CN103996815A - Single-side polymer coated diaphragm and preparation method thereof - Google Patents
Single-side polymer coated diaphragm and preparation method thereof Download PDFInfo
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- CN103996815A CN103996815A CN201410245473.8A CN201410245473A CN103996815A CN 103996815 A CN103996815 A CN 103996815A CN 201410245473 A CN201410245473 A CN 201410245473A CN 103996815 A CN103996815 A CN 103996815A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 97
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000000576 coating method Methods 0.000 claims abstract description 52
- 239000011248 coating agent Substances 0.000 claims abstract description 50
- 239000011148 porous material Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 11
- 230000004888 barrier function Effects 0.000 claims description 53
- -1 polytetrafluoroethylene Polymers 0.000 claims description 27
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- 239000004743 Polypropylene Substances 0.000 claims description 17
- 238000003618 dip coating Methods 0.000 claims description 17
- 229920001155 polypropylene Polymers 0.000 claims description 16
- 108010010803 Gelatin Proteins 0.000 claims description 14
- 229920000159 gelatin Polymers 0.000 claims description 14
- 239000008273 gelatin Substances 0.000 claims description 14
- 235000019322 gelatine Nutrition 0.000 claims description 14
- 235000011852 gelatine desserts Nutrition 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000004698 Polyethylene Substances 0.000 claims description 9
- 229920000573 polyethylene Polymers 0.000 claims description 8
- 210000002469 basement membrane Anatomy 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- 229920006302 stretch film Polymers 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 3
- 150000001298 alcohols Chemical group 0.000 claims description 3
- 229920006231 aramid fiber Polymers 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000012528 membrane Substances 0.000 abstract description 7
- 239000011247 coating layer Substances 0.000 abstract description 6
- 239000002002 slurry Substances 0.000 abstract description 6
- 230000001351 cycling effect Effects 0.000 abstract 1
- 239000002356 single layer Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 54
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
- 229910052744 lithium Inorganic materials 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 230000009977 dual effect Effects 0.000 description 8
- 229920000098 polyolefin Polymers 0.000 description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- 210000004379 membrane Anatomy 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 230000032798 delamination Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000013047 polymeric layer Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005213 imbibition Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Cell Separators (AREA)
Abstract
The invention discloses a preparation method of a single-side polymer coated diaphragm. The method comprises the following steps: (1) layering a dry-process multilayer stretched membrane or compositing monolayer porous diaphragms under the condition of a corona or high temperature, so as to obtain a bilayer diaphragm; (2) preparing polymer slurry, coating the two outside surfaces of the bilayer diaphragm with the polymer slurry, and drying, so as to form polymer coating layers with three-dimensional pore structures on the two outside surfaces of the bilayer diaphragm; (3) layering the coated bilayer diaphragm, thereby obtaining the single-side polymer coated diaphragm. The invention further discloses the diaphragm prepared by the preparation method. According to the single-side polymer coated diaphragm and the preparation method thereof, the production efficiency is high, and the adhesion between a polymer coating layer and a positive pole piece of the prepared single-side polymer coated diaphragm is good, so that the cycling performance and safety of a battery can be improved.
Description
Technical field
The present invention relates to lithium ion battery separator, especially relate to a kind of preparation method and composite diaphragm that can improve the safety in utilization of lithium ion battery and promote the lithium ion battery combination property one side polymer-coated barrier film that production efficiency is high simultaneously.
Background technology
Barrier film is as one of lithium battery four large materials, although do not participate in the electrochemical reaction in battery, but significant components in lithium battery, diaphragm material is also one of key technology of the lithium battery development of restriction China and application simultaneously.The key performance of the batteries such as capacity, cycle performance and the charging and discharging currents density of battery all has direct relation with barrier film.The improvement of membrane properties plays an important role to the combination property that improves lithium battery.
At present, commercial lithium battery diaphragm is taking polyolefin (PP, PE) single thin film or plural layers as main.The absorption of polyolefin polymers to electrolyte and hold facility a little less than, the efficiency for charge-discharge of lithium battery is had a certain impact; Meanwhile, between the positive pole of liquid lithium ionic cell, negative pole and barrier film, have space, the free electrolyte of battery electrolyte in cyclic process can affect consistency and the fail safe of battery.In order to improve the performance of polyalkene diaphragm, on polyalkene diaphragm, apply the polymer coating that one deck imbibition and liquid-keeping property are strong and replace simple polyolefin lithium battery diaphragm, can greatly reduce like this electrolyte of free state in lithium ion battery, polymeric layer and pole piece can be fitted well simultaneously, gap between pole piece and barrier film has also reduced, and stability and the fail safe of battery are improved.But, in suitability for industrialized production, the methods that adopt dip-coating obtain the two-sided lithium battery diaphragm that is coated with polymer painting that has more, this method application rate is slow, production efficiency is low, polymeric layer and anodal laminating fine, but and negative pole substantially there is no stickiness, this is because positive pole adopts oiliness adhesive, and negative pole adopts Aqueous Adhesives.
Summary of the invention
For overcoming above-mentioned shortcoming, provide a kind of and can improve the safety in utilization of lithium ion battery and promote lithium ion battery combination property one side polymer-coated barrier film that production efficiency is high simultaneously and preparation method thereof.
The object of the invention is to realize by following technical measures, a kind of preparation method of one side polymer-coated barrier film, comprises the steps:
(1), utilize the layering of dry method multilayer stretch film to obtain double-deck barrier film, or compound under corona or hot conditions with individual layer porous septum, obtain double-deck barrier film;
(2), prepare polymer paste, two outer surfaces by polymer paste dip-coating at double-deck barrier film, form the polymer coating with three-D pore structure at two outer surfaces of double-deck barrier film after dry;
(3), the double-deck barrier film after above-mentioned coating is carried out to layering, obtain one side polymer-coated barrier film.
As a kind of optimal way, in described step (2), polymer paste comprises gelatin polymer, pore former and organic solvent.
Preferably, described gelatin polymer be that polytetrafluoroethylene, Kynoar, Kynoar-hexafluoropropylene copolymer, polyimides, polypropylene are fine, one or more in aramid fiber resin.Preferably Kynoar or Kynoar-hexafluoropropylene copolymer.
Preferably, described gelatin polymer molecular weight is 5,000～1, between 000,000.Molecular weight is too low, is difficult to form polymer coating in coating process, and molecular weight is too high, and the dissolubility of polymer is too low, and the viscosity of slurry is too high, is unfavorable for actual production.
Preferably, in described polymer paste, the mass fraction of gelatin polymer (wt%) is 0.2%～20%.The mass fraction (wt%) of pore former is 1%～20%, as preferably 3%～8%.As preferably 1%～10%.If the content of gelatin polymer is too low, in dip-coating process, be difficult to form polymer coating, too high levels, the viscosity of slurry is very large, polymer free settling, the bad control of pore-creating character.
Preferably, described pore former is alcohols (as ethanol, propyl alcohol or butanols) and water.
Preferably, described organic solvent is any one or more the mixture in acetone, dimethyl formamide, chloroform, cyclohexane, METHYLPYRROLIDONE.
As a kind of optimal way, the thickness of described polymer coating one side is 0.1～10 μ m, further preferred 1～4 μ m.Polymer coating is too thin, and in battery, absorb and keep the ability of electrolyte very weak, and not good enough with the laminating of pole piece.If coating is too thick, composite diaphragm passes to lithium ion and can be affected.
As a kind of optimal way, the speed of described dip-coating is 2～5m/min.Be subject to the restriction of drying channel of coating machine length and baking temperature, delivery speed is unsuitable too fast, otherwise not exclusively dry, easily causes the defects such as delamination.Drying tunnel baking temperature in described dry run is 60～130 DEG C.If baking temperature is too low, solvent or pore former are removed not thorough, easily cause delamination or other quality problems.If temperature is higher than 130 DEG C, polyolefin base membrane can be at high temperature impaired, and physical property declines.If polyethylene based film, temperature is preferably lower than 110 DEG C.The average diameter of described three-dimensional perforate is 0.1～10 μ m.
The invention also discloses a kind of according to the prepared one side polymer-coated barrier film of above-mentioned preparation method, described coating basement membrane is the double-layer porous film of polyethylene, the double-layer porous film of polypropylene or polypropylene, polyethylene two-layer compound porous membrane, basement membrane thickness scope is at 8～100 μ m, porosity ranges is 30%～80%, and average pore size is at 0.01～10 μ m.
With respect to prior art, the present invention has the following advantages: the polymer coating of (1) one side polymer-coated barrier film has good absorption and keeps the ability of electrolyte, reduce free state electrolyte in battery, improved cycle performance and the fail safe of battery; (2) polymer coating of one side polymer-coated barrier film and positive plate have good bonding force, and the lithium ion battery of producing has good mechanical performance; (3) preparation method of this kind of coating barrier film has improved two times of left and right compared with prior art productivity ratio, thereby has greatly improved production efficiency.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of polymer coating in the embodiment of the present invention 2.
Fig. 2 is the scanning electron microscope (SEM) photograph of polymer coating in the embodiment of the present invention 3.
Embodiment
Below in conjunction with embodiment and contrast accompanying drawing the present invention is described in further detail.
A preparation method for one side polymer-coated barrier film, comprises the steps:
(1), utilize the layering of dry method multilayer stretch film to obtain double-deck barrier film, or compound under corona or hot conditions with individual layer porous septum, obtain double-deck barrier film; Coating basement membrane is the double-layer porous film of polyethylene, the double-layer porous film of polypropylene or polypropylene, polyethylene two-layer compound porous membrane, and basement membrane thickness scope is at 8～100 μ m, and porosity ranges is 30%～80%, and average pore size is at 0.01～10 μ m;
(2), prepare polymer paste, two outer surfaces by polymer paste dip-coating at double-deck barrier film, form the polymer coating with three-D pore structure at two outer surfaces of double-deck barrier film after dry;
(3), the double-deck barrier film after above-mentioned coating is carried out to layering, obtain one side polymer-coated barrier film.
The preparation method of one side polymer-coated barrier film of the present invention, on the basis of previous technique scheme, concrete is that in step (2), polymer paste comprises gelatin polymer, pore former and organic solvent.Preferably, described gelatin polymer be that polytetrafluoroethylene, Kynoar, Kynoar-hexafluoropropylene copolymer, polyimides, polypropylene are fine, one or more in aramid fiber resin.Preferably Kynoar or Kynoar-hexafluoropropylene copolymer.Described gelatin polymer molecular weight is 5,000～1, between 000,000.Molecular weight is too low, is difficult to form polymer coating in coating process, and molecular weight is too high, and the dissolubility of polymer is too low, and the viscosity of slurry is too high, is unfavorable for actual production.In described polymer paste, the mass fraction of gelatin polymer (wt%) is 0.2%～20%.The mass fraction (wt%) of pore former is 1%～20%, as preferably 3%～8%.As preferably 1%～10%.If the content of gelatin polymer is too low, in dip-coating process, be difficult to form polymer coating, too high levels, the viscosity of slurry is very large, polymer free settling, the bad control of pore-creating character.Described pore former is alcohols (as ethanol, propyl alcohol or butanols) and water.Described organic solvent is any one or more the mixture in acetone, dimethyl formamide, chloroform, cyclohexane, METHYLPYRROLIDONE.
The preparation method of one side polymer-coated barrier film of the present invention, on the basis of previous technique scheme, concrete, the thickness of polymer coating one side is 0.1～10 μ m, further preferred 1～4 μ m.Polymer coating is too thin, and in battery, absorb and keep the ability of electrolyte very weak, and not good enough with the laminating of pole piece.If coating is too thick, composite diaphragm passes to lithium ion and can be affected.
The preparation method of one side polymer-coated barrier film of the present invention, on the basis of previous technique scheme, concrete, the speed of dip-coating is 2～5m/min.Be subject to the restriction of drying channel of coating machine length and baking temperature, delivery speed is unsuitable too fast, otherwise not exclusively dry, easily causes the defects such as delamination.Drying tunnel baking temperature in described dry run is 60～130 DEG C.If baking temperature is too low, solvent or pore former are removed not thorough, easily cause delamination or other quality problems.If temperature is higher than 130 DEG C, polyolefin base membrane can be at high temperature impaired, and physical property declines.If polyethylene based film, temperature is preferably lower than 110 DEG C.The average diameter of described three-dimensional perforate is 0.1～10 μ m.
Below in conjunction with embodiment, such scheme is described further.In following examples, coating basement membrane is that the layering of dry method multilayer stretch film obtains the double-deck microporous barrier of polypropylene, and thickness is 25 μ, and porosity is 42%.
Embodiment 1
Step 1, polymer paste preparation:
(1) 20gPVDF-HFP is joined in 1000g acetone solvent, in the agitator tank of 50 DEG C, stirring and dissolving 10～60 minutes is all dissolved to PVDF-HFP, then stops heating, is cooled to room temperature, and it is as clear as crystal that solution is;
(2) in upper solution, add 40g n-butanol, at room temperature stir 10～30 minutes, it is as clear as crystal that solution is.
Step 2, dip-coating is dried:
Utilize the mode of dip-coating to be coated on the double-deck barrier film of polypropylene both sides the polymer paste in step 1, coating speed is 4m/s, drying tunnel temperature is 110 DEG C, between air humidity 40%～50%, the polymer dual coating barrier film that obtains having three-dimensional porous coating after oven dry, one side coating layer thickness is 2 μ.
Step 3, layering:
Polymer dual coating barrier film layering in step 2 is obtained to one side polymer-coated film, and the speed of layering is 80m/min.
Embodiment 2
Step 1, polymer paste preparation:
(1) 30gPVDF-HFP is joined in 1000g acetone solvent, in the agitator tank of 50 DEG C, stirring and dissolving 10～60 minutes is all dissolved to PVDF-HFP, then stops heating, is cooled to room temperature, and it is as clear as crystal that solution is;
(2) in upper solution, add 40g ethanol, at room temperature stir 10～30 minutes, it is as clear as crystal that solution is.
Step 2, dip-coating is dried:
Utilize the mode of dip-coating to be coated on the double-deck barrier film of polypropylene both sides the polymer paste in step 1, coating speed is 3m/s, drying tunnel temperature is 100 DEG C, between air humidity 70%～80%, the polymer dual coating barrier film that obtains having three-dimensional porous coating after oven dry, one side coating layer thickness is 2 μ.
Step 3, layering:
Polymer dual coating barrier film layering in step 2 is obtained to one side polymer-coated film, and the speed of layering is 80m/min.Fig. 1 is the scanning electron microscope (SEM) photograph of the polymer coating of embodiment 2 prepared products.
Embodiment 3
Step 1, polymer paste preparation:
(1) 20g pure water is joined in 1000g acetone solvent, at room temperature stirs 10 minutes, mix all with;
(2) 20gPVDF-HFP is joined in the mixed solvent of above-mentioned acetone and water, in the agitator tank of 50 DEG C, stirring and dissolving 10～60 minutes is all dissolved to PVDF-HFP, then stops heating, is cooled to room temperature, and it is as clear as crystal that solution is;
(2) in upper solution, add 40g ethanol, at room temperature stir 10～30 minutes, it is as clear as crystal that solution is.
Step 2, dip-coating is dried:
Utilize the mode of dip-coating to be coated on the double-deck barrier film of polypropylene both sides the polymer paste in step 1, coating speed is 3m/s, drying tunnel temperature is 110 DEG C, between air humidity 40%～50%, the polymer dual coating barrier film that obtains having three-dimensional porous coating after oven dry, one side coating layer thickness is 2 μ.
Step 3, layering:
Polymer dual coating barrier film layering in step 2 is obtained to one side polymer-coated film, and the speed of layering is 80m/min.Fig. 2 is the scanning electron microscope (SEM) photograph of the polymer coating of embodiment 3 prepared products.
Embodiment 4
Step 1, polymer paste preparation:
(1) 30g pure water is joined in 1000g acetone solvent, at room temperature stirs 10 minutes, mix all with;
(2) 20gPVDF-HFP is joined in the mixed solvent of above-mentioned acetone and water, in the agitator tank of 50 DEG C, stirring and dissolving 10～60 minutes is all dissolved to PVDF-HFP, then stops heating, is cooled to room temperature, and it is as clear as crystal that solution is;
(2) in upper solution, add 30g n-butanol and 20g cyclohexane, at room temperature stir 10～30 minutes, it is as clear as crystal that solution is.
Step 2, dip-coating is dried:
Utilize the mode of dip-coating to be coated on the double-deck barrier film of polypropylene both sides the polymer paste in step 1, coating speed is 3m/s, drying tunnel temperature is 110 DEG C, between air humidity 40%～50%, the polymer dual coating barrier film that obtains having three-dimensional porous coating after oven dry, one side coating layer thickness is 2 μ.
Step 3, layering:
Polymer dual coating barrier film layering in step 2 is obtained to one side polymer-coated film, and the speed of layering is 80m/min.
Comparative example 1
Basilar partition is selected 12 μ dry method simple tension microporous polypropylene membranes, and porosity is 42%.
Other conditions and technique are with embodiment 3.
Comparative example 2
16 μ dry method simple tension microporous polypropylene membranes, porosity is 42%.
Table 1 embodiment and comparative example performance comparison
Note: zero represents good bonding, × expression Poor cohesion.
The method of testing of pick up: get three samples that specification is 100mm × 100mm of certain sample, each sample is weighed and is designated as m1; Sample is placed in electrolyte and is soaked 2 hours, take out and dry remained on surface electrolyte, weigh and be designated as m2; Pick up L=(m2-m1)/m1*100%.The i.e. pick up of sample for this reason of the average ratio of absorbing liquid of three samples.
The adhesiveness of table 1 septation and pole piece refers to the bonding situation of making after lithium battery.As can be seen from Table 1, in each sample, embodiment 3 and comparative example 1 polymer-coated layer three-D pore structure are better.The barrier film of double spread, with respect to the barrier film of one side coating, is that the adhesiveness aspect of pole piece does not have advantage, and the pick up of double spread barrier film is slightly high, and this is because its coating is thicker.
More than that one side polymer-coated barrier film of the present invention and preparation method thereof is set forth; be used for helping to understand the present invention; but embodiments of the present invention are not restricted to the described embodiments; anyly do not deviate from the change done under the principle of the invention, modification, substitute, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (10)
1. a preparation method for one side polymer-coated barrier film, is characterized in that comprising the steps:
(1), utilize the layering of dry method multilayer stretch film to obtain double-deck barrier film, or with the double-deck barrier film of individual layer porous septum compound acquisition under corona or hot conditions;
(2), prepare polymer paste, two outer surfaces by polymer paste dip-coating at double-deck barrier film, form the polymer coating with three-D pore structure at two outer surfaces of double-deck barrier film after dry;
(3), the double-deck barrier film after above-mentioned coating is carried out to layering, obtain one side polymer-coated barrier film.
2. preparation method according to claim 1, is characterized in that: in described step (2), polymer paste comprises gelatin polymer, pore former and organic solvent.
3. preparation method according to claim 2, is characterized in that: described gelatin polymer is that polytetrafluoroethylene, Kynoar, Kynoar-hexafluoropropylene copolymer, polyimides, polypropylene are fine, one or more in aramid fiber resin.
4. preparation method according to claim 2, is characterized in that: described gelatin polymer molecular weight is 5,000～1, between 000,000.
5. according to claim 2 or described preparation method, it is characterized in that: in described polymer paste, the mass fraction of gelatin polymer is 0.2%～20%, and the mass fraction of pore former is 1%～20%.
6. preparation method according to claim 2, is characterized in that: described pore former is alcohols and water.
7. preparation method according to claim 1, is characterized in that: described organic solvent is any one or more the mixture in acetone, dimethyl formamide, chloroform, cyclohexane, METHYLPYRROLIDONE.
8. preparation method according to claim 1, is characterized in that: the thickness of described polymer coating one side is 0.1～10 μ m.
9. preparation method according to claim 1, is characterized in that: the speed of described dip-coating is 2～5m/min, and the drying tunnel baking temperature in described dry run is 60～130 DEG C, and the average diameter of described three-dimensional perforate is 0.1～10 μ m.
10. one kind according to the prepared barrier film of arbitrary preparation method described in claim 1-9, described coating basement membrane is the double-layer porous film of polyethylene, the double-layer porous film of polypropylene or polypropylene, polyethylene two-layer compound porous membrane, basement membrane thickness scope is at 8～100 μ m, porosity ranges is 30%～80%, and average pore size is at 0.01～10 μ m.
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| CN201410245473.8A CN103996815A (en) | 2014-06-04 | 2014-06-04 | Single-side polymer coated diaphragm and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106898721A (en) * | 2017-02-28 | 2017-06-27 | 沧州明珠隔膜科技有限公司 | A kind of lithium ion battery separator for being suitable to hot dry-pressing and preparation method thereof |
| CN107230766A (en) * | 2017-06-13 | 2017-10-03 | 深圳市星源材质科技股份有限公司 | A kind of multinuclear single shell structure gelatin polymer coating barrier film and preparation method thereof |
| CN109004165A (en) * | 2018-08-01 | 2018-12-14 | 上海钱丰纺织品有限公司 | Heat-resisting lithium ion battery separator and preparation method thereof |
| CN109192902A (en) * | 2018-07-10 | 2019-01-11 | 深圳中兴新材技术股份有限公司 | A kind of preparation method and lithium battery diaphragm of multilevel security protection lithium battery diaphragm |
| CN112018311A (en) * | 2020-09-10 | 2020-12-01 | 青岛蓝科途膜材料有限公司 | Lithium ion battery diaphragm, preparation method and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106898721A (en) * | 2017-02-28 | 2017-06-27 | 沧州明珠隔膜科技有限公司 | A kind of lithium ion battery separator for being suitable to hot dry-pressing and preparation method thereof |
| CN107230766A (en) * | 2017-06-13 | 2017-10-03 | 深圳市星源材质科技股份有限公司 | A kind of multinuclear single shell structure gelatin polymer coating barrier film and preparation method thereof |
| CN107230766B (en) * | 2017-06-13 | 2019-10-18 | 深圳市星源材质科技股份有限公司 | A kind of multicore-single shell structure gelatin polymer coating diaphragm and preparation method thereof |
| CN109192902A (en) * | 2018-07-10 | 2019-01-11 | 深圳中兴新材技术股份有限公司 | A kind of preparation method and lithium battery diaphragm of multilevel security protection lithium battery diaphragm |
| CN109004165A (en) * | 2018-08-01 | 2018-12-14 | 上海钱丰纺织品有限公司 | Heat-resisting lithium ion battery separator and preparation method thereof |
| CN112018311A (en) * | 2020-09-10 | 2020-12-01 | 青岛蓝科途膜材料有限公司 | Lithium ion battery diaphragm, preparation method and application thereof |
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