CN109065811B - Water-based PVDF (polyvinylidene fluoride) coated diaphragm and preparation method and application thereof - Google Patents
Water-based PVDF (polyvinylidene fluoride) coated diaphragm and preparation method and application thereof Download PDFInfo
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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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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- 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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- 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
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- 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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention provides a water-based PVDF (polyvinylidene fluoride) coated diaphragm as well as a preparation method and application thereof, wherein the preparation process comprises the following steps: firstly, preparing modified water-based PVDF powder, further preparing PVDF coating slurry, and further preparing a water-based PVDF coating membrane. The prepared aqueous PVDF coating slurry obviously improves the dispersibility and stability of PVDF particles in aqueous solution by modifying PVDF, and further obviously improves the comprehensive performance of the lithium ion battery diaphragm.
Description
Technical Field
The invention relates to the technical field of battery diaphragm materials, in particular to a water-based PVDF (polyvinylidene fluoride) coated diaphragm and a preparation method and application thereof.
Background
Due to the increasing serious energy and environmental problems and the vigorous development of the electronic information industry, more and more focuses are focused on energy materials with high specific energy, safety and no toxicity. The lithium ion secondary battery has the characteristics of high energy density, long cycle life and no memory effect, and has the advantages of safety, environmental friendliness, reliability, rapid charge and discharge and the like. Therefore, the energy storage device becomes a hot spot of energy storage technology research in recent years, is widely applied to portable electronic products such as mobile phones, notebook computers and digital cameras, and will certainly become a preferred energy storage device of hybrid electric vehicles and electric vehicles.
Currently, the separator used in power batteries is a ceramic or polymer coated separator. PVDF is used as a coating, the PVDF is mainly used as an adhesive layer to bond a pole piece and a diaphragm, the bonding has the advantages that the battery is harder and firmer, and has great advantages in production and transportation, and the PVDF adhesive layer has the other advantage of absorbing liquid and ensures the safety of the battery. Therefore, PVDF coatings are currently used most inside smart phones.
The PVDF coating process mainly includes oil coating and water coating. The adoption of the oil coating process requires the use of a large amount of organic solvents, which causes great environmental pollution and high cost. The water-based coating mainly adopts a coating process using water as a solvent, has little pollution to the environment, and is the development direction of mass production of PVDF coating membranes. However, PVDF as a hydrophobic polymer has poor dispersibility in water, and particles are prone to agglomeration and sedimentation, so that the PVDF coating after coating has a strong granular feel, and it is difficult to form a coating with uniformly distributed PVDF particles.
Disclosure of Invention
Aiming at the technical problems in the related art, the invention provides the water-based PVDF coating diaphragm and the preparation method and the application thereof, which obviously improve the dispersibility and the stability of PVDF particles in an aqueous solution, and further obviously improve the comprehensive performance of the lithium ion battery diaphragm.
In order to achieve the technical purpose, the technical scheme of the invention is realized as follows:
in one aspect, the invention provides a preparation method of modified aqueous PVDF powder, which comprises the following steps:
1) preparing emulsion A: mixing PVDF powder, a first fluoride ion surfactant, perfluoroalkyl acrylate, methyl methacrylate, long-carbon-chain benzene alkene and first deionized water to obtain PVDF mixed emulsion, and grinding the PVDF mixed emulsion to obtain emulsion A;
2) preparing a solution B: under the nitrogen atmosphere, mixing an initiator, a second fluoride ion surfactant and second deionized water, heating and stirring to prepare a solution B;
3) preparation of modified aqueous PVDF powder: and slowly adding the emulsion A into the solution B under the nitrogen atmosphere, heating and stirring, carrying out suction filtration, washing and drying to obtain the modified water-based PVDF powder.
Further, the PVDF powder, the first fluoride ion surfactant, the perfluoroalkyl acrylate, the methyl methacrylate, the long-carbon-chain benzene alkene and the first deionized water are in a mass part ratio of 8-20: 0.11-0.75: 0.1-0.5: 0.3-0.9: 1-2: 70-90.
Further, the grinding is carried out in a grinding machine for 0.5-3 h.
Further, the initiator, the second fluorine ion surfactant and the second deionized water are in a ratio of 0.1-1: 0.1-0.5: 80-100 in parts by mass.
Further, in the step 2), the heating and stirring are performed for 0.5-8 hours at 50-80 ℃.
Further, in the step 3), the ratio of the emulsion A to the solution B is 20-50: 50-80 in parts by weight.
Further, in the step 3), the heating and stirring are performed for 0.5-8 hours at 50-80 ℃.
In one aspect, the invention provides a preparation method of a water-based PVDF coating membrane, which comprises the following steps:
mixing and stirring the modified aqueous PVDF powder prepared by the invention, an adhesive, a thickening agent, a wetting agent and deionized water to obtain aqueous PVDF coating slurry;
and (3) coating the obtained aqueous PVDF coating slurry on a polyolefin diaphragm, and drying to obtain the aqueous PVDF coating diaphragm.
Further, the modified water-based PVDF powder, the adhesive, the thickening agent, the wetting agent and the deionized water are in a ratio of 10-20: 0.05-0.7: 0.01-0.6: 0.01-0.7: 78-89.93 in parts by weight.
Further, the stirring time is 2-8 h.
Further, the drying temperature is 40-70 ℃.
The fluoride ion surfactant comprises one or more of ammonium perfluorooctanoate, perfluoroheptanoic acid and sodium perfluorododecyl sulfonate.
The perfluoroalkyl acrylate comprises one or more of perfluoroalkyl ethyl acrylate, perfluorooctanol acrylate, 2- (perfluorohexyl) ethyl methacrylate and tridecyl octyl acrylate.
The long-carbon alkaphene comprises one or more of 4-phenyl-1-butene, 1-phenyl pentene and phenyl propene.
The grinding machine grinds the zirconium oxide micro-beads with the particle size of 0.1-0.5mm, the mass ratio of the zirconium oxide micro-beads to the PVDF mixed emulsion is 1: 3-5 during grinding, and the rotating speed of the grinding machine is 10-50 revolutions per minute.
The initiator comprises: azobisisobutyronitrile, ammonium persulfate or di-tert-amyl peroxide.
The binder comprises one or more of styrene-butadiene latex, styrene-acrylic latex, polyvinyl alcohol, ethylene-vinyl acetate copolymer and polyurethane;
the thickening agent comprises one or more of hydroxyethyl cellulose, methyl hydroxyethyl cellulose, sodium carboxymethyl cellulose, polyacrylamide and sodium alginate;
the wetting agent comprises one or more of fluoroalkyl methoxy ether alcohol, fluoroalkyl ethoxy ether alcohol, alkylphenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether and fatty acid polyoxyethylene ether.
In another aspect, the present invention provides a water-based PVDF-coated separator prepared by the method of the invention.
In another aspect, the present invention provides a lithium ion battery comprising a positive electrode material and a negative electrode material, with the above aqueous PVDF-coated separator therebetween.
According to the invention, the amphipathy of the fluorine ion surfactant is utilized, and PVDF particles can be completely coated by the modified monomer, so that PVDF can be effectively and uniformly dispersed in water, and the adhesion of modified PVDF powder is improved.
According to the invention, the long carbon chain benzene alkene is added, and the characteristic that the glass transition temperature of the material can be improved by utilizing the benzene ring chain segment is utilized, so that the thermal stability of the material is improved.
According to the invention, the cross-linking effect of the perfluoroalkyl acrylate, the methyl methacrylate and the long-carbon-chain benzene alkene is utilized, the crystallinity of the PVDF is improved, the storage stability and the dilution stability of the PVDF coating slurry prepared by the modified PVDF powder are realized, the subsequent film forming is facilitated, and the application performance of the modified PVDF powder, especially the PVDF coating slurry, is improved.
The invention has the beneficial effects that:
the invention provides a water-based PVDF (polyvinylidene fluoride) coated diaphragm as well as a preparation method and application thereof, and the water-based PVDF coated diaphragm has the following advantages:
1) firstly, water is used as a PVDF modified solvent to obtain modified PVDF powder; in the modification process, the adopted fluorine-containing monomer has better affinity to the PVDF surface, so that PVDF particles can be completely coated by the modified monomer, the dispersibility of the modified PVDF particles in water is improved, and the prepared modified PVDF powder is more uniform and better in stability and distribution; and modifying the PVDF by using a monomer with ultralow concentration, so that the PVDF has a stable structure before and after modification.
2) The PVDF coating slurry is further prepared in water, and the modified PVDF powder is adopted, so that the prepared coating slurry is stable in storage, and the situation that PVDF particles block holes during subsequent coating of a diaphragm is avoided; the prepared coating membrane has the advantages of regular and compact particle arrangement, good air permeability, high liquid absorption rate and ionic conductivity and high coating peeling strength.
3) After the coating slurry prepared by the invention is coated on the diaphragm, particles in the modified PVDF coating can be mutually bonded, so that the use amount of the bonding agent is greatly reduced; the prepared coating slurry has good stability.
4) The preparation method has simple process, little environmental pollution and strong adaptability to the existing equipment, and is suitable for industrial production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
Fig. 1 is an SEM image of a waterborne PVDF-coated separator prepared in a preferred embodiment of the invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the embodiments given herein are intended to be within the scope of the present invention.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specified, the reagents and materials used in the present invention are commercially available products or products obtained by a known method.
Example 1
8g of PVDF powder, 0.5g of perfluoroheptanoic acid, 0.1g of perfluoroalkylethyl acrylate, 0.4g of tridecyl octyl acrylate, 0.3g of methyl methacrylate, 1g of 4-phenyl-1-butene and 85.3g of deionized water were mixed to obtain a PVDF mixed emulsion.
The grinding machine uses zirconia micro-beads with the particle size of 0.1mm, the mass ratio of the zirconia micro-beads to the PVDF mixed emulsion is 1: 3, the rotating speed of the grinding machine is 50 r/min, and the PVDF mixed emulsion is ground in the grinding machine for 3h to obtain emulsion A.
In N20.6g of azobisisobutyronitrile, 0.1g of perfluoroheptanoic acid and 99.3g of deionized water were mixed under a gas blanketThen, the mixture was stirred at 50 ℃ for 8 hours to prepare a solution B.
In N250g of emulsion A were slowly added to 80g of solution B under a gas blanket and stirred at 50 ℃ for 6 h. And obtaining modified PVDF mixed solution after the reaction is finished. And (3) carrying out suction filtration on the modified PVDF mixed solution by using a vacuum suction filter, washing the mixed solution for 5 times by using deionized water, and drying the mixed solution to obtain modified PVDF powder.
12g of modified PVDF particles, 0.3g of styrene-butadiene latex, 0.4g of ethylene-vinyl acetate copolymer, 0.01g of hydroxyethyl cellulose and 0.7g of fatty alcohol-polyoxyethylene ether are mixed and stirred for 8 hours to obtain modified PVDF coating slurry.
And coating the modified PVDF coating slurry on a polyolefin diaphragm, and drying at 70 ℃ to obtain the water-based PVDF coating diaphragm.
The aqueous PVDF coating slurry prepared in this example did not settle after standing at room temperature for 7 days.
The coating thickness of the coated separator prepared in this example was 2 μm, and the air permeability increased by 10s (100 cc/in) after coating2) The decomposition voltage was 4.9V, the thermal shrinkage after baking at 105 ℃ for 2 hours was 0.43% (MD direction) and 0.12% (TD direction), the liquid absorption was 263.7%, the film rupture temperature was 159 ℃, and the lithium ion conductivity was 1.26X 10-3S/cm, the transference number of lithium ions is 0.61, and the peel strength of the coating is 305N/m.
And (3) assembling the lithium cobaltate, the lithium sheet, the electrolyte and the water-based PVDF coating diaphragm into a button cell, testing the performance of the button cell, and keeping the capacity retention rate of 86.9% after 500 cycles under the charge-discharge rate of 3C.
Example 2
20g of PVDF powder, 0.45g of ammonium perfluorooctanoate, 0.3g of sodium perfluorododecylsulfate, 0.1g of perfluorooctanol acrylate, 0.61g of methyl methacrylate, 0.9g of 1-phenylpentene, 0.8 g of phenylpropylene and 70g of deionized water were mixed to obtain a PVDF mixed emulsion.
The grinding machine uses zirconia micro-beads with the particle size of 0.5mm, the mass ratio of the zirconia micro-beads to the PVDF mixed emulsion is 1: 4, the rotating speed of the grinding machine is 30 r/min, and the PVDF mixed emulsion is ground in the grinding machine for 0.5h to obtain emulsion A.
In N2Gas shieldNext, 0.6g of di-t-amyl peroxide, 0.1g of ammonium perfluorooctanoate and 99.3g of deionized water were mixed and stirred at 80 ℃ for 0.5 hour to prepare a solution B.
In N220g of emulsion A were slowly added to 65g of solution B under a gas blanket and stirred at 80 ℃ for 0.5 h. And obtaining modified PVDF mixed solution after the reaction is finished. And (3) carrying out suction filtration on the modified PVDF mixed solution by using a vacuum suction filter, washing for 3 times by using deionized water, and drying to obtain modified PVDF powder.
10g of modified PVDF particles, 0.05g of polyvinyl alcohol, 0.6g of methylhydroxyethyl cellulose, 0.38g of fluoroalkyl methoxy ether alcohol and 88.97g of deionized water were mixed and stirred for 3 hours to obtain a modified PVDF coating slurry. And coating the modified PVDF coating slurry on a polyolefin diaphragm, and drying at 40 ℃ to obtain the water-based PVDF coating diaphragm.
The aqueous PVDF coating slurry prepared in this example did not settle after standing at room temperature for 7 days.
The coating thickness of the waterborne PVDF coated membrane prepared in this example was 2 μm, and the air permeability increased by 8s (100 cc/in) after coating2) The decomposition voltage was 4.7V, the thermal shrinkage after baking at 105 ℃ for 2 hours was 0.58% (MD direction) and 0.21% (TD direction), the liquid absorption was 257.9%, the film rupture temperature was 167 ℃, and the lithium ion conductivity was 1.31X 10-3S/cm, the transference number of lithium ions is 0.69, and the peel strength of the coating is 327N/m.
And (3) assembling the lithium cobaltate, the lithium sheet, the electrolyte and the water-based PVDF coating diaphragm into a button cell, testing the performance of the button cell, and keeping the capacity retention rate of 88.4% after 500 cycles under the charge-discharge rate of 3C.
Example 3
15g of PVDF powder, 0.11g of sodium perfluorododecyl sulfate, 0.3g of 2- (perfluorohexyl) ethyl methacrylate, 0.9g of methyl methacrylate, 2g of 1-phenylpentene and 90g of deionized water were mixed to obtain a PVDF mixed emulsion.
The grinding machine uses zirconia micro-beads with the particle size of 0.3mm, the mass ratio of the zirconia micro-beads to the PVDF mixed emulsion is 1: 5, the rotating speed of the grinding machine is 10 r/min, and the PVDF mixed emulsion is ground in the grinding machine for 1.5h to obtain emulsion A.
In N20.6g of ammonium persulfate, 0.1g of perfluorododecyl sodium sulfate and 99.3g of deionized water are mixed under the protection of gas, and stirred for 5 hours at the temperature of 75 ℃ to prepare a solution B.
In N2Under a gas blanket, 30g of emulsion A were slowly added to 50g of solution B and stirred at 60 ℃ for 8 h. And obtaining modified PVDF mixed solution after the reaction is finished. And (3) carrying out suction filtration on the modified PVDF mixed solution by using a vacuum suction filter, washing the modified PVDF mixed solution for 4 times by using deionized water, and drying the washed modified PVDF mixed solution to obtain modified PVDF powder.
20g of modified PVDF particles, 0.3g of polyurethane, 0.37g of sodium carboxymethylcellulose, 0.2g of sodium alginate, 0.01g of fatty acid polyoxyethylene ether and 79.12g of deionized water are mixed and stirred for 2 hours to obtain modified PVDF coating slurry. And coating the modified PVDF coating slurry on a polyolefin diaphragm, and drying at 55 ℃ to obtain the water-based PVDF coating diaphragm.
The aqueous PVDF coating slurry prepared in this example did not settle after standing at room temperature for 7 days.
The coating thickness of the waterborne PVDF coated separator prepared in this example was 2 μm, and the air permeability increased by 11s (100 cc/in) after coating2) The decomposition voltage was 4.9V, the thermal shrinkage after baking at 105 ℃ for 2 hours was 0.57% (MD direction) and 0.18% (TD direction), the liquid absorption was 235.7%, the film breaking temperature was 173 ℃, and the lithium ion conductivity was 1.79X 10-3S/cm, the transference number of lithium ions is 0.63, and the peel strength of the coating is 294N/m.
And (3) assembling the lithium cobaltate, the lithium sheet, the electrolyte and the water-based PVDF coating diaphragm into a button cell, testing the performance of the button cell, and keeping the capacity retention rate of 91.3% after 500 cycles under the charge-discharge rate of 3C.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (9)
1. A preparation method of modified water-based PVDF powder is characterized by comprising the following steps:
preparing emulsion A: mixing PVDF powder, a first fluoride ion surfactant, perfluoroalkyl acrylate, methyl methacrylate, long-carbon-chain benzene alkene and first deionized water to obtain PVDF mixed emulsion, and grinding the PVDF mixed emulsion to obtain emulsion A;
preparing a solution B: under the nitrogen atmosphere, mixing an initiator, a second fluoride ion surfactant and second deionized water, heating and stirring to prepare a solution B;
preparation of modified aqueous PVDF powder: slowly adding the emulsion A into the solution B under the nitrogen atmosphere, heating and stirring, carrying out suction filtration, washing and drying to obtain modified water-based PVDF powder;
the first fluoride ion surfactant comprises one or more of ammonium perfluorooctanoate, perfluoroheptanoic acid and sodium perfluorododecyl sulfonate;
the second fluoride ion surfactant comprises one or more of ammonium perfluorooctanoate, perfluoroheptanoic acid and sodium perfluorododecyl sulfonate;
the perfluoroalkyl acrylate comprises one or more of perfluoroalkyl ethyl acrylate, perfluorooctanol acrylate, 2- (perfluorohexyl) ethyl methacrylate and tridecyl octyl acrylate;
the long-carbon alkaphene comprises one or more of 4-phenyl-1-butene, 1-phenyl pentene and phenylpropylene;
the initiator comprises azobisisobutyronitrile, ammonium persulfate or di-tert-amyl peroxide.
2. The preparation method of the modified aqueous PVDF powder as claimed in claim 1, wherein the PVDF powder, the first fluoride ion surfactant, the perfluoroalkyl acrylate, the methyl methacrylate, the long-carbon strebene and the first deionized water are in a ratio of 8-20: 0.11-0.75: 0.1-0.5: 0.3-0.9: 1-2: 70-90 in parts by weight;
and grinding is carried out in a grinding machine for 0.5-3 h.
3. The preparation method of the modified aqueous PVDF powder as claimed in claim 1, wherein the initiator, the second ionic fluoride surfactant and the second deionized water are in a ratio of 0.1-1: 0.1-0.5: 80-100 in parts by mass;
in the step 2), the heating and stirring are performed for 0.5-8 hours at 50-80 ℃.
4. The method for preparing modified aqueous PVDF powder as claimed in claim 1, wherein in step 3), the ratio of emulsion A to solution B is 20-50: 50-80 parts;
the heating and stirring means stirring at 50-80 ℃ for 0.5-8 h.
5. A preparation method of a water-based PVDF coating membrane is characterized by comprising the following steps:
mixing and stirring the modified aqueous PVDF powder prepared according to any one of claims 1 to 4, an adhesive, a thickening agent, a wetting agent and deionized water to obtain aqueous PVDF coating slurry;
and (3) coating the obtained aqueous PVDF coating slurry on a polyolefin diaphragm, and drying to obtain the aqueous PVDF coating diaphragm.
6. The preparation method of the water-based PVDF coating membrane as claimed in claim 5, wherein the modified water-based PVDF powder, the adhesive, the thickener, the wetting agent and the deionized water are in a ratio of 10-20: 0.05-0.7: 0.01-0.6: 0.01-0.7: 78-89.93 in parts by weight;
the stirring time is 2-8 h;
the drying temperature is 40-70 ℃.
7. The method of claim 5, wherein the binder comprises one or more of styrene-butadiene latex, styrene-acrylic latex, polyvinyl alcohol, ethylene-vinyl acetate copolymer, polyurethane;
the thickening agent comprises one or more of hydroxyethyl cellulose, methyl hydroxyethyl cellulose, sodium carboxymethyl cellulose, polyacrylamide and sodium alginate;
the wetting agent comprises one or more of fluoroalkyl methoxy ether alcohol, fluoroalkyl ethoxy ether alcohol, alkylphenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether and fatty acid polyoxyethylene ether.
8. A water-based PVDF-coated separator prepared by the method according to any one of claims 5 to 7.
9. A lithium ion battery comprising a positive electrode material and a negative electrode material with the aqueous PVDF-coated separator according to claim 8 therebetween.
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| CN110112348B (en) * | 2019-03-19 | 2021-09-28 | 上海恩捷新材料科技有限公司 | Battery coating film slurry, battery diaphragm, secondary battery and preparation method thereof |
| CN110707266A (en) * | 2019-09-23 | 2020-01-17 | 河北金力新能源科技股份有限公司 | PVDF (polyvinylidene fluoride) mixed coating slurry, preparation method thereof and diaphragm |
| CN111180638A (en) * | 2020-01-17 | 2020-05-19 | 江苏厚生新能源科技有限公司 | PVDF (polyvinylidene fluoride) modified diaphragm and preparation method thereof |
| CN111341974B (en) * | 2020-03-13 | 2022-03-11 | 江苏厚生新能源科技有限公司 | PVDF (polyvinylidene fluoride) coated diaphragm and preparation method thereof, PVDF coated layer and lithium battery |
| CN111816826B (en) * | 2020-07-24 | 2021-12-14 | 佛山市金辉高科光电材料股份有限公司 | Aqueous polymer functional slurry and preparation method and application thereof |
| CN112795247B (en) * | 2021-01-08 | 2022-05-03 | 厦门大学 | High-viscosity PVDF (polyvinylidene fluoride) coated diaphragm and preparation method thereof |
| CN114292554B (en) * | 2022-01-27 | 2022-07-26 | 上海水立方新材料有限公司 | Modified nano-silica reinforced aqueous PVDF coating and preparation method thereof |
| CN114716775B (en) * | 2022-03-21 | 2023-09-12 | 惠州市豪鹏科技有限公司 | Material for electrolyte separator, preparation method and battery |
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