CN105449141A - Preparation method of battery diaphragm and battery membrane - Google Patents
Preparation method of battery diaphragm and battery membrane Download PDFInfo
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- CN105449141A CN105449141A CN201510988670.3A CN201510988670A CN105449141A CN 105449141 A CN105449141 A CN 105449141A CN 201510988670 A CN201510988670 A CN 201510988670A CN 105449141 A CN105449141 A CN 105449141A
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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
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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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
- 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
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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
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
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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
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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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
- H01M50/411—Organic material
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- 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 application discloses a preparation method of battery membrane and a battery membrane. The preparation method of the invention comprises: evenly dispersing irregularly shaped inorganic particles with D50 of 0.4-2.0 mum and organic particles with particle diameters less than 1 mum in solvent, preparing into slurry, coating the slurry on base membrane, drying, removing the solvent, and obtaining the battery membrane; the solvent comprises deionized water and organic solvent; the volume ratio of the deionized water to the organic solvent is 50-100:1. The preparation method of the application is simple, convenient and easy in operation; the heat resistance of the battery membrane is ensured and the cohesiveness of the battery membrane and the cathode and anode sheets is improved by using inorganic particles and organic particles of different sizes and shapes in the slurry, simultaneously using the deionized water and the organic solvent and using complementation of the two kinds of particles; the liquid absorptivity and liquid retention rate of the battery membrane are improved by mixed use of the two kinds of solvents; the circulation of the battery is improved, and the foundation for preparing high safety performance lithium ion battery is established.
Description
Technical field
The application relates to battery diaphragm field, particularly relates to a kind of preparation method of battery diaphragm, and the battery diaphragm of preparation.
Background technology
Lithium battery is made up of positive pole, negative pole, barrier film and electrolyte.Barrier film as one of large material of lithium battery four, although do not participate in the electrochemical reaction in battery, but the significant components in lithium battery.As the barrier film of lithium ion battery, take microporous polyolefin film as the barrier film of representative, in lithium ion battery, play the positive/negative pole piece of isolation and the effect providing ion conduction channel, its performance has material impact to the security performance of lithium ion battery and electrical property.In addition, the key performances such as the capacity of battery, cycle performance and charging and discharging currents density all have direct relation with barrier film, and the improvement of membrane properties is to the combination property important role improving lithium ion battery.
At present, commercial lithium battery diaphragm with polyolefin, as polyethylene (abbreviation PE), polypropylene (abbreviation PP), single thin film or plural layers be main.But, polyolefin polymers to the absorption of electrolyte and hold facility more weak, this has a certain impact to the efficiency for charge-discharge of lithium battery.In addition, when the situations such as microporous polyolefin film is short-circuited at inside battery, overcharge cause temperature to raise, can heat fusing be there is and its internal capillary be closed, microcellular structure becomes non-porous structure, make resistance sharply increase, electrode reaction stops, and plays closedown (shutdown) effect.But universal along with the lightening and Large Electric automobile of portable set, the energy density of lithium ion battery constantly increases, and this not only requires that barrier film has closing function, and requires that barrier film is heat-resisting.And microporous polyolefin film cannot meet high-capacity battery for the heat-resisting safety requirements of barrier film.
The existing research for barrier film security performance mainly comprises: (1) adopts three layers of barrier film PP/PE/PP; this is Celagrd house journal technology US006080507A; outer field two PP layers serve as protective layer; internal layer PE material serves as closed pore layer, and when battery generation thermal runaway, battery temperature raises; when temperature reaches PE layer fusing point; PE layer starts fusing, closes micropore, blocks battery current.And PP layer thermal endurance is better, fusing, does not serve as protective layer.The deficiency of this patented technology is that three layers of barrier film are general thicker, and thickness is usually more than 16 μm, and PP layer fusing point is 165 DEG C, and heat resistance is limited, and battery safety is inadequate.(2) adopt composite diaphragm, composite bed main material is ceramic particle, and heat resistance is better than three layers of polyalkene diaphragm.Such as, mention in patent application CN103733380A and adopt inorganic particulate coating porous substrate, form composite diaphragm; But, this kind of composite diaphragm and the adhesive property between battery anode slice and negative plate poor, battery performance does not reach desirable effect.Mention in patent application CN102569701 and adopt twice coating process on diaphragm material, for the first time coating ceramic particle, second time coated polymeric, polymer plays cementation; But the shortcoming of this mode is that twice coating cost is higher, and the porosity of two layers of coatings is inconsistent, the aperture tortuosity of composite diaphragm is increased, affects battery performance.
Summary of the invention
The object of the application is to provide a kind of preparation method of battery diaphragm and the battery diaphragm of preparation thereof.
To achieve these goals, the application have employed following technical scheme:
The one side of the application discloses a kind of preparation method of battery diaphragm, comprise D50 in irregular shape is that the organic filler that the inorganic particulate of 0.4-2.0 μm and particle diameter are less than 1 μm is dispersed in solvent, be prepared into slurry, then slurry is coated on basement membrane, namely dry removal solvent obtains the battery diaphragm of the application, and solvent comprises deionized water and organic solvent.
It should be noted that, the preparation method of the application is by two of particular size, shape and performance kinds of particles, i.e. inorganic particulate and organic filler mixing, for the preparation of the battery diaphragm of compound, wherein inorganic particulate can improve the thermal endurance of battery diaphragm, and organic filler then can strengthen barrier film and the caking property between positive plate and negative plate, thus decrease the distortion of battery, improve the yield of battery, and organic filler can also improve the pick up of barrier film and protect liquid rate.
Also it should be noted that, the preparation method of the application, adopt deionized water and organic solvent to prepare slurry, the first simultaneously, avoid the safety and environmental issue that all adopt organic solvent to bring; The second, deionized water and organic solvent used in combination, organic solvent has " softening " effect to organic filler, can increase the imbibition ability of prepared battery diaphragm, and this adopts separately deionized water as not available for solvent.In addition, have caking property after organic filler is partly dissolved, slurry system no longer needs to add other binding agent.
Preferably, the weight ratio of inorganic particulate and organic filler is 10-1:1.
It should be noted that, the consumption of inorganic particulate and organic filler directly affects thermal endurance, caking property, the performance such as pick up and guarantor's liquid rate of battery diaphragm, the application is through a large amount of experiments and research, and for making battery diaphragm reach optimal effectiveness, the weight ratio of preferred both control is 10-1:1.Be appreciated that in more secondary scheme or some specific demands, inorganic particulate and organic filler can not in accordance with the application's limited ranges.
Preferably, the inorganic particle that inorganic particulate is is Main Ingredients and Appearance with at least one in aluminium oxide, aluminium hydroxide, silica, titanium oxide, zirconia, barium titanate and barium sulfate.
Preferably, organic filler is homopolymers or the copolymer of methyl methacrylate, vinylidene, acrylonitrile, hexafluoropropylene etc.
Preferably, solvent comprises deionized water and organic solvent, and organic solvent is selected from least one in acetone, 1-METHYLPYRROLIDONE, ethanol, ether, ethyl acetate.
Preferably, the volume ratio of deionized water and organic solvent is 50-100:1.
Preferably, basement membrane is the microporous polyolefin film of single or multiple lift.In preferred scheme, basement membrane is polypropylene or the polyethylene of individual layer.It should be noted that, wherein the microporous polyolefin film of multilayer, be generally the sandwich construction of microporous polypropylene membrane and polyethene microporous membrane formation.
Preferably, water soluble dispersing agent and wetting agent is also comprised in slurry.
It should be noted that, the object of adding water soluble dispersing agent and wetting agent in slurry is only used to make inorganic particulate and organic filler dispersion more evenly, avoids it to reunite, affects coating quality.Be appreciated that if the mode of physics can be adopted to make inorganic particulate and organic filler be uniformly dispersed, water soluble dispersing agent and wetting agent can not be added.
The another side of the application also discloses a kind of battery diaphragm, it coating at least one surface comprising basement membrane and be coated in described basement membrane, wherein, coating is mainly the organic filler that the inorganic particulate of 0.4-2.0 μm and particle diameter are less than 1 μm containing D50 in irregular shape.
Preferably, the weight ratio of inorganic particulate and organic filler is 10-1:1.
It should be noted that, in fact the battery diaphragm of the application is exactly the battery diaphragm prepared by preparation method adopting the application.
The another side of the application also discloses a kind of lithium ion battery adopting the battery diaphragm of the application.
Be appreciated that, the battery diaphragm of the application is by improving and optimizating its coating, battery diaphragm is made namely to have good thermal endurance, ensure again the caking property between battery diaphragm and positive plate, negative plate, meanwhile, also there is good pick up and protect liquid rate, making, adopt the lithium ion battery of the battery diaphragm of the application, the performance of each side all increases.
Owing to adopting above technical scheme, the beneficial effect of the application is:
The preparation method of the battery diaphragm of the application, simply, conveniently, is easy to operation.And, the application uses inorganic particulate and the organic filler of different size size and shape in the slurry simultaneously, utilize two kinds of particle properties complementations, namely the thermal endurance of battery diaphragm has been ensured, turn improve battery diaphragm and the caking property between positive plate and negative plate, simultaneously, adopt deionized water and organic solvent in preparation method simultaneously, the pick up of battery diaphragm is all improved with guarantor's liquid rate, this contributes to the battery performances such as the cyclicity of raising battery, also for providing the lithium ion battery of high safety performance to lay a good foundation.
Accompanying drawing explanation
Fig. 1 is the structural representation of battery diaphragm in the embodiment of the present application, and wherein 1 is basement membrane, and 2 is coating, and 3 is organic filler, and 4 is inorganic particulate;
Fig. 2 is the pressure-sensitive adhesive tape 180o peeling strength test schematic diagram of battery diaphragm in the embodiment of the present application, and wherein 21 is battery diaphragm, and 22 is double faced adhesive tape, and 23 is metallic plate, and 24 is pressure-sensitive adhesive tape.
Embodiment
In the composite battery separator film of coating inorganic particle, the ceramic particle consumption playing heat resistance in coating is large, and thickness is thicker, and this is unfavorable for the lightening of lithium ion battery; And the bad adhesion between inorganic particulate coating and battery positive/negative plate, makes battery integraty bad; Meanwhile, the composite battery separator film of inorganic coating, its electrolyte wettability and absorbent all poor; These all have impact to the overall performance of battery, limit the application of lithium ion battery.
And the preparation method of the application and the battery diaphragm of preparation thereof, the particle of two kinds of sizes, pattern and performances is included in its coating, inorganic particulate has ensured the thermal endurance of battery diaphragm, organic filler has ensured the caking property of battery diaphragm, pick up and guarantor's liquid rate, adopt the battery diaphragm of the application, thus coordinated the performance of lithium ion battery each side on the whole, thus improve cycle performance and the security performance of battery.In addition, the battery diaphragm preparation method of the application, adopt deionized water and organic solvent to prepare slurry simultaneously, both make use of organic solvent to act on organic filler " softening ", the absorbent of the battery diaphragm prepared by raising, turn avoid a large amount of with an organic solvent to problems such as the pollutions of environment.
Below by specific embodiments and the drawings, the application is described in further detail.Following examples are only further described the application, should not be construed as the restriction to the application.
Embodiment one
The battery diaphragm of this example as shown in Figure 1, comprises basement membrane 1 and the coating 2 being coated on membrane surface, containing organic filler 3 and irregular inorganic particulate 4 in coating 2.This example with the microporous polypropylene membrane of 12 μm for basement membrane, inorganic particulate adopts D50 to be the alumina particle of 700nm, organic filler adopts the vinylidene of particle diameter 200nm and the copolymer pellet of hexafluoropropylene, solvent adopts deionized water and 1-METHYLPYRROLIDONE respectively, water soluble dispersing agent adopts Sulfonates, and wetting agent adopts ethanol.
The preparation method of the battery diaphragm of this example is as follows:
Take 25.2g inorganic particulate, 10.8g organic filler, 0.72g water soluble dispersing agent, 3.5g wetting agent, 1.2g viscosity modifier, 88.1g deionized water, 1.5g organic solvent, all adds all materials in mixer, 2000r/min dispersed with stirring 2h, 1000r/min sand milling dispersion 0.5h, dispersion mixes, and obtains the slurry of this example.The slurry of preparation is coated on uniformly a surface of basement membrane, 40 DEG C of dryings, removes solvent, namely obtain the battery diaphragm of this example.
Performance test is carried out to the battery diaphragm of this example.Thickness adopts calibrator test.Air permeability Gurley value adopts air permeability Gurley instrument thermometrically, and air permeability Gurley value refers to 100cc air under a certain pressure through the time needed for 1 square inch of film.
Adopt the hot strength of GB1040-2006 testing film.
Pick up test is adopted with the following method: the battery diaphragm of this example is cut into longitudinal direction MD=10cm, the part of horizontal direction TD=10cm, weighs respectively and obtain w1, be i.e. dry weight; Then put it in electrolyte and soak 12 hours, it is solvent that electrolyte adopts mass ratio to be the dimethyl carbonate of 1:1 and ethylene carbonate, and molar concentration is 1.0mol/L.Soak after 12 hours and take out, wipe the surplus liquid of membrane surface, weigh and obtain w2, be i.e. weight in wet base.Pick up is calculated as follows:
Example weight w1 before pick up=(after soaking, example weight w2-soaks front example weight w1)/immersion.
Peel strength test method is with reference to GB/T2792-1998 pressure-sensitive adhesive tape 180o peeling strength test method, the schematic diagram of test as shown in Figure 2, battery diaphragm 21 double faced adhesive tape 22 is pasted onto on metallic plate 23, then adopts pressure-sensitive adhesive tape 24 pairs of coatings to be separated, test its peel strength.
Thermal contraction is adopted and is tested with the following method: the battery diaphragm of this example is all cut into longitudinal direction MD=10cm, the part of horizontal direction TD=10cm, put it in the baking oven being heated to 150 DEG C in advance, take out after 30 minutes, measured its length and width respectively by vernier caliper, percent thermal shrinkage is calculated as follows:
Sample longitudinal length before longitudinal thermal contraction=(before heat treatment after sample longitudinal length-heat treatment sample longitudinal length)/heat treatment;
Sample lateral length before horizontal thermal contraction=(before heat treatment after sample lateral length-heat treatment sample lateral length)/heat treatment.
Test result is as shown in table 1.
Embodiment two
The battery diaphragm of this example is identical with embodiment one, just inorganic particulate adopts D50 to be the boehmite particles of 710nm, organic filler adopts the acrylonitrile of particle diameter 500nm and the copolymer pellet of methyl methacrylate, the inorganic particulate of alternative embodiment one and organic filler, inorganic particulate is identical with embodiment one with the consumption of organic filler, preparation method is identical with embodiment one, and all the other each components of slurry and consumption are all identical with embodiment one.The identical method of embodiment one is adopted to prepare battery diaphragm.
Same, adopt the battery diaphragm of identical method of testing to this example to test, test result is as shown in table 1.
Embodiment three
The battery diaphragm of this example is identical with embodiment one, just inorganic particulate adopts D50 to be the alumina particle of 750nm, organic filler adopts the poly methyl methacrylate particle of particle diameter 300nm, the inorganic particulate of alternative embodiment one and organic filler, inorganic particulate is identical with embodiment one with the consumption of organic filler, preparation method is identical with embodiment one, and all the other each components of slurry and consumption are all identical with embodiment one.The identical method of embodiment one is adopted to prepare battery diaphragm.
Same, adopt the battery diaphragm of identical method of testing to this example to test, test result is as shown in table 1.
Embodiment four
The battery diaphragm of this example is identical with embodiment one, just inorganic particulate adopts D50 to be the alumina particle of 700nm, organic filler adopts the acrylonitrile of particle diameter 500nm and the copolymer pellet of methyl methacrylate, the inorganic particulate of alternative embodiment one and organic filler, inorganic particulate is identical with embodiment one with the consumption of organic filler, preparation method is identical with embodiment one, and all the other each components of slurry and consumption are all identical with embodiment one.The identical method of embodiment one is adopted to prepare battery diaphragm.
Same, adopt the battery diaphragm of identical method of testing to this example to test, test result is as shown in table 1.
Embodiment five
The battery diaphragm of this example is identical with embodiment one, just inorganic particulate adopts D50 to be the alumina particle of 700nm, organic filler adopts the poly methyl methacrylate particle of particle diameter 300nm, the inorganic particulate of alternative embodiment one and organic filler, inorganic particulate is identical with embodiment one with the consumption of organic filler, preparation method is identical with embodiment one, and all the other each components of slurry and consumption are all identical with embodiment one.The identical method of embodiment one is adopted to prepare battery diaphragm.
Same, adopt the battery diaphragm of identical method of testing to this example to test, test result is as shown in table 1.
Embodiment six
The battery diaphragm of this example is identical with embodiment one, just inorganic particulate adopts D50 to be the boehmite particles of 710nm, organic filler adopts the vinylidene of particle diameter 200nm and the copolymer pellet of hexafluoropropylene, the inorganic particulate of alternative embodiment one and organic filler, inorganic particulate is identical with embodiment one with the consumption of organic filler, preparation method is identical with embodiment one, and all the other each components of slurry and consumption are all identical with embodiment one.The identical method of embodiment one is adopted to prepare battery diaphragm.
Same, adopt the battery diaphragm of identical method of testing to this example to test, test result is as shown in table 1.
Embodiment seven
The battery diaphragm of this example is identical with embodiment one, just inorganic particulate adopts D50 to be the boehmite particles of 710nm, organic filler adopts the poly methyl methacrylate particle of particle diameter 300nm, the inorganic particulate of alternative embodiment one and organic filler, inorganic particulate is identical with embodiment one with the consumption of organic filler, preparation method is identical with embodiment one, and all the other each components of slurry and consumption are all identical with embodiment one.The identical method of embodiment one is adopted to prepare battery diaphragm.
Same, adopt the battery diaphragm of identical method of testing to this example to test, test result is as shown in table 1.
Embodiment eight
The battery diaphragm of this example is identical with embodiment one, just inorganic particulate adopts D50 to be the alumina particle of 750nm, organic filler adopts the vinylidene of particle diameter 200nm and the copolymer pellet of hexafluoropropylene, the inorganic particulate of alternative embodiment one and organic filler, inorganic particulate is identical with embodiment one with the consumption of organic filler, and all the other each components of slurry and consumption are all identical with embodiment one.The identical method of embodiment one is adopted to prepare battery diaphragm.
Same, adopt the battery diaphragm of identical method of testing to this example to test, test result is as shown in table 1.
Embodiment nine
The battery diaphragm of this example is identical with embodiment one, just inorganic particulate adopts D50 to be the alumina particle of 750nm, organic filler adopts the acrylonitrile of particle diameter 500nm and the copolymer pellet of methyl methacrylate, the inorganic particulate of alternative embodiment one and organic filler, inorganic particulate is identical with embodiment one with the consumption of organic filler, and all the other each components of slurry and consumption are all identical with embodiment one.The identical method of embodiment one is adopted to prepare battery diaphragm.
Same, adopt the battery diaphragm of identical method of testing to this example to test, test result is as shown in table 1.
Embodiment ten
The battery diaphragm of this example is identical with embodiment one, and each component of slurry, the preparation method of battery diaphragm are identical with embodiment one, and just in slurry, the consumption of each component adjusts to some extent, specific as follows:
Take 18.0g inorganic particulate, 18.0g organic filler, 0.72g water soluble dispersing agent, 3.5g wetting agent, 1.2g viscosity modifier, 88.1g deionized water, 1.5g organic solvent, all adds all materials in mixer, 2000r/min dispersed with stirring 2h, 1000r/min sand milling dispersion 0.5h dispersion mixes, and obtains the slurry of this example.The slurry of preparation is coated on uniformly a surface of basement membrane, 40 DEG C of dryings, removes solvent, namely obtain the battery diaphragm of this example.
Same, adopt the identical battery diaphragm of method of testing to this example of embodiment one to test, test result is as shown in table 1.
Embodiment 11
The batter separator structures of this example is identical with embodiment one, comprises basement membrane and the coating being coated on membrane surface, containing organic filler and irregular inorganic particulate in coating.This example with the microporous polypropylene membrane of 12 μm for basement membrane, inorganic particulate adopts D50 to be the alumina particle of 700nm, organic filler adopts the acrylonitrile of particle diameter 500nm and the copolymer pellet of methyl methacrylate, solvent adopts deionized water and 1-METHYLPYRROLIDONE respectively, water soluble dispersing agent adopts Sulfonates, and wetting agent adopts ethanol.The preparation method of the battery diaphragm of this example is as follows:
Take 18.0g inorganic particulate, 18.0g organic filler, 0.72g water soluble dispersing agent, 3.5g wetting agent, 1.2g viscosity modifier, 88.1g deionized water, 1.5g organic solvent, all adds all materials in mixer, 2000r/min dispersed with stirring 2h, 1000r/min sand milling dispersion 0.5h dispersion mixes, and obtains the slurry of this example.The slurry of preparation is coated on uniformly a surface of basement membrane, 40 DEG C of dryings, removes solvent, namely obtain the battery diaphragm of this example.
Same, adopt the identical battery diaphragm of method of testing to this example of embodiment one to test, test result is as shown in table 1.
Comparative example 1
The battery diaphragm of this example is the microporous polypropylene membrane of 12 μm, namely in embodiment 1-11 as basement membrane use microporous polypropylene membrane.
Same, adopt the identical microporous polypropylene membrane of method of testing to this example of embodiment one to test, test result is as shown in table 1.
Comparative example 2
The battery diaphragm of this example comprises basement membrane and is coated on the coating of membrane surface, only containing organic filler in coating.This example with the microporous polypropylene membrane of 12 μm for basement membrane, organic filler adopts the acrylonitrile of particle diameter 200nm and the copolymer pellet of methyl methacrylate, solvent adopts deionized water and 1-METHYLPYRROLIDONE respectively, and water soluble dispersing agent adopts Sulfonates, and wetting agent adopts ethanol.The preparation method of the battery diaphragm of this example is as follows:
Take 36.0g organic filler, 0.72g water soluble dispersing agent, 3.5g wetting agent, 1.2g viscosity modifier, 88.1g deionized water, 1.5g organic solvent, all materials are all added in mixer, 2000r/min dispersed with stirring 2h, 1000r/min sand milling dispersion 0.5h dispersion mixes, and obtains the slurry of this example.The slurry of preparation is coated on uniformly a surface of basement membrane, 40 DEG C of dryings, removes solvent, namely obtain the battery diaphragm of this example.
Same, adopt the identical battery diaphragm of method of testing to this example of embodiment one to test, test result is as shown in table 1.
Comparative example 3
The battery diaphragm of this example comprises basement membrane and is coated on the coating of membrane surface, only containing inorganic particulate in coating.This example is with the microporous polypropylene membrane of 12 μm for basement membrane, and inorganic particulate adopts D50 to be the alumina particle of 700nm, and solvent is deionized water, and water soluble dispersing agent adopts Sulfonates, and wetting agent adopts ethanol, and binding agent is esters of acrylic acid.The preparation method of the battery diaphragm of this example is as follows:
Take 36.0g inorganic particulate, 0.72g water soluble dispersing agent, 3.5g wetting agent, 1.2g viscosity modifier, 88.1g deionized water, 1.5g organic solvent, all materials are all added in mixer, 2000r/min dispersed with stirring 2h, 1000r/min sand milling dispersion 0.5h dispersion mixes, and obtains the slurry of this example.The slurry of preparation is coated on uniformly a surface of basement membrane, 40 DEG C of dryings, removes solvent, namely obtain the battery diaphragm of this example.
It should be noted that, this example adopts separately deionized water as solvent, therefore, needs to add binding agent in addition in slurry, to ensure the stability of coating.
Comparative example 4
The battery diaphragm of this example comprises basement membrane and is coated on the coating of membrane surface, containing inorganic particulate and organic filler in coating.This example with the microporous polypropylene membrane of 12 μm for basement membrane, inorganic particulate adopts D50 to be the alumina particle of 700nm, organic filler adopts the vinylidene of particle diameter 200nm and the copolymer pellet of hexafluoropropylene, solvent is deionized water, water soluble dispersing agent adopts Sulfonates, wetting agent adopts ethanol, and binding agent is esters of acrylic acid.The preparation method of the battery diaphragm of this example is as follows:
Take 25.2g inorganic particulate, 10.8g organic filler, 0.72g water soluble dispersing agent, 3.5g wetting agent, 1.2g viscosity modifier, 88.1g deionized water, 1.5g organic solvent, all adds all materials in mixer, 2000r/min dispersed with stirring 2h, 1000r/min sand milling dispersion 0.5h dispersion mixes, and obtains the slurry of this example.The slurry of preparation is coated on uniformly a surface of basement membrane, 40 DEG C of dryings, removes solvent, namely obtain the battery diaphragm of this example.
Same, although this example has interpolation organic filler, solvent is deionized water, deionized water does not have emollescence to organic filler, and organic filler is insoluble in deionized water completely, therefore, in slurry, same needs add binding agent in addition, to ensure the stability of coating.
Comparative example 5
The battery diaphragm of this example comprises basement membrane and is coated on the coating of membrane surface, containing inorganic particulate and organic filler in coating.This example with the microporous polypropylene membrane of 12 μm for basement membrane, inorganic particulate adopts D50 to be the alumina particle of 700nm, organic filler adopts the vinylidene of particle diameter 200nm and the copolymer pellet of hexafluoropropylene, solvent is acetone and 1-METHYLPYRROLIDONE, and pore former is ethanol: water: cyclohexane=1:1:1.The preparation method of the battery diaphragm of this example is as follows:
Take 25.2g inorganic particulate, 10.8g organic filler, 0.72g oiliness dispersant, 540g acetone, 56gN-methyl pyrrolidone, 1.5g pore former, after organic filler and inorganic particulate are dissolved respectively or having disperseed, again two kinds of slurries are mixed, add pore former simultaneously, obtain the slurry of this example.Organic filler adopts acetone to be solvent, dispersed with stirring 2h under 40 DEG C of water-baths and 1000r/min condition.Inorganic particulate adopts 1-METHYLPYRROLIDONE to be solvent, adds oiliness dispersant, 2000r/min dispersed with stirring 2h, 1000r/min emulsion dispersion 0.5h simultaneously.The slurry of preparation is coated on uniformly two surfaces of basement membrane, 80 DEG C of dryings, removes solvent, namely obtain the battery diaphragm of this example.The oiliness dispersant of this example is acrylic esters oiliness dispersant.
The test result of all embodiments and comparative example is as shown in table 1.
Table 1 membrane properties test result
As can be seen from the test result of table 1, the vertical and horizontal thermal contraction of composite membrane is significantly less than the common batteries barrier film in comparative example 1 and 2, illustrates that the hot property of composite membrane improves a lot.In addition, the thermal contraction adding the composite diaphragm of organic filler and inorganic particulate is also less than the composite membrane of the comparative example 2 of only adding organic filler.Simultaneously pick up be also embodiment 1-11 composite membrane higher than only add inorganic particulate comparative example 3 and only employing deionized water be the composite membrane of the comparative example 4 of solvent.Visible, the composite membrane effect of adding two kinds of particles while the application is better than not adding coating or only adding the properties of coating of inorganic particulate or organic filler.
This example is further, and the barrier film of embodiment 1-11 and the barrier film of comparative example 1-5 are dressed up battery, the battery performances such as test acupuncture, circulation and multiplying power discharging, every test survey 32 batteries.The negative pole of the lithium ion battery that test adopts is Delanium, just very cobalt acid lithium, and electrolyte is the DMC/DEC/PC that 1.0mol/L lithium hexafluoro phosphate is dissolved in 1:1:1.With the test of 1000mAh053450 polymer battery core, the mean value of the test result of 32 batteries, as shown in table 2.
Table 2 battery performance test
In addition, every Battery pack is got 5 and is carried out lancing test.Result shows, barrier film adopts the battery acupuncture temperature of embodiment 1-11 to be starkly lower than the battery of the barrier film by comparative example 1,2,3,4,5, illustrates that composite diaphragm of the present invention can improve the security performance of battery.The result display of table 2, the embodiment of the present application 1-11 capability retention after 500 circulations is all high than comparative example 1-5, and 3C multiplying power discharging property is also apparently higher than comparative example 1-5, and the composite diaphragm of visible the application can improve circulation and the multiplying power discharging property of battery.
Above content is the further description done the application in conjunction with concrete execution mode, can not assert that the concrete enforcement of the application is confined to these explanations.For the application person of an ordinary skill in the technical field, under the prerequisite not departing from the application's design, some simple deduction or replace can also be made, all should be considered as the protection range belonging to the application.
Claims (10)
1. the preparation method of a battery diaphragm, it is characterized in that: comprising D50 in irregular shape is that the spherical organic filler that the inorganic particulate of 0.4-2.0 μm and particle diameter are less than 1 μm is dispersed in solvent, be prepared into slurry, then be coated on basement membrane by described slurry, namely dry solvent of removing obtains described battery diaphragm; Described solvent comprises deionized water and organic solvent, and the volume ratio of described deionized water and organic solvent is 50-100:1.
2. preparation method according to claim 1, is characterized in that: the weight ratio of described inorganic particulate and organic filler is 10-1:1.
3. preparation method according to claim 1, is characterized in that: the inorganic particle that described inorganic particulate is is Main Ingredients and Appearance with at least one in aluminium oxide, aluminium hydroxide, silica, titanium oxide, zirconia, barium titanate and barium sulfate; Described organic filler is homopolymers or the copolymer of methyl methacrylate, vinylidene, acrylonitrile, hexafluoropropylene etc.
4. preparation method according to claim 1, is characterized in that: described organic solvent is selected from least one in acetone, 1-METHYLPYRROLIDONE, ethanol, ether, ethyl acetate.
5. the preparation method according to any one of claim 1-4, is characterized in that: described basement membrane is the microporous polyolefin film of single or multiple lift.
6. the preparation method according to any one of claim 1-4, is characterized in that: also comprise water soluble dispersing agent and wetting agent in described slurry.
7. a battery diaphragm, comprises basement membrane and is coated in the coating at least one surface of described basement membrane, it is characterized in that: described coating is mainly the organic filler that the inorganic particulate of 0.4-2.0 μm and particle diameter are less than 1 μm containing D50 in irregular shape.
8. battery diaphragm according to claim 7, is characterized in that: the weight ratio of described inorganic particulate and organic filler is 10-1:1.
9. the battery diaphragm according to claim 7 or 8, is characterized in that: described battery diaphragm adopts the preparation method's preparation described in any one of claim 1-6.
10. one kind adopts the lithium ion battery of the battery diaphragm described in any one of claim 7-9.
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| CN201510988670.3A CN105449141A (en) | 2015-12-24 | 2015-12-24 | Preparation method of battery diaphragm and battery membrane |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2017185519A1 (en) * | 2016-04-29 | 2017-11-02 | 沧州明珠隔膜科技有限公司 | Aqueous ceramic-coated separator for lithium ion battery and preparation method therefor |
| CN109004153A (en) * | 2018-06-28 | 2018-12-14 | 中国电力科学研究院有限公司 | A kind of ultrathin electrodes support type anodic aluminium oxide membrane and preparation method thereof |
| CN109256516A (en) * | 2018-09-20 | 2019-01-22 | 上海恩捷新材料科技有限公司 | For the isolation film of electrochemical appliance, electrochemical appliance and preparation method thereof |
| CN110911620A (en) * | 2019-10-19 | 2020-03-24 | 东莞东阳光科研发有限公司 | Spotted coating diaphragm slurry, composite diaphragm and preparation method thereof |
| CN114843703A (en) * | 2022-05-18 | 2022-08-02 | 江苏厚生新能源科技有限公司 | Battery diaphragm with irregular-shaped particle coating and preparation method thereof |
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| CN103515564A (en) * | 2013-10-15 | 2014-01-15 | 深圳市星源材质科技有限公司 | Composite diaphragm and method for preparing same |
| CN104600230A (en) * | 2014-12-12 | 2015-05-06 | 深圳中兴创新材料技术有限公司 | Battery diaphragm and application thereof |
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| CN103515564A (en) * | 2013-10-15 | 2014-01-15 | 深圳市星源材质科技有限公司 | Composite diaphragm and method for preparing same |
| CN104600230A (en) * | 2014-12-12 | 2015-05-06 | 深圳中兴创新材料技术有限公司 | Battery diaphragm and application thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2017185519A1 (en) * | 2016-04-29 | 2017-11-02 | 沧州明珠隔膜科技有限公司 | Aqueous ceramic-coated separator for lithium ion battery and preparation method therefor |
| CN109004153A (en) * | 2018-06-28 | 2018-12-14 | 中国电力科学研究院有限公司 | A kind of ultrathin electrodes support type anodic aluminium oxide membrane and preparation method thereof |
| CN109256516A (en) * | 2018-09-20 | 2019-01-22 | 上海恩捷新材料科技有限公司 | For the isolation film of electrochemical appliance, electrochemical appliance and preparation method thereof |
| CN110911620A (en) * | 2019-10-19 | 2020-03-24 | 东莞东阳光科研发有限公司 | Spotted coating diaphragm slurry, composite diaphragm and preparation method thereof |
| CN110911620B (en) * | 2019-10-19 | 2022-04-29 | 东莞东阳光科研发有限公司 | Spotted coating diaphragm slurry, composite diaphragm and preparation method thereof |
| CN114843703A (en) * | 2022-05-18 | 2022-08-02 | 江苏厚生新能源科技有限公司 | Battery diaphragm with irregular-shaped particle coating and preparation method thereof |
| CN114843703B (en) * | 2022-05-18 | 2023-09-22 | 江苏厚生新能源科技有限公司 | Battery separator with irregularly-shaped particle coating and preparation method thereof |
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Address after: 518120 No. 8 Binhai Road, Dapeng street, Dapeng New District, Shenzhen, Guangdong, China. Applicant after: Shenzhen Zhongxing new material technology Limited by Share Ltd Address before: 518020 Shenzhen, Guangdong Dapeng New District Dapeng street water head community Zhongxing Xinzhou complete equipment Co., Ltd. 3 plant 102 Applicant before: Shenzhen ZTE Innovation Material Technology Co., Ltd. |
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Application publication date: 20160330 |