of compound lithium ion battery separator and preparation method thereof Download PDF

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Publication number
CN104766938B
CN104766938B CN201510069176.7A CN201510069176A CN104766938B CN 104766938 B CN104766938 B CN 104766938B CN 201510069176 A CN201510069176 A CN 201510069176A CN 104766938 B CN104766938 B CN 104766938B
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coating
electrostatic spinning
woven fabrics
layer
lithium ion
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CN104766938A (en
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刘向文
胡志彪
李文锋
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Longyan University
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Longyan Cercis Innovation Research Institute
Longyan University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/44—Fibrous material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a kind of compound lithium ion battery separator, includes non-woven fabrics base material layer, electrostatic spinning layer and polyalcohol stephanoporate coating；Structure combination is as follows：Polyalcohol stephanoporate coating/electrostatic spinning layer/non-woven fabrics base material layer/electrostatic spinning layer/polyalcohol stephanoporate coating, non-woven fabrics base material layer/electrostatic spinning layer/polyalcohol stephanoporate coating or polyalcohol stephanoporate coating/non-woven fabrics base material layer/electrostatic spinning layer/polyalcohol stephanoporate coating.Compound lithium ion battery separator disclosed by the invention, base material is done with non-woven fabrics, ensure that the high porosity and heat resistance of membrane；Electrostatic spinning layer is set in non-woven fabrics base material upper and lower surface, reduces non-woven fabrics pore size so that uniform pore diameter, solves the problems, such as that nonwoven cloth diaphragm causes short circuit due to local macropore；The setting of polyalcohol stephanoporate coating at the same time, improves the ability that membrane absorbs and keeps electrolyte, and can bond battery plus-negative plate, strengthens battery machine performance, ensure that the security of battery.Prepared compound lithium ion battery separator, disclosure satisfy that the security requirement run under high power capacity, the large current density of high-power power battery and severe rugged environment.

Description

A kind of compound lithium ion battery separator and preparation method thereof
Technical field
The present invention relates to battery diaphragm technical field, and in particular to a kind of compound lithium ion battery separator and its preparation side Method.
Background technology
Lithium-ion-power cell is the key core component of new-energy automobile, high power capacity, high power type lithium ion power electric The demand of the pond aspect of performance such as high-power output, fast charging and discharging in a dynamic condition proposes the security of lithium battery great Challenge, its demand to proposing higher every film strength, thermal dimensional stability and heat chemistry, electrochemical stability.Tradition is drawn Polyalkene diaphragm electrolyte obtained by stretching process absorbs and holding capacity difference influences battery capacity, and not high (40% left side of porosity It is right) multiplying power discharging property and service life cycle of battery are influenced, in addition heat resistance is no more than 150 DEG C, influences the safety of battery Property.Meanwhile size distortion is obvious at high temperature for polyolefine material, and fusing point is generally below 170 DEG C, when power battery is big During current discharge, battery local pyrexia reaches this temperature, and membrane, which will melt, makes positive and negative anodes short-circuit rapidly, thermal runaway row occurs For.Therefore, polyolefine material membrane cannot meet the new demand that lithium-ion-power cell proposes membrane, and restrict lithium ion Key point of the power battery in the quick application development of new energy field.
3 D stereo pore structure is presented in the compound membrane of non-woven fabrics nanofiber, can effectively prevent Li dendrite short circuit, it is high Porosity is conducive to the improvement of high rate discharge for lithium ion battery and cycle performance, passes through polyamide (PI), polyester (PET), the heat-resisting material such as polysulfones (PES), cellulose, aramid fiber so that non-woven fabrics exceedes as the membrane temperature in use of base material 170 DEG C, but non-woven fabrics aperture is mostly in the micron-scale not, and uniform pore diameter is poor, can not be directly used as in lithium battery diaphragm, Especially cheap domestic non-woven fabrics, it is therefore necessary to modifying the aperture of non-woven fabrics.
It is mainly the following nonwoven cloth diaphragm technology of preparing at present, first, the coating ceramic material on PET non-woven fabrics, Winning wound Degussa and preparing in this way with high temperature resistant and thermal shrinkage energy, can generally bear 200 DEG C or so of height Temperature, improves battery safety.Second, the polymer such as PVDF are coated on non-woven fabrics, non-woven fabrics aperture is modified, every Film properties are excellent, it is difficult to avoid the presence of local macropore or weak spot, security is relatively low, pressure-resistant poor insulativity, battery it is short Road rate is higher, can not commercial application.3rd, electrostatic spinning is carried out on non-woven fabrics.Electrostatic spinning is that a kind of efficiently preparation is high Molecule nano fibre diaphragm technology, the technology utilize polymeric solution in the high voltage electrostatic field of thousands of to tens of thousands of volts Under, overcome the surface tension of Polymer Solution to form electrified jet, and acceleration, stretching phenomenon constantly occurs, waved with solvent Hair, finally obtains nano-scale fiber film on the reception device.Certainly there are many patent reports directly with electrostatic spinning technique system Standby lithium ion battery separator, such as patent 103219483A disclose one kind and meet lithium ion battery separator, by upper strata Nanowire Tie up film, middle micrometer fibers film and lower floor's nano fibrous membrane to form, the membrane porosity is high, security is good, temperature tolerance is good, but imitates Rate is low, and mechanical strength is low, can not produce in batches and be industrially used.For this reason, patent CN103085442A disclose it is a kind of with Prepared PET based polymer solutions are carried out electrostatic spinning, obtained for lithium battery by PP non-woven fabrics on it as base material PP/PET nano fiber diaphragms.Patent CN103122555A discloses a kind of preparation of the nano fibrous membrane based on PET non-woven fabrics Method, carries out continuous electrostatic spinning by prepared TPU solution, obtains the TPU/PET nano fiber diaphragms for lithium battery, should Lithium ion battery separator has higher resistance to elevated temperatures and longer battery life, disclosure satisfy that the big electricity of larger capacity batteries Flow charge and discharge.2 months 2012, the wide rapids paper processed of Japan was put on display using polyolefin (PP, PE) non-woven fabrics as base material, by polyvinyl alcohol nano Lithium electric separator made of fibre spinning is more heat-resisting compared with common polyalkene diaphragm.Disclosed in patent CN103840112A Phase transfer method prepares the technology of polyalcohol stephanoporate coating, the technology can prepare lithium ion battery containing loose structure every Film.Membrane prepared by this method needs to consider compound ability of the electrostatic spinning layer on non-woven fabrics, it is impossible to is easily peeled off, Er Qiebiao The nanofiber in face easily abrades during transport and use, causes battery performance defect.
The content of the invention
It is simple quiet to solve it is an object of the invention to provide a kind of compound lithium ion battery separator and preparation method thereof Electricity spinning fibre film-strength and low production efficiency, the easy short-circuit, existing non-woven fabrics/electrostatic of existing non-woven polymers coating membrane Fibrous layer easily abrades the problem of destruction in spining technology.
To achieve these goals, the technical solution adopted in the present invention is as follows：
A kind of compound lithium ion battery separator, includes non-woven fabrics base material layer, electrostatic spinning layer and polyalcohol stephanoporate coating； Structure combination is as follows：Polyalcohol stephanoporate coating/electrostatic spinning layer/non-woven fabrics base material layer/electrostatic spinning layer/polyalcohol stephanoporate Coating, non-woven fabrics base material layer/electrostatic spinning layer/polyalcohol stephanoporate coating or polyalcohol stephanoporate coating/non-woven fabrics base material layer/electrostatic Spinning layer/polyalcohol stephanoporate coating.
Non-woven fabrics material in the non-woven fabrics base material layer is preferably polypropylene, polyethylene, polyimides, polyamide, poly- It is sulfone, polyacrylonitrile, polyester, cellulose, polyether-ether-ketone, polyphosphazene, polyphenylene sulfide, polyacrylate, polyvinyl alcohol imidazoline, poly- To one or more of benzamide, poly(p-phenylene terephthalamide) and poly (aryl ether sulfone ketone), aramid fiber and PSA fiber.
The manufacture craft of the non-woven fabrics is preferably meltblown, spun-bond process, wet papermaking, spun lacing method, needle point method and hot rolling One or more of method.
The non-woven fabrics specifications parameter is preferably：Grammes per square metre 3-50g/m2, 5-40 μm of thickness, thickness deviation is less than ± 2 μm, hole Gap rate >=30%, pore-size distribution≤300 μm.
The material of the electrostatic spinning layer is preferably polyimides (PI), aramid fiber, polyacrylonitrile (PAN), PSA fiber, poly- inclined In vinyl fluoride (PVDF), Kynoar-hexafluoropropene (PVDF-HFP) and polymethyl methacrylate (PMMA) it is a kind of with On.
The thickness in monolayer scope of the electrostatic spinning layer is 1-15 μm, and electrospun fibers diameter range is 10-1500nm.
The polyalcohol stephanoporate coating, for the list for carrying out one side coating using traditional coating method or prepared by coated on both sides Straight polymer coating or the polymer coating of nano-ceramic particle doping, its signal layer coating thickness are 1-10 μm, the hole of micropore Footpath is 0.01-1 μm.
The polyalcohol stephanoporate coating, its polymeric material are preferably polymethyl methacrylate, polymethylacrylic acid second It is ester, polypropylmethacryla,es, polybutyl methacrylate, polyisobutyl methacrylate, polyallylmethacrylate, poly- Methyl acrylate, polyethyleneglycol diacrylate, polyacrylonitrile, acrylonitrile butadiene rubber, acrylonitrile vinyl chloride resin, acrylonitrile Methacrylic resin, acrylonitrile acrylic resin, Kynoar (PVDF), polytetrafluoroethylene (PTFE) (PTFE), Kynoar-six One or more of fluoropropene (PVDF-HFP), polyacrylonitrile (PAN) and aromatic polyamide.
A kind of compound lithium ion battery separator, its preparation method comprise the following steps：
It is prepared by the 1st step, electrostatic spinning solution：Polymer used in electrostatic spinning layer is dissolved in a solvent, wherein polymer Mass percent concentration in the solution is 5-30wt%, measures the viscosity of the solution between 100-3000mPa.S；
2nd step, electrostatic spinning：By prepared electrostatic spinning solution by nanofiber spinning-drawing machine on non-woven fabrics base material Single or double continuous electrostatic spinning is carried out, obtains non-woven fabrics/nano-fiber composite film, the condition of the electrostatic spinning is:Temperature 10-40 DEG C of degree, positive voltage 20-50kV, negative voltage bear that 5- bears 30kV, spinning speed is every meter of wide cut 1-10g per minute, spinning speed The single side thickness spent for every meter of wide cut 1-10g per minute, nano fibrous membrane is：1-10μm；
The composite membrane obtained after the completion of spinning is post-processed:It is hot-forming to first pass through 80-200 DEG C of roller, then at 120 DEG C It is 1-5 minutes dry in baking oven, so as to obtain the non-woven fabrics of electrostatic spinning modification；
3rd step, phase transfer method prepare polyalcohol stephanoporate coating：By polymer and solvent (reagent that polymer can be dissolved), Non-solvent (polymer but the reagent that can be dissolved each other with solvent cannot be dissolved), the mixing of inorganic particulate ratio, inorganic particulate and polymer Quality compare scope：1:100-10:100, the solution that configuration polymer concentration is 4-12wt%, is coated on modification nonwoven cloth base material On, a kind of compound lithium ion battery separator is prepared in drying, and single side coating layer thickness controls at 1-6 μm, is coated changing Property non-woven fabrics base material on, single side coating layer thickness is controlled at 1-6 μm, and a kind of compound lithium-ion electric is prepared in drying Pond membrane.
3rd step, solvent is n,N-Dimethylformamide (DMF), n,N-dimethylacetamide (DMAc), acetone, N- One or more of methyl pyrrolidone (NMP), tetrahydrofuran (THF) and hexafluoroisopropanol.
3rd step, non-solvent are one or more of water, ethanol, glycerine.
3rd step, nano inoganic particle is alundum (Al2O3), silica, titanium dioxide, barium titanate, magnesia, oxygen Change one or more of zirconium, zinc oxide and carborundum.
3rd step, coating method are preferably one kind in dip-coating, roller coat, blade coating, intaglio plate coating and nick coating.
3rd step, drying condition are：80-150 DEG C of temperature, -5 minutes 30 seconds time.
A kind of compound lithium ion battery separator, its gross thickness are 10-100 μm.
After using the above scheme, the present invention is for the deficiency of publication and technology, such as simple electrospun fibers In film-strength and low production efficiency, the easy short-circuit, existing non-woven fabrics/electrostatic spinning technique of existing non-woven polymers coating membrane Fibrous layer easily abrades the problem of destruction, and creative has used non-woven fabrics base material layer/electrostatic spinning layer/polyalcohol stephanoporate coating The membrane of multiple layer combination, and illustrate technology of preparing.The present invention with non-woven fabrics does base material, ensure that the high porosity of membrane and heat-resisting Property；Electrostatic spinning layer is set in non-woven fabrics base material upper and lower surface, reduces non-woven fabrics pore size so that uniform pore diameter, solves Nonwoven cloth diaphragm is due to the problem of local macropore causes short circuit；The setting of polyalcohol stephanoporate coating at the same time, improves membrane absorption Ability with electrolyte is kept, and can bond battery plus-negative plate, strengthen battery machine performance, ensure that the safety of battery Property.Prepared compound lithium ion battery separator, disclosure satisfy that high power capacity, the large current density of high-power power battery and severe Carve the security requirement run under environment.
In short, the combination of the present invention has three advantages：First, with reference to non-woven fabrics fusing point high-fire resistance it is good the advantages of；Second, Non-woven fabrics aperture has been modified by electrostatic spinning layer, battery short circuit rate has been reduced, is conducive to large-scale industrialized production；3rd： Polyalcohol stephanoporate coating can not only protect the layers of nanofibers of electrostatic spinning, can also improve the electrolyte absorbability of membrane With membrane and electrode adhesion ability, the performance of battery is improved.
Prepared compound lithium ion battery separator, disclosure satisfy that high power capacity, the high current of high-power power battery is filled Put and severe rugged environment under the security requirement that runs.
Brief description of the drawings
Fig. 1 is the electromicroscopic photograph on unmodified nonwoven sample surface；
Fig. 2 is the electromicroscopic photograph of the modified sample surfaces of electrostatic spinning on non-woven fabrics；
Fig. 3 is the electromicroscopic photograph that modification nonwoven cloth carries out sample surfaces after PVDF-HFP coating preparations；
Fig. 4 is the electromicroscopic photograph that modification nonwoven cloth carries out sample section after PVDF-HFP coating preparations.
Embodiment
Embodiment 1
1) prepared by electrostatic spinning solution：Polyimides is dissolved in DMAc (n,N-dimethylacetamide), polyimides matter It is 5wt% to measure volume by volume concentration concentration, and the viscosity for measuring the polyimide solution is 100mPa.S.
2) electrostatic spinning：By prepared polyimide solution electrostatic spinning solution by nanofiber spinning-drawing machine in PET Single side continuous electrostatic spinning is carried out on non-woven fabrics base material, obtains PI/PET nano-fiber composite films, the condition of the electrostatic spinning For：10 DEG C of temperature, positive voltage 20kV, negative voltage bear 530kV, spinning speed is every meter of wide cut 1g per minute；
The composite membrane obtained after the completion of spinning is post-processed:It is hot-forming to first pass through 80 DEG C of rollers, then in 120 DEG C of baking ovens Middle drying 1 minute.
The electromicroscopic photograph on unmodified nonwoven sample surface is as shown in Figure 1, the modified sample table of electrostatic spinning on non-woven fabrics The electromicroscopic photograph in face is as shown in Figure 2.
3) phase transfer method prepares polyalcohol stephanoporate coating：By PVDF-HFP (French A Kema, LBG) and solvent acetone, non- Etoh solvent mixes, and configuration polymer concentration is 4wt%.The method of the polymer solution dip-coating of gained is coated in composite membrane Both sides, then the dry 30s under the conditions of 80 DEG C, obtains a kind of compound lithium ion battery separator.
In polymer coating preparation, the technology that universal disclosed phase transfer method prepares polyalcohol stephanoporate coating is with reference to, Such as patent CN103840112A.So the part particular content is not specifically noted herein.
Modification nonwoven cloth carries out the electromicroscopic photograph of sample surfaces and section such as Fig. 3 and Fig. 4 institutes after PVDF-HFP coating preparations Show.
Embodiment 2
1) prepared by electrostatic spinning solution：It is prepared by electrostatic spinning solution：Polyimides is dissolved in DMAc (N, N- dimethylacetamides Amine) in, polyimides mass volume ratio concentration is 30wt%, and the viscosity for measuring the polyimide solution is 3000mPa.S.
2) electrostatic spinning：By prepared polyimide solution electrostatic spinning solution by nanofiber spinning-drawing machine in PET Two-sided continuous electrostatic spinning is carried out on non-woven fabrics base material, obtains PI/PET nano-fiber composite films, the condition of the electrostatic spinning For：40 DEG C of temperature, positive voltage 50kV, negative voltage bear 30kV, spinning speed is every meter of wide cut 10g per minute；
The composite membrane obtained after the completion of spinning is post-processed:It is hot-forming to first pass through 200 DEG C of rollers, then in 120 DEG C of bakings It is 5 minutes dry in case.
3) phase transfer method prepares polyalcohol stephanoporate coating：By PVDF-HFP (French A Kema, LBG) and solvent acetone, non- Solvent, n-butanol mixes, and configuration polymer concentration is 12wt%.By the method for the polymer solution roller coat of gained coated in multiple The both sides of film are closed, then the dry 5min under the conditions of 150 DEG C, obtains a kind of compound lithium ion battery separator.
Embodiment 3
1) prepared by electrostatic spinning solution：It is prepared by electrostatic spinning solution：Polyacrylonitrile (PAN) is dissolved in NMP, polyacrylonitrile Mass volume ratio concentration is 10wt%, and the viscosity for measuring the polyimide solution is 1000mPa.S.
2) electrostatic spinning：By prepared polyacrylonitrile solution electrostatic spinning solution by nanofiber spinning-drawing machine PP without Single side continuous electrostatic spinning is carried out on woven fabric base material, obtains PAN/PP nano-fiber composite films, the condition of the electrostatic spinning is： 30 DEG C of temperature, positive voltage 20kV, negative voltage bear 30kV, spinning speed is every meter of wide cut 5g per minute；
The composite membrane obtained after the completion of spinning is post-processed:It is hot-forming to first pass through 100 DEG C of rollers, then in 120 DEG C of bakings It is 4 minutes dry in case.
3) phase transfer method prepares polyalcohol stephanoporate coating：By PVDF-HFP (French A Kema, LBG) and solvent acetone, non- Solvent, n-butanol, nano silicon oxide mixing, configuration polymer concentration is 10wt%, wherein content of inorganic particles nano silicon oxide： PMMA=1:100.The method that the polymer solution of gained is coated with nick is coated in the both sides of composite membrane, then at 100 DEG C Under the conditions of dry 1min, obtain a kind of compound lithium ion battery separator.
Embodiment 4
1) prepared by electrostatic spinning solution：It is prepared by electrostatic spinning solution：Polyacrylonitrile (PAN) is dissolved in NMP, polyacrylonitrile Mass volume ratio concentration is 15wt%, and the viscosity for measuring the polyimide solution is 1500mPa.S.
2) electrostatic spinning：By prepared polyacrylonitrile solution electrostatic spinning solution by nanofiber spinning-drawing machine PE without Two-sided continuous electrostatic spinning is carried out on woven fabric base material, obtains PAN/PE nano-fiber composite films, the condition of the electrostatic spinning is： 25 DEG C of temperature, positive voltage 50kV, negative voltage bear 15kV, spinning speed is every meter of wide cut 6g per minute；
The composite membrane obtained after the completion of spinning is post-processed:It is hot-forming to first pass through 200 DEG C of rollers, then in 120 DEG C of bakings It is 2 minutes dry in case.
3) phase transfer method prepares polyalcohol stephanoporate coating：By PMMA and solvent acetone, non-solvent deionized water, nano oxidized Aluminium mixes, and configuration polymer concentration is 11wt%, wherein content of inorganic particles nano aluminium oxide：PMMA=1:100.By gained The method of polymer solution dip-coating is coated in the both sides of composite membrane, then 2 minutes dry under the conditions of 150 DEG C, obtains one kind Compound lithium ion battery separator.
Embodiment 5
1) prepared by electrostatic spinning solution：It is prepared by electrostatic spinning solution：Polyacrylonitrile (PAN) is dissolved in NMP, polyacrylonitrile Mass volume ratio concentration is 12wt%, and the viscosity for measuring the polyimide solution is 1350mPa.S.
2) electrostatic spinning：By prepared polyacrylonitrile solution electrostatic spinning solution by nanofiber spinning-drawing machine PE without Two-sided continuous electrostatic spinning is carried out on woven fabric base material, obtains PAN/PE nano-fiber composite films, the condition of the electrostatic spinning is： 25 DEG C of temperature, positive voltage 30kV, negative voltage bear 20kV, spinning speed is every meter of wide cut 6g per minute；
The composite membrane obtained after the completion of spinning is post-processed:It is hot-forming to first pass through 200 DEG C of rollers, then in 120 DEG C of bakings It is 2 minutes dry in case.
3) phase transfer method prepares polyalcohol stephanoporate coating：By PMMA and solvent butanone, non-solvent deionized water, nano barium titanate Barium mixes, and configuration polymer concentration is 11wt%, wherein content of inorganic particles nano barium phthalate：PMMA=1:100.By gained The method of polymer solution blade coating is coated in the both sides of composite membrane, then 2 minutes dry under the conditions of 150 DEG C, obtains one kind Compound lithium ion battery separator.
Comparative example 1:Commercialized polyethylene diagrams.
Comparative example 2:PET nonwoven cloth diaphragms.
Comparative example 3:PET non-woven fabrics carries out membrane made from PVDF-HFP coatings.Concrete technology is:Compound concentration is 10% PVDF-HFP (French A Kema, LBG) solution.The method of the polymer solution dip-coating of gained is coated in the two of composite membrane Side, then dries 2min under the conditions of 100 DEG C.
To in a kind of compound lithium ion battery separator and comparative example obtained by embodiment 1-6 membrane carry out thickness, Porosity, gas permeability, electrolyte absorptivity, tensile strength, the characterization of thermal stability, the results are shown in Table 1.
1 basic performance test result of table
As can be seen here:Compared with existing commercialized PP non-woven fabrics, a kind of compound lithium ion battery provided by the present invention Membrane has the advantages that porosity is high, electrolyte absorption is more, thermal stability is good, mechanical strength is suitable, is more suitable for doing power lithium Ion battery membrane.
The puncture short of resistance to insulating properties is tested:
Each embodiment prepares 100 batteries, and in preparation process, battery core toasts 24h in 85 DEG C of vacuum drying ovens, then The puncture short of resistance to insulating properties test is done to battery core, and listened number to count on the battery of different voltages test, test result is such as Shown in table 2.
2 puncture short of resistance to insulating properties test result of table
Embodiment is numbered The resistance to puncture short test percent of pass % of 10V The resistance to puncture short test percent of pass % of 1000V
Embodiment 1 100 100
Embodiment 2 100 100
Embodiment 3 100 100
Embodiment 4 100 100
Embodiment 5 100 100
Comparative example 2 3 1
Comparative example 3 87 76
As can be seen from Table 2, when common non-woven fabric directly makes lithium ion battery, resistance to puncture short test percent of pass pole Low, after carrying out PVDF coatings to non-woven fabrics, resistance to puncture short test percent of pass increases substantially, but percent of pass does not reach electricity also The requirement of pond producer, cannot be introduced into the industrialization stage.A kind of compound lithium ion battery separator technology system provided by the present invention Standby compound lithium ion battery separator technology, by modifying the macropore of non-woven fabrics, is then carrying out polymer-coated, Resistance to puncture short test percent of pass reaches 100%, reaches the security requirement of lithium ion battery.
The above embodiment is only the preferred embodiment of the present invention, it is impossible to the scope of protection of the invention is limited with this, The change and replacement for any unsubstantiality that those skilled in the art is done on the basis of the present invention belong to institute of the present invention Claimed scope.

Claims (7)

  1. A kind of 1. compound lithium ion battery separator, it is characterised in that：Include non-woven fabrics base material layer, electrostatic spinning layer and polymer Porous coating；Structure combination is as follows：Polyalcohol stephanoporate coating/electrostatic spinning layer/non-woven fabrics base material layer/electrostatic spinning layer/ Polyalcohol stephanoporate coating or polyalcohol stephanoporate coating/non-woven fabrics base material layer/electrostatic spinning layer/polyalcohol stephanoporate coating；
    Preparation method comprises the following steps：
    It is prepared by the 1st step, electrostatic spinning solution：By polymer dissolving used in electrostatic spinning layer, in a solvent, wherein polymer is molten Mass percent concentration in liquid is 5-30wt%, measures the viscosity of the solution between 100-3000mPa.S；
    2nd step, electrostatic spinning：Prepared electrostatic spinning solution is carried out by nanofiber spinning-drawing machine on non-woven fabrics base material Single or double continuous electrostatic spinning, obtains non-woven fabrics/nano-fiber composite film, and the condition of the electrostatic spinning is:Temperature 10-40 DEG C, positive voltage 20-50kV, negative voltage bear that 5- bears 30kV, spinning speed is every meter of wide cut 1-10g per minute, nanofiber The single side thickness of film is：1-10μm；
    The composite membrane obtained after the completion of spinning is post-processed:It is hot-forming to first pass through 80-200 DEG C of roller, then in 120 DEG C of baking ovens Middle dry 1-5 minutes, so as to obtain the non-woven fabrics of electrostatic spinning modification；
    3rd step, phase transfer method prepare polyalcohol stephanoporate coating：Polymer and solvent, non-solvent, inorganic particulate ratio are mixed, The quality of inorganic particulate and polymer compares scope：1:100-10:100, configuration polymer concentration is the solution of 4-12wt%, then applies Cloth is on the both sides of modification nonwoven cloth base material, and at 1-6 μm, drying is prepared described one kind and answers the control of single side coating layer thickness Mould assembly lithium ion battery separator；
    3rd step, solvent is n,N-Dimethylformamide DMF, n,N-dimethylacetamide DMAc, acetone, N- methyl pyrroles One or more of pyrrolidone NMP, tetrahydrofuran THF and hexafluoroisopropanol；
    3rd step, non-solvent are one or more of water, ethanol, glycerine.
  2. A kind of 2. compound lithium ion battery separator as claimed in claim 1, it is characterised in that：In the non-woven fabrics base material layer Non-woven fabrics material for polypropylene, polyethylene, polyimides, polyamide, polysulfones, polyacrylonitrile, polyester, cellulose, polyethers ether It is ketone, polyphosphazene, polyphenylene sulfide, polyacrylate, polyvinyl alcohol imidazoline, poly- to benzamide, poly(p-phenylene terephthalamide) One or more of with poly (aryl ether sulfone ketone), aramid fiber and PSA fiber；
    The manufacture craft of the non-woven fabrics is one in meltblown, spun-bond process, wet papermaking, spun lacing method, needle point method and Hot rolling More than kind；
    The non-woven fabrics specifications parameter is：Grammes per square metre 3-50g/m2, 5-40 μm of thickness, thickness deviation is less than ± 2 μm, porosity of= 30%, pore-size distribution≤300 μm.
  3. A kind of 3. compound lithium ion battery separator as claimed in claim 1, it is characterised in that：The material of the electrostatic spinning layer Expect for polyimides PI, aramid fiber, polyacrylonitrile (PAN), PSA fiber, Kynoar PVDF, Kynoar-hexafluoropropene One or more of PVDF-HFP and polymetylmethacrylate；
    The thickness in monolayer scope of the electrostatic spinning layer is 1-10 μm, and electrospun fibers diameter range is 10-1500nm.
  4. A kind of 4. compound lithium ion battery separator as claimed in claim 1, it is characterised in that：The polyalcohol stephanoporate applies Layer, to carry out the polymer coating of the nano-ceramic particle doping of coated on both sides preparation using traditional coating method, its individual layer applies Layer thickness is 1-6 μm, and the aperture of micropore is 0.01-1 μm.
  5. A kind of 5. compound lithium ion battery separator as claimed in claim 1, it is characterised in that：The polyalcohol stephanoporate applies Layer, its polymeric material is polymethyl methacrylate, polyethyl methacrylate, polypropylmethacryla,es, poly- methyl-prop Olefin(e) acid butyl ester, polyisobutyl methacrylate, polyallylmethacrylate, polymethyl acrylate, polyethylene glycol diacrylate Ester, acrylonitrile butadiene rubber, acrylonitrile vinyl chloride resin, acrylonitrile methacrylic resin, acrylonitrile acrylic resin, poly- inclined fluorine Ethene PVDF, polytetrafluoroethylene PTFE, Kynoar-hexafluoropropene PVDF-HFP, polyacrylonitrile (PAN) and aromatic polyamide One or more of.
  6. A kind of 6. compound lithium ion battery separator as claimed in claim 1, it is characterised in that：3rd step, inorganic particulate For in alundum (Al2O3), silica, titanium dioxide, barium titanate, magnesia, zirconium oxide, zinc oxide and carborundum it is a kind of with On；
    3rd step, coating method are one kind in dip-coating, roller coat, blade coating, intaglio plate coating and nick coating；
    3rd step, drying condition are：80-150 DEG C of temperature, -5 minutes 30 seconds time.
  7. A kind of 7. compound lithium ion battery separator as claimed in claim 1, it is characterised in that：Gross thickness is 10-100 μm.
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