CN202534721U - Composite porous film - Google Patents
Composite porous film Download PDFInfo
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- CN202534721U CN202534721U CN2011204946014U CN201120494601U CN202534721U CN 202534721 U CN202534721 U CN 202534721U CN 2011204946014 U CN2011204946014 U CN 2011204946014U CN 201120494601 U CN201120494601 U CN 201120494601U CN 202534721 U CN202534721 U CN 202534721U
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Abstract
The utility model provides a composite porous film, comprising a porous film matrix, inorganic particles and/or thermo-sensitive particles and a binder, wherein the inorganic particles and/or thermo-sensitive particles are bonded at one side or two sides of the porous film matrix by using the binder, so that an independent inorganic particle coating and/or independent thermo-sensitive particle coating and/or an inorganic particle and thermo-sensitive particle mixed coating are/is formed, and no binder and/or inorganic particles and/or thermo-sensitive particles exist in holes inside the porous film matrix. The composite porous film disclosed by the utility model has good high-temperature resistance and relative high porosity, and is suitable for preparing power lithium ion batteries with high discharge multiplying power.
Description
Technical field
The utility model relates to a kind of perforated membrane and manufacturing approach thereof, in particular to compound perforated membrane of a kind of organic-inorganic and preparation method thereof.
Background technology
Lithium ion battery has been penetrated into the every aspect of life; Except that being widely used in digital electronic goods such as the daily mobile phone of knowing, notebook computer and MP3, also bringing into use aspect some high-power drive ponds such as electric motor car, electric bicycle, electric tool in recent years.Power lithium-ion battery has the power/energy density higher than communication lithium ion battery, and the security performance of power lithium-ion battery is had higher requirement.Barrier film plays a part to intercept both positive and negative polarity and the lithium ion transmission channel is provided in lithium ion battery, and the high-temperature thermal stability performance of barrier film will directly influence the security performance of power lithium-ion battery.
The lithium ion battery separator of existing marketization is mainly and is fit to the polyolefin composite membrane that polyalkene diaphragm that the communication lithium ion battery uses comprises monolayer polyethylene, single-layer polypropylene and three layers.Because about 130 ℃ of poly fusing point; About 160 ℃ of polypropylene fusing point; Be elevated to polyolefinic fusing point when above in the battery local temperature; Might cause between the both positive and negative polarity directly forming short circuit because of the fusing of barrier film, so no matter be that single-layer septum or three layers of composite membrane all exist potential potential safety hazard when in power lithium-ion battery, using with the barrier film of polyolefin material, the high-temperature thermal stability performance of barrier film still has much room for improvement.
The low-melting problem that exists to the polyalkene diaphragm of the marketization; In CN1735983, CN1679182, CN1717820, CN1717821, CN1883063, CN1868012, CN1638850 and CN1851957, disclosing several kinds is carrier with non-polymer fiber of knitting or weaving or glass fiber; In carrier,, utilize inorganic coating to improve the high temperature stability performance of barrier film with surperficial composite diaphragm and the manufacturing approach thereof that contains nonconducting inorganic coating.But these are knitted or textile fabric is the composite diaphragm of carrier with non-; Because the accumulation of fiber forms big hole; May there be the micron order duct suitable in the composite diaphragm with the electrode material size; Might between electrode, move in the electrode material charge and discharge process that comes off and cause the reduction even the short circuit of battery performance, have potential safety hazard.
The polyalkene diaphragm aperture of existing marketization is generally 30-100nm; Particle size less than electrode material; Can effectively intercept the migration of the electrode material that comes off at inside battery; Therefore be the macropore problem that exists in the composite diaphragm of carrier formation in order to solve with the fiber, it is the research of the composite diaphragm of carrier that a lot of patents have been carried out with the polyalkene diaphragm.A kind of manufacturing approach that can form the composite diaphragm of gel with electrolyte is disclosed in CN101662042.A kind of manufacturing approach that is suitable for the organic-inorganic composite proton exchange membrane of vanadium cell is disclosed in CN101931070.Crosslinked ceramic coating barrier film of a kind of ion-containing polymer and preparation method thereof is disclosed in CN101989651.In CN101281961, disclose a kind of coating composition of lithium ion battery separator, can be used for applying polyalkene diaphragm.A kind of composite diaphragm that forms in the porous substrate surface-coated with inorganic porous particle and adhesive is disclosed in CN101317284.A kind of method at the temperature sensitive production of coatings composite diaphragm of polyalkene diaphragm surface-coated is disclosed in CN101343374.The common 30-70% of polyalkene diaphragm porosity; The size of micropore is less than 200nm, in above-mentioned disclosed method since the process floating coat solution that applies penetrate into can be blocking microporous in the micropore; The composite diaphragm porosity that causes forming reduces, and influences the transmission performance of lithium ion in micro channel.Therefore, need new composite diaphragm and preparation method thereof, could well guarantee the performance of power lithium-ion battery barrier film.The utility model provides composite diaphragm that a kind of suitable power lithium-ion battery that is the basis with the polyalkene diaphragm of the marketization uses and preparation method thereof.
The utility model content
In order to solve the problems referred to above that exist in the prior art; The first aspect of the utility model provides a kind of composite porous film; Comprise perforated membrane matrix and inorganic particle and/or temperature sensitive property particle and adhesive; Said inorganic particle and/or temperature sensitive property particle pass through adhesives in said perforated membrane matrix one or both sides; Thereby form the mixed coating of inorganic particle coating independently or temperature sensitive property grain coating or inorganic particle and temperature sensitive property particle, wherein said perforated membrane matrix does not have adhesive or inorganic particle or temperature sensitive property particle in the inner hole.
According to the composite porous film of the utility model first aspect, wherein said perforated membrane matrix is a polyolefin porous membrane.The thickness of said polyolefin porous membrane is 15 to 40 μ m.The perforated membrane matrix that is used for the utility model can be commercially available conventional lithium ion battery separator; The polyalkene diaphragm of the dry method simple tension of U.S. Celgard company for example; The wet method polyethylene barrier film of Japan eastern combustion company, and the polypropylene diaphragm of homemade biaxial tension etc.
According to the composite porous film of the utility model first aspect, the porosity of wherein said perforated membrane matrix is preferably 35% to 70% greater than 30%, and more preferably 40% to 60%.
According to the composite porous film of the utility model first aspect, the thickness of the mixed coating of wherein said inorganic particle coating and/or temperature sensitive property grain coating and/or inorganic particle and temperature sensitive property particle is 1 to 20 μ m, is preferably 3 to 15 μ m.
Composite porous film according to the utility model first aspect; The content of wherein said inorganic particle in said inorganic particle coating and/or inorganic particle and/or temperature sensitive property particle mixed coating is 0 weight %-95 weight %; Preferred 20 weight %-90 weight %, more preferably 30 weight %-70 weight %.
According to the composite porous film of the utility model first aspect, wherein said inorganic particle is selected from one or more in silicon dioxide, titanium dioxide, lanthana, zirconium dioxide, alundum (Al, barium sulfate, calcium carbonate and the carborundum.But the inorganic particle that uses in the composite porous film of the utility model is not limited thereto, so long as in the electrochemical environment of battery charging and discharging, keep the inorganic particle of stable physical and chemical state in the composite membrane of the utility model, to use.
According to the composite porous film of the utility model first aspect, wherein said inorganic particle and/or temperature sensitive property particle grain size are 0.001-5 μ m, are preferably 0.005-2 μ m, most preferably are 0.01-1 μ m.
Composite porous film according to the utility model first aspect; The content of wherein said temperature sensitive property particle in said temperature sensitive property grain coating and/or inorganic particle and/or temperature sensitive property particle mixed coating is 0 weight %-95 weight %; Preferred 20 weight %-85 weight %; More preferably 30 weight %-70 weight %, most preferably 40 weight %-60 weight %.
Composite porous film according to the utility model first aspect; Wherein said temperature sensitive property particle can fusion under specific temperature and is sealed the micropore of perforated membrane; Can select fusing point or melting range material according to different needs in the different temperatures scope; For example when the needs perforated membrane is closed during at 100-120 ℃, can use Tissuemat E powder or polypropylene wax powder as temperature sensitive property particle.
According to the composite porous film of the utility model first aspect, wherein said adhesive is selected from one or more in Kynoar, vinylidene fluoride-hexafluoropropylene copolymer, acrylic acid ester, polyvinyl chloride, polytetrafluoroethylene, butadiene-styrene rubber, polyurethane, acrylonitrile-butadiene rubber, cellulose derivative and the polyvinyl alcohol.
Composite porous film according to the utility model first aspect; The content of wherein said adhesive in the mixed coating of said inorganic particle coating and/or temperature sensitive property grain coating and/or inorganic particle and temperature sensitive property particle is 0.5 weight %-60 weight %; Be preferably 2 weight %-50 weight %, more preferably 5 weight %-40 weight %.
Composite porous film according to the utility model first aspect; Also comprise dispersant in the wherein said coating, said dispersant is selected from one or more in APEO, polyethenoxy ether, poly carboxylic acid derivative's (for example polyacrylic acid, polymethylacrylic acid or its salt etc.), gelatin and the algin; The content of said dispersant in the mixed coating of said inorganic particle coating and/or temperature sensitive property grain coating and/or inorganic particle and temperature sensitive property particle is 0-5 weight %, preferred 2 weight %-3 weight %.
According to the composite porous film of the utility model first aspect owing to have the inorganic particle coating; Therefore has excellent temperature tolerance; Has extremely low percent thermal shrinkage; This has improved the fail safe of battery greatly, and because adhesive and/or inorganic particle are not contained in perforated membrane matrix inside, so have and essentially identical gas permeability of polyolefin porous membrane matrix and ion permeability; Therefore use the lithium ion battery of the compound porous film preparation of the utility model can keep good cycle characteristics, and be applicable to the electrokinetic cell of preparation high charge-discharge magnification.
The second aspect of the utility model provides a kind of method for preparing the composite porous film of the utility model, may further comprise the steps:
Preparation applies slurry;
The perforated membrane matrix is immersed in makes the preimpregnation medium be full of the micropore of perforated membrane matrix in the preimpregnation medium;
On the one or both sides of the perforated membrane matrix that is full of the preimpregnation medium, apply the coating slurry of preparation; And
With coated perforated membrane drying to remove preimpregnation medium and solvent.
According to the method for the utility model second aspect, wherein said perforated membrane matrix is a polyolefin porous membrane.The thickness of said polyolefin porous membrane is 15 to 40 μ m.The perforated membrane matrix that is used for the utility model can be commercially available conventional batteries barrier film, the polyalkene diaphragm of the dry method simple tension of U.S. Celgard company for example, and the wet method polyethylene barrier film of Japanese eastern combustion company, and the polypropylene diaphragm of homemade biaxial tension etc.
Method according to the utility model second aspect; The porosity of wherein said perforated membrane matrix does not have special qualification; But consider that from the purposes as battery diaphragm those skilled in the art can select the different perforated membrane matrix of porosity as required, the porosity of said perforated membrane matrix is preferably greater than 30%; More preferably 35% to 70%, most preferably be 40% to 60%.
According to the method for the utility model second aspect, the thickness of the mixed coating of wherein said inorganic particle coating and/or temperature sensitive property grain coating and/or inorganic particle and temperature sensitive property particle is 1 to 20 μ m, is preferably 3 to 15 μ m.
According to the method for the utility model second aspect, wherein said coating slurry comprises inorganic particle and/or temperature sensitive property particle, adhesive and solvent.
Method according to the utility model second aspect; The preparation of wherein said coating slurry comprises: with adhesive dissolving or be dispersed in and obtain binder solution or emulsion in the solvent, then inorganic particle and/or temperature sensitive property Dispersion of Particles are formed the coating slurry that contains inorganic particle and/or temperature sensitive property particle in gained solution.
Method according to the utility model second aspect; Wherein said inorganic particle is selected from one or more in silicon dioxide, titanium dioxide, lanthana, zirconium dioxide, alundum (Al, barium sulfate, calcium carbonate and the carborundum; But the inorganic particle that uses in the utility model method is not limited thereto, so long as in the electrochemical environment of battery charging and discharging, keep the inorganic particle of stable physical and chemical state in the method for the utility model, to use.
Method according to the utility model second aspect; The content of wherein said inorganic particle in said inorganic particle coating and/or inorganic particle and/or temperature sensitive property particle mixed coating is 0 weight %-95 weight %; Preferred 20 weight %-80 weight %, more preferably 30 weight %-70 weight %.
According to the method for the utility model second aspect, wherein said temperature sensitive property particle includes, but not limited to Tissuemat E or polypropylene wax.
Method according to the utility model second aspect; The content of wherein said temperature sensitive property particle in said temperature sensitive property grain coating and/or inorganic particle and/or temperature sensitive property particle mixed coating is 0 weight %-95 weight %; Preferred 20 weight %-85 weight %; More preferably 30 weight %-70 weight %, most preferably 40 weight %-60 weight %.
According to the method for the utility model second aspect, wherein said inorganic particle or temperature sensitive property particle grain size are 0.001-5 μ m, are preferably 0.05-2 μ m, and more preferably 0.05-1 μ m most preferably is 0.01-1 μ m.
Method according to the utility model second aspect; Wherein said adhesive is selected from one or more in Kynoar, vinylidene fluoride-hexafluoropropylene copolymer, acrylic acid ester, polyvinyl chloride, polytetrafluoroethylene, butadiene-styrene rubber, polyurethane, acrylonitrile-butadiene rubber, cellulose derivative and the polyvinyl alcohol; But the adhesive that uses in the utility model is not limited thereto; Adhesive role in the utility model only be with inorganic particle and/or temperature sensitive property particle bond on the surface of perforated membrane matrix, as long as therefore can realize that the adhesive of this function all is included in the scope of the utility model.
Method according to the utility model second aspect; The content of wherein said adhesive in the mixed coating of said inorganic particle coating and/or temperature sensitive property grain coating and/or inorganic particle and temperature sensitive property particle is 0.5 weight %-60 weight %; Be preferably 2 weight %-50 weight %, more preferably 5 weight %-40 weight %.
Method according to the utility model second aspect; Wherein said solvent species is confirmed according to the adhesive kind of using; As long as can adhesive dissolving or swelling can be used in the utility model with the solvent that forms solution or emulsion; Suitable solvent comprises; N-N-methyl-2-2-pyrrolidone N-, N, one or more in dinethylformamide, oxolane, water, toluene, xylenes, acetone, halogenated hydrocarbons, ketone and the esters solvent, but employed solvent is not limited thereto in the utility model; The effect of solvent is dissolving or dispersing binder formation solution or emulsion just, therefore so long as can adhesive dissolving or the solvent that disperses all be included in the scope of the utility model.The addition of solvent is adjusted according to the thickness of coating and the viscosity of solution or emulsion; When solvent adding amount was higher, the viscosity that applies slurry was less, thereby the coating layer thickness that applies is thinner; Vice versa; The weight ratio of the solid constituent in usual solvents and the coating coating slurry (being inorganic particle and/or temperature sensitive property particle) is 90: 10～50: 50, is preferably 80: 20～40: 30, more preferably 70: 30～30: 20.
Method according to the utility model second aspect; Wherein said preimpregnation medium is selected from N-N-methyl-2-2-pyrrolidone N-, N; In dinethylformamide, oxolane, toluene, xylenes, acetone, halogenated hydrocarbons, ketone and the esters solvent one or more; But the preimpregnation medium that uses in the utility model is not limited to this; The effect of preimpregnation medium is that it can be penetrated in the inner hole of perforated membrane matrix, thereby occupies the space of perforated membrane internal holes, and adhesive in the feasible coating slurry and inorganic particle and/or temperature sensitive property particle can not enter into the inside of perforated membrane matrix; Thereby only on the surface of perforated membrane matrix, form coating, can not cause the obstruction of perforated membrane matrix micropore.
Method according to the utility model second aspect; Wherein said coating slurry also comprises dispersant; Suitable dispersant includes, but not limited to APEO, polyethenoxy ether, poly carboxylic acid derivative's (like polyacrylic acid, polymethylacrylic acid or its salt etc.), gelatin, algin or its combination; The content of said dispersant in the mixed coating of said inorganic particle coating and/or temperature sensitive property grain coating and/or inorganic particle and temperature sensitive property particle is 0-5 weight %, preferred 2 weight %-3 weight %.
According to the method for the utility model second aspect, wherein will apply slurry the method on the said perforated membrane matrix of being coated in and to adopt the conventional method in this area, methods such as for example spraying, dip-coating, brushing, spin coating, extruding, transfer printing.
Under the situation of the method for using the utility model second aspect, owing to when applying, apply slurry and can not be penetrated into perforated membrane matrix inside, thereby only on the surface of perforated membrane matrix, form coating.So the composite porous film of preparation has guaranteed that also gas permeability and ion trafficability characteristic can significantly not reduce when having excellent thermal stability.
The third aspect of the utility model provides a kind of method for preparing composite porous film, may further comprise the steps:
Preparation applies slurry, wherein adhesive is dissolved into and forms binder solution in the aqueous solvent system, then inorganic particle and/or temperature sensitive property Dispersion of Particles is formed the coating slurry in said binder solution;
Said coating slurry is coated in the one or both sides of perforated membrane matrix; And
With the perforated membrane drying after applying to remove said aqueous solvent.
According to the method for the utility model third aspect, wherein said perforated membrane matrix is a polyolefin porous membrane.The thickness of said polyolefin porous membrane is 15 to 40 μ m.The perforated membrane matrix that is used for the utility model can be commercially available conventional batteries barrier film, the polyalkene diaphragm of the dry method simple tension of U.S. Celgard company for example, and the wet method polyethylene barrier film of Japanese eastern combustion company, and the polypropylene diaphragm of homemade biaxial tension etc.
Method according to the utility model third aspect; The porosity of wherein said perforated membrane matrix does not have special qualification; But consider that from the purposes as battery diaphragm those skilled in the art can select the different perforated membrane matrix of porosity as required, the porosity of said perforated membrane matrix is preferably greater than 30%; More preferably 35% to 70%, most preferably be 40% to 60%.
According to the method for the utility model third aspect, the thickness of the mixed coating of wherein said inorganic particle coating and/or temperature sensitive property grain coating and/or inorganic particle and temperature sensitive property particle is 1 to 20 μ m, is preferably 3 to 15 μ m.
Method according to the utility model third aspect; Wherein said inorganic particle is selected from one or more in silicon dioxide, titanium dioxide, lanthana, zirconium dioxide, alundum (Al, barium sulfate, calcium carbonate and the carborundum; But the inorganic particle that uses in the utility model method is not limited thereto, so long as in the electrochemical environment of battery charging and discharging, keep the inorganic particle of stable physical and chemical state in the method for the utility model, to use.
Method according to the utility model third aspect; The content of wherein said inorganic particle in said inorganic particle coating and/or inorganic particle and/or temperature sensitive property particle mixed coating is 50 weight %-95 weight %; Preferred 20 weight %-90 weight %, more preferably 30 weight %-70 weight %.
According to the method for the utility model third aspect, wherein said temperature sensitive property particle includes, but not limited to Tissuemat E or polypropylene wax.
Method according to the utility model third aspect; The content of wherein said temperature sensitive property particle in said temperature sensitive property grain coating and/or inorganic particle and/or temperature sensitive property particle mixed coating is 0 weight %-95 weight %; Preferred 20 weight %-85 weight %; More preferably 30 weight %-70 weight %, most preferably 40 weight %-70 weight %.
According to the method for the utility model third aspect, wherein said inorganic particle or temperature sensitive property particle grain size are 0.001-5 μ m, are preferably 0.05-4 μ m, more preferably 0.1-1 μ m.
Method according to the utility model third aspect; Wherein said adhesive is selected from one or more in Kynoar, vinylidene fluoride-hexafluoropropylene copolymer, acrylic acid ester, polyvinyl chloride, polytetrafluoroethylene, butadiene-styrene rubber, polyurethane, acrylonitrile-butadiene rubber, cellulose derivative and the polyvinyl alcohol; But the adhesive that uses in the utility model is not limited thereto; Adhesive role in the utility model only be with inorganic particle and/or temperature sensitive property particle bond on the surface of perforated membrane matrix, as long as therefore can realize that the adhesive of this function all is included in the scope of the utility model.
Method according to the utility model third aspect; The content of wherein said adhesive in the mixed coating of said inorganic particle coating and/or temperature sensitive property grain coating and/or inorganic particle and temperature sensitive property particle is 0.5 weight %-60 weight %; Be preferably 2 weight %-50 weight %, more preferably 5 weight %-40 weight %.
According to the method for the utility model third aspect, wherein said aqueous solvent is the mixed solvent system of water or water and organic solvent, any organic solvent of said organic solvent for dissolving each other with water, for example ethanol, oxolane, acetone etc.; The contact angle of said aqueous solvent and said porous membrane substrate preferably 60 ° to 150 ° scope, more has 80 ° to 120 ° the scope that is selected in 45 ° to 180 ° scope, most preferably 90 ° to 110 ° scope; The addition of said aqueous solvent is adjusted according to the thickness of coating and the viscosity of solution or emulsion; When the aqueous solvent addition was higher, the viscosity that applies slurry was less, thereby the coating layer thickness that applies is thinner; Vice versa; Usually the weight ratio of the solid constituent (being inorganic particle and/or temperature sensitive property particle) in aqueous solvent and the coating coating slurry is 90: 10～50: 50, is preferably 80: 20～40: 30, more preferably 70: 30～30: 20.
Method according to the utility model third aspect; Wherein said coating slurry also comprises dispersant; Suitable dispersant comprises; But be not limited to APEO, polyethenoxy ether, poly carboxylic acid derivative's (like polyacrylic acid, polymethylacrylic acid or its salt etc.), gelatin, cellulose, algin or its combination; The content of said dispersant in the mixed coating of said inorganic particle coating and/or temperature sensitive property grain coating and/or inorganic particle and temperature sensitive property particle is 0-5 weight %, preferred 2 weight %-3 weight %.
According to the method for the utility model third aspect, wherein will apply slurry the method on the said perforated membrane matrix of being coated in and to adopt the conventional method in this area, methods such as for example spraying, dip-coating, brushing, spin coating, extruding, transfer printing.
Under the situation of the method for using the utility model third aspect; Owing to use aqueous solvent in the said slurry; Under capillary effect; Apply slurry and can't be penetrated into the inside of perforated membrane matrix, thereby only on the surface of perforated membrane matrix, form coating, make adhesive and/or inorganic particle and/or temperature sensitive property particle can not enter into perforated membrane matrix inside and cause the obstruction in hole.The prepared composite perforated membrane has excellent thermal stability, has guaranteed also that simultaneously gas permeability and ion trafficability characteristic can significantly not reduce.In addition, use aqueous solvent system to significantly reduce the use of poisonous organic solvent, thereby greatly reduced influence operator ' s health.
The fourth aspect of the utility model provides the thorough fare of composite porous film in the preparation lithium ion battery, the particularly purposes in the preparation power lithium-ion battery according to the utility model first aspect.Resistance to elevated temperatures and fail safe that the compound porous film preparation lithium ion battery of use the utility model first aspect can improve battery effectively; Can prepare electrokinetic cell high-power, high-discharge-rate, for example be used for the large-sized power lithium ion battery of electric automobile etc.
Description of drawings
Fig. 1 is the sketch map of the composite porous film of the utility model preferred embodiment; Wherein Fig. 1 a is the composite porous film of one-sided coating inorganic grain coating; Fig. 1 b is the composite porous film of two-sided coatings inorganic particle coating; Fig. 1 c is the composite porous film that a side coating inorganic grain coating opposite side applies temperature sensitive property grain coating; Fig. 1 d is the composite porous film of two-sided coatings inorganic particle and temperature sensitive property particle mixed coating; Fig. 1 e is the composite porous film of one-sided coating inorganic particle and temperature sensitive property particle mixed coating.
Embodiment
Below with reference to accompanying drawings, with the mode of exemplary embodiment composite porous film and preparation method thereof of the utility model and the lithium ion battery that uses the composite porous film of the utility model are described in more detail.Accompanying drawing is not to draw in proportion, and in order to be clearly shown that the characteristic of the utility model, Comparative Examples has been carried out exaggerative processing.And it is in order to make this specification fully with complete that these embodiment are provided, so that those skilled in the art can make much of and implement the utility model, but the utility model is not defined as the listed exemplary embodiment of this paper.
Embodiment 1
Vinylidene fluoride-hexafluoropropylene copolymer (Kynar2801) (20 weight portion) is joined in the mixed solvent (600 weight portion) of N-methyl 2-Pyrrolidone (NMP) and acetone (NMP: acetone v/v=7: 3) wherein; Under stirring condition, fully obtain solution after the dissolving; In solution, slowly add alundum (Al (85 weight portions; Average grain diameter 0.5 μ m) and gelatin (5 weight portion), under ultrasonic and strong shearing condition, continue to stir, form stable suspension-turbid liquid and be coating coating slurry.With the thickness of wet method preparation is that the thick polyethylene single-layer septum of 25 μ m (porosity 35%) makes barrier film inside be full of NMP among the immersion NMP earlier; After removing the unnecessary NMP in surface; Blade coating one deck coating coating slurry on a surface of barrier film; It is the aluminum oxide coating of 5 μ m that dry back forms thickness, and the thickness that obtains the single face coating is 30 μ m composite diaphragms (its schematic cross-section is shown in Fig. 1 a).Detecting thermal contraction performance under gas permeability and 140 ℃ of composite membrane is listed in the table below in 1.
Embodiment 2
Polyurethane (10 weight portion) is joined in the ethyl acetate (500 weight portion); Under agitation fully obtain solution after the dissolving; In solution, add zirconium dioxide (50 weight portions, average grain diameter 1.0 μ m), Tissuemat E (40 weight portions, average grain diameter 0.5 μ m) and APEO (3 weight portion); Under ultrasonic and strong shearing condition, continue to stir, form stable suspension-turbid liquid and be the coating slurry.With the thickness of dry method simple tension is that the thick polypropylene single-layer septum of 25 μ m (porosity 45%) makes barrier film inside be full of acetone in the immersion acetone earlier; After the solvent evaporates of membrane surface; Print-on coating one deck applies slurry on a surface of barrier film; It is the composite coating of 7 μ m that dry back forms thickness, and the thickness that obtains the single face coating is 32 μ m composite diaphragms (its schematic cross-section is shown in Fig. 1 e).Detecting thermal contraction performance under gas permeability and 140 ℃ of composite membrane is listed in the table below in 1.
Embodiment 3
In polyurethane aqueous dispersion (20 weight portions (solid content 30%)), add silicon dioxide (70 weight portions; Average grain diameter 2 μ m), Sodium Polyacrylate (3 weight portion) and gelatin (7 weight portion); After adding an amount of water, under ultrasonic and strong shearing condition, stir the stable suspension-turbid liquid of formation and be the coating slurry.With the thickness of dry method biaxial tension is the surperficial two-sided dip-coating of the thick polypropylene single-layer septum of 40 μ m (porosity 42%); It is the silica dioxide coating of 5 μ m that dry back forms thickness, and the thickness that obtains dual coated is 50 μ m composite diaphragms (its schematic cross-section is shown in Fig. 1 b).Detecting thermal contraction performance under gas permeability and 140 ℃ of composite membrane is listed in the table below in 1.
Embodiment 4
Vinylidene fluoride-hexafluoropropylene copolymer (Kynar2801) (10 weight portion) is joined (NMP: the acetone v/v=7: 3) wherein of (600 weight portion) in the mixed solvent of N-methyl 2-Pyrrolidone (NMP) and acetone; Under stirring condition, fully obtain solution after the dissolving; In solution, slowly add silicon dioxide (40 weight portions; Average grain diameter 3 μ m) and gelatin (5 weight portion), under ultrasonic and strong shearing condition, continue to stir, form stable suspension-turbid liquid and be coating coating slurry.With the thickness of wet method preparation is that the thick polyethylene single-layer septum of 25 μ m (porosity 35%) makes barrier film inside be full of NMP among the immersion NMP earlier; After removing the unnecessary NMP in surface; Blade coating one deck coating coating slurry on a surface of barrier film; It is the composite coating of 5 μ m that dry back forms thickness, and the thickness that obtains the single face coating is 30 μ m composite diaphragms (its schematic cross-section is shown in Fig. 1 e).Detecting thermal contraction performance under gas permeability and 140 ℃ of composite membrane is listed in the table below in 1.
Embodiment 5
Vinylidene fluoride-hexafluoropropylene copolymer (Kynar2801) (10 weight portion) is joined in the mixed solvent (600 weight portion) of N-methyl 2-Pyrrolidone (NMP) and acetone (NMP: acetone v/v=7: 3) wherein; Under stirring condition, fully obtain solution after the dissolving; In solution, slowly add alundum (Al (85 weight portions; Average grain diameter 5 μ m) and carboxymethyl cellulose (5 weight portion), under ultrasonic and strong shearing condition, continue to stir, form stable suspension-turbid liquid and be coating coating slurry.With the thickness of wet method preparation is that the thick polyethylene single-layer septum of 25 μ m (porosity 35%) makes barrier film inside be full of NMP among the immersion NMP earlier; After removing the unnecessary NMP in surface; Blade coating one deck coating coating slurry on a surface of barrier film; It is the aluminum oxide coating of 7 μ m that dry back forms thickness, and the thickness that obtains the single face coating is 32 μ m composite diaphragms (its schematic cross-section is shown in Fig. 1 a).Detecting thermal contraction performance under gas permeability and 140 ℃ of composite membrane is listed in the table below in 1.
Embodiment 6
Acrylonitrile-butadiene rubber adhesive (10 weight portion) is joined in the ethyl acetate (800 weight portion); Under stirring condition, fully obtain solution after the dissolving; In solution, slowly add alundum (Al (90 weight portions; Average grain diameter 0.5 μ m), under ultrasonic and strong shearing condition, continues to stir, form stable suspension-turbid liquid and be coating coating slurry.With the thickness of wet method preparation is that the thick polyethylene single-layer septum of 25 μ m (porosity 45%) makes barrier film inside be full of ethyl acetate in the immersion ethyl acetate earlier; After removing the unnecessary ethyl acetate in surface; Blade coating one deck coating coating slurry on a surface of barrier film; It is the aluminum oxide coating of 3 μ m that dry back forms thickness, and the thickness that obtains the single face coating is 28 μ m composite diaphragms (its schematic cross-section is shown in Fig. 1 a).Detecting thermal contraction performance under gas permeability and 140 ℃ of composite membrane is listed in the table below in 1.
Embodiment 7
Kynoar (15 weight portion) is joined N; In the dinethylformamide (700 weight portion); Under stirring condition, fully obtain solution after the dissolving, in solution, slowly add titanium dioxide (85 weight portions, average grain diameter 2 μ m); Under ultrasonic and strong shearing condition, continue to stir, form stable suspension-turbid liquid and be coating coating slurry.With the thickness of wet method preparation is that the thick polyethylene single-layer septum of 25 μ m makes barrier film inside be full of acetone in the immersion acetone earlier; After removing the unnecessary acetone in surface; Blade coating one deck coating coating slurry on a surface of barrier film; It is the coating of titanium dioxide of 5 μ m that dry back forms thickness, and the thickness that obtains the single face coating is 30 μ m composite diaphragms (its schematic cross-section is shown in Fig. 1 a).Detecting thermal contraction performance under gas permeability and 140 ℃ of composite membrane is listed in the table below in 1.
Embodiment 8
With styrene-butadiene latex (40 weight portions; (solid content 30%)) join in the water (100 weight portion), under stirring condition, fully obtain solution after the dissolving, in solution, slowly add zirconium dioxide (80 weight portions; Average grain diameter 0.01 μ m) and Tissuemat E (15 weight portions; Average grain diameter 0.02 μ m), under ultrasonic and strong shearing condition, continues to stir, form stable suspension-turbid liquid and be coating coating slurry.Using the thickness of dry method biaxial tension method preparation is that the thick polypropylene single-layer septum of 20 μ m (porosity 45%) is as the perforated membrane matrix; Blade coating one deck coating coating slurry on two surfaces of barrier film; It is the zirconium dioxide particle of 7 μ m and the composite coating of polyethylene wax pellets that dry back forms thickness, and the thickness that obtains dual coated is 34 μ m composite diaphragms (its schematic cross-section is shown in Fig. 1 d).Detecting thermal contraction performance under gas permeability and 140 ℃ of composite membrane is listed in the table below in 1.
Embodiment 9
Polyvinyl chloride (12 weight portion) is joined in the oxolane (400 weight portion); Under stirring condition, fully obtain solution after the dissolving; In solution, slowly add barium sulfate (60 weight portions, average grain diameter 0.1 μ m) and polypropylene wax powder (26 weight portions, average grain diameter 1 μ m) and carboxymethyl cellulose (2 weight portion); Under ultrasonic and strong shearing condition, continue to stir, form stable suspension-turbid liquid and be coating coating slurry.With the thickness of wet method preparation is that the thick polyethylene single-layer septum of 25 μ m (porosity 40%) is immersed in earlier and makes barrier film inside be full of oxolane in the oxolane; After removing the unnecessary oxolane in surface; Difference blade coating one deck coating coating slurry on two surfaces of barrier film; It is the barium sulfate particle composite coating of 5 μ m that dry back forms thickness, and the thickness that obtains dual coated is 35 μ m composite diaphragms (its schematic cross-section is shown in Fig. 1 d).Detecting thermal contraction performance under gas permeability and 140 ℃ of composite membrane is listed in the table below in 1.
Embodiment 10
Vinylidene fluoride-hexafluoropropylene copolymer (Kynar2801) (9 weight portion) is joined in the mixed solvent (500 weight portion) of N-methyl 2-Pyrrolidone (NMP) and acetone (NMP: acetone v/v=7: 3) wherein; Under stirring condition, fully obtain solution after the dissolving; In solution, slowly add lanthana (50 weight portions; Average grain diameter 2 μ m) and polypropylene wax powder (40 weight portions; Average grain diameter 1 μ m) and algin (1 weight portion), under ultrasonic and strong shearing condition, continue to stir, form stable suspension-turbid liquid and be coating coating slurry.With the thickness of wet method preparation is that the thick polyethylene single-layer septum of 20 μ m (porosity 40%) makes barrier film inside be full of NMP among the immersion NMP earlier; After removing the unnecessary NMP in surface; Difference blade coating one deck coating coating slurry on two surfaces of barrier film; It is the lanthana of 7 μ m and the composite coating of polypropylene wax that dry back forms thickness, and the thickness that obtains dual coated is 34 μ m composite diaphragms (its schematic cross-section is shown in Fig. 1 d).Detecting thermal contraction performance under gas permeability and 140 ℃ of composite membrane is listed in the table below in 1.
Embodiment 11
Polyvinyl alcohol (3 weight portion) is added in the hot water (300 weight portion); Under stirring condition, fully obtain solution after the dissolving; In solution, slowly add calcium carbonate (40 weight portions, average grain diameter 2 μ m) and polypropylene wax powder (55 weight portions, average grain diameter 1 μ m) and gelatin (1 weight portion) and algin (1 weight portion); Under ultrasonic and strong shearing condition, continue to stir, form stable suspension-turbid liquid and be coating coating slurry.With the thickness of wet method preparation is that the thick polyethylene single-layer septum of 20 μ m (porosity 42%) makes barrier film inside be full of ethanol in the immersion ethanol earlier; After removing the unnecessary ethanol in surface; Difference blade coating one deck coating coating slurry on two surfaces of barrier film; It is calcium carbonate and the Tissuemat E powder mixed coating of 7 μ m that dry back forms thickness, and the thickness that obtains dual coated is 34 μ m composite diaphragms (its schematic cross-section is shown in Fig. 1 d).Detecting thermal contraction performance under gas permeability and 140 ℃ of composite membrane is listed in the table below in 1.
Embodiment 12
Ethyl cellulose (5 weight portion) is joined in the mixed solvent (600 weight portion) of toluene and methyl alcohol (toluene: methyl alcohol v/v=6: 4) wherein; Under stirring condition, fully obtain solution after the dissolving; In solution, slowly add carborundum (30 weight portions, average grain diameter 2 μ m) and polypropylene wax powder (60 weight portions, average grain diameter 0.5 μ m) and APEO (5 weight portion); Under ultrasonic and strong shearing condition, continue to stir, form stable suspension-turbid liquid and be coating coating slurry.With the thickness of wet method preparation is that the thick polyethylene single-layer septum of 20 μ m (porosity 35%) makes barrier film inside be full of toluene in the immersion toluene earlier; After removing the unnecessary toluene in surface; Difference dip-coating one deck coating coating slurry on two surfaces of barrier film; It is the silicon-carbide particle of 7 μ m and the mixed coating of polypropylene wax powder that dry back forms thickness, and the thickness that obtains dual coated is 34 μ m composite diaphragms (its schematic cross-section is shown in Fig. 1 d).Detecting thermal contraction performance under gas permeability and 140 ℃ of composite membrane is listed in the table below in 1.
Embodiment 13
Acrylonitrile-butadiene rubber latex (20 weight portion 40%) is added in the entry (800 weight portion); Under stirring condition, fully obtain the adhesive emulsion after the dissolving; In emulsion, slowly add alundum (Al (90 weight portions; Average grain diameter 2 μ m) and gelatin (2 weight portion), under ultrasonic and strong shearing condition, continue to stir, form stable suspension-turbid liquid and be coating coating slurry.With the thickness of dry method simple tension preparation is that three layers of barrier film of the thick polypropylene, polyethylene/polypropylene of 25 μ m (porosity 40%) make barrier film inside be full of acetone in the immersion acetone earlier; After removing the unnecessary acetone in surface; Difference blade coating one deck coating coating slurry on two surfaces of barrier film; It is the aluminum oxide coating of 5 μ m that dry back forms thickness, and obtaining thickness is 35 μ m composite diaphragms (its schematic cross-section is shown in Fig. 1 b).Detecting thermal contraction performance under gas permeability and 140 ℃ of composite membrane is listed in the table below in 1.
Embodiment 14
Acrylonitrile-butadiene rubber latex (20 weight portion 40%) is added in the entry (800 weight portion); Under stirring condition, fully obtain the adhesive emulsion after the dissolving; In emulsion, slowly add alundum (Al (85 weight portions, average grain diameter 2 μ m) and polypropylene wax powder (5 weight portions, average grain diameter 1 μ m) and gelatin (2 weight portion); Under ultrasonic and strong shearing condition, continue to stir, form stable suspension-turbid liquid and be coating coating slurry.The thickness that uses biaxial tension is that the polypropylene diaphragm (porosity 35%) of 16 μ m is as the perforated membrane matrix; Difference dip-coating one deck coating coating slurry on two surfaces of barrier film; It is the alundum (Al of 7 μ m and the mixed coating of polypropylene wax powder that dry back forms thickness, and the thickness that obtains dual coated is 30 μ m composite diaphragms (its schematic cross-section is shown in Fig. 1 d).Detecting thermal contraction performance under gas permeability and 140 ℃ of composite membrane is listed in the table below in 1.
Embodiment 15
Polyvinyl alcohol (3 weight portion) is added in the hot water (300 weight portion); Under stirring condition, fully obtain solution after the dissolving; In solution, slowly add calcium carbonate (40 weight portions, average grain diameter 0.001 μ m) and Tissuemat E powder (55 weight portions, average grain diameter 0.02 μ m) and gelatin (1 weight portion) and algin (1 weight portion); Under ultrasonic and strong shearing condition, continue to stir, form stable suspension-turbid liquid and be coating coating slurry.The thickness that uses biaxial tension is that the polypropylene diaphragm (porosity 35%) of 16 μ m is as the perforated membrane matrix; Dip-coating one deck coating coating slurry on two surfaces of barrier film; It is calcium carbonate and the Tissuemat E powder mixed coating of 4 μ m that dry back forms thickness, and the thickness that obtains dual coated is 24 μ m composite diaphragms (its schematic cross-section is shown in Fig. 1 d).Detecting thermal contraction performance under gas permeability and 140 ℃ of composite membrane is listed in the table below in 1.
Embodiment 16
Vinylidene fluoride-hexafluoropropylene copolymer (Kynar2801) (20 weight portion) is joined in the mixed solvent (500 weight portion) of N-methyl 2-Pyrrolidone (NMP) and acetone (NMP: acetone v/v=7: 3) wherein; Under stirring condition, fully obtain solution after the dissolving; In solution, slowly add lanthana (50 weight portions; Average grain diameter 5 μ m) and algin (1 weight portion), under ultrasonic and strong shearing condition, continue to stir, form stable suspension-turbid liquid and be coating coating slurry.With the thickness of wet method preparation is that the thick polypropylene single-layer septum of 40 μ m (porosity 60%) makes barrier film inside be full of NMP among the immersion NMP earlier; After removing the unnecessary NMP in surface; Blade coating one deck coating coating slurry on a surface of barrier film; It is the lanthana of 15 μ m and the composite coating of polypropylene wax that dry back forms thickness, and the thickness that obtains the single face coating is 55 μ m composite diaphragms (its schematic cross-section is shown in Fig. 1 e).Detecting thermal contraction performance under gas permeability and 140 ℃ of composite membrane is listed in the table below in 1.
Embodiment 17
Vinylidene fluoride-hexafluoropropylene copolymer (Kynar2801) (50 weight portion) is joined in the mixed solvent (600 weight portion) of N-methyl 2-Pyrrolidone (NMP) and acetone (NMP: acetone v/v=7: 3) wherein; Under stirring condition, fully obtain solution after the dissolving; In solution, slowly add alundum (Al (45 weight portions; Average grain diameter 5 μ m) and gelatin (5 weight portion), under ultrasonic and strong shearing condition, continue to stir, form stable suspension-turbid liquid and be coating coating slurry.With the thickness of wet method preparation is that the thick polypropylene single-layer septum of 25 μ m (porosity 65%) makes barrier film inside be full of NMP among the immersion NMP earlier; After removing the unnecessary NMP in surface; Blade coating one deck coating coating slurry on a surface of barrier film; It is the aluminum oxide coating of 15 μ m that dry back forms thickness, and the thickness that obtains the single face coating is 40 μ m composite diaphragms (its schematic cross-section is shown in Fig. 1 a).Detecting thermal contraction performance under gas permeability and 140 ℃ of composite membrane is listed in the table below in 1.
Embodiment 18
Polyurethane binder (30 weight portion) is joined in the ethyl acetate (500 weight portion); Under agitation fully obtain solution after the dissolving; In solution, add zirconium dioxide (67 weight portions; Average grain diameter 2 μ m) and APEO (3 weight portion), under ultrasonic and strong shearing condition, continue to stir, forms stable suspension-turbid liquid and be coating slurry A.Polyurethane binder (20 weight portion) is joined in the ethyl acetate (500 weight portion); Under agitation fully obtain solution after the dissolving; In solution, add Tissuemat E (75 weight portions; Average grain diameter 0.5 μ m) and APEO (5 weight portion), under ultrasonic and strong shearing condition, continue to stir, forms stable suspension-turbid liquid and be coating slurry B.With the thickness of dry method simple tension is that the thick polypropylene single-layer septum of 25 μ m (porosity 55%) makes barrier film inside be full of acetone in the immersion acetone earlier; After the solvent evaporates of membrane surface; Blade coating one deck applies slurry A on a surface of barrier film; Apply slurry B at another surperficial blade coating one deck; Forming zirconia coating and the thickness that thickness is 7 μ m after the drying respectively is the Tissuemat E coating of 5 μ m, and the thickness that obtains dual coated is 37 μ m composite diaphragms (its schematic cross-section is shown in Fig. 1 c).Detecting thermal contraction performance under gas permeability and 140 ℃ of composite membrane is listed in the table below in 1.
Comparative Examples 1
The method for preparing coating liquid is identical with embodiment 1, and different is that the polyethylene single-layer septum is not immersed among the NMP in coating process, directly is coated with.
Comparative Examples 2
The method for preparing coating liquid is identical with embodiment 2, and different is that the polypropylene single-layer septum is not immersed in the acetone in coating process, directly is coated with.The performance of film such as following table 1.
Method of measurement
The gas permeability test: under the static pressure of 310mm water column, measuring 40ml gas is 6.45cm through the Validity Test area
2The needed time of sample be the gas permeability value of barrier film.
Thermal contraction performance: cut and be of a size of 5 * 5cm
2Sample be placed in 140 ℃ the baking oven, take out sample behind the 1h, the length L of the vertical and horizontal of measuring samples respectively behind the cool to room temperature, calculate the percent thermal shrinkage Δ L of the vertical and horizontal of barrier film according to following formula:
Table 1
Though the mode with specific embodiment has described composite porous film of the utility model and preparation method thereof in detail; But it will be apparent to those skilled in the art that; Under the situation of spirit that does not break away from appended claims and scope, can carry out variations and modifications to the utility model, these variations and modification are included in the scope of the utility model equally.
Claims (7)
1. composite porous film; Comprise perforated membrane matrix and inorganic particle and/or temperature sensitive property particle and adhesive; Said inorganic particle and/or temperature sensitive property particle pass through adhesives in said perforated membrane matrix one or both sides; Thereby form inorganic particle coating independently, the mixed coating of temperature sensitive property grain coating or inorganic particle and temperature sensitive property particle independently, wherein said perforated membrane matrix does not have adhesive, inorganic particle and temperature sensitive property particle in the inner hole.
2. composite porous film as claimed in claim 1, wherein said perforated membrane matrix is a polyolefin porous membrane, and the thickness of said perforated membrane matrix is 15 to 40 μ m, and porosity is 30% to 70%.
3. composite porous film as claimed in claim 1, the thickness of the mixed coating of wherein said inorganic particle coating, temperature sensitive property grain coating or inorganic particle and temperature sensitive property particle is 1 to 20 μ m; Said inorganic particle be selected from silicon dioxide, titanium dioxide, lanthana, zirconium dioxide, alundum (Al, barium sulfate, calcium carbonate and the carborundum one or more; Said temperature sensitive property particle is Tissuemat E powder or polypropylene wax powder; Said inorganic particle or temperature sensitive property particle grain size are 0.001-5 μ m.
4. composite porous film as claimed in claim 3, the thickness of the mixed coating of wherein said inorganic particle coating, temperature sensitive property grain coating or inorganic particle and temperature sensitive property particle is 3 to 15 μ m.
5. composite porous film as claimed in claim 3, wherein said inorganic particle or temperature sensitive property particle grain size are 0.01-1 μ m.
6. composite porous film as claimed in claim 1, wherein said adhesive is selected from one or more in Kynoar, vinylidene fluoride-hexafluoropropylene copolymer, acrylic acid ester, polyvinyl chloride, polytetrafluoroethylene, butadiene-styrene rubber, polyurethane, acrylonitrile-butadiene rubber, cellulose derivative and the polyvinyl alcohol; The content of said adhesive in the mixed coating of said inorganic particle coating or temperature sensitive property grain coating or inorganic particle and temperature sensitive property particle is 0.5 weight %-50 weight %.
7. composite porous film as claimed in claim 1 also comprises dispersant in the wherein said coating, said dispersant is selected from one or more in APEO, poly carboxylic acid derivative, gelatin and the algin.
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| CN102437303A (en) * | 2011-12-01 | 2012-05-02 | 北京师范大学 | Composite porous membrane and preparation method thereof |
| CN103247770A (en) * | 2013-04-25 | 2013-08-14 | 东莞新能源科技有限公司 | Lithium-ion battery separator and manufacturing method thereof |
| CN104312002A (en) * | 2014-11-07 | 2015-01-28 | 合肥大安印刷有限责任公司 | Anti-skip polypropylene gasket for floors |
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| CN103247770A (en) * | 2013-04-25 | 2013-08-14 | 东莞新能源科技有限公司 | Lithium-ion battery separator and manufacturing method thereof |
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| CN104377328A (en) * | 2013-08-14 | 2015-02-25 | 三星Sdi株式会社 | Rechargeable lithium battery |
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| CN104312002A (en) * | 2014-11-07 | 2015-01-28 | 合肥大安印刷有限责任公司 | Anti-skip polypropylene gasket for floors |
| CN106531937A (en) * | 2015-09-09 | 2017-03-22 | 丰田自动车株式会社 | Separator for battery, secondary battery including the same, and method of manufacturing separator for battery |
| CN106531937B (en) * | 2015-09-09 | 2020-03-13 | 丰田自动车株式会社 | Separator for battery, secondary battery including the same, and method of manufacturing separator for battery |
| CN108630863A (en) * | 2017-03-21 | 2018-10-09 | 旭成（福建）科技股份有限公司 | A kind of preparation method of high porosity ceramic diaphragm |
| CN108807802A (en) * | 2018-08-20 | 2018-11-13 | 湖南烁普新材料有限公司 | Highly-breathable polymer-coated diaphragm and its preparation method and application |
| CN109524597A (en) * | 2018-11-20 | 2019-03-26 | 哈尔滨理工大学 | A kind of preparation method of the polyethylene wax microballoon with automatic shutoff function/PVDF composite lithium ion cell diaphragm |
| CN109524597B (en) * | 2018-11-20 | 2021-07-23 | 哈尔滨理工大学 | Preparation method of polyethylene wax microsphere/PVDF lithium ion battery diaphragm |
| CN111326697A (en) * | 2018-12-14 | 2020-06-23 | 田口智浩 | Coated diaphragm and preparation method thereof |
| CN112786961A (en) * | 2021-03-23 | 2021-05-11 | 上海电气集团股份有限公司 | Biomass-based gel electrolyte, lithium ion battery, preparation method and application |
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