CN115558344B - PVDF hollow porous nanoparticle coating slurry, preparation method and modified composite membrane thereof - Google Patents
PVDF hollow porous nanoparticle coating slurry, preparation method and modified composite membrane thereof Download PDFInfo
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- 239000002033 PVDF binder Substances 0.000 title claims abstract description 113
- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 113
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 99
- 239000006255 coating slurry Substances 0.000 title claims abstract description 39
- 239000002131 composite material Substances 0.000 title claims description 28
- 239000012528 membrane Substances 0.000 title claims description 21
- 238000002360 preparation method Methods 0.000 title claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 44
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 17
- 239000012498 ultrapure water Substances 0.000 claims abstract description 17
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 13
- 239000002270 dispersing agent Substances 0.000 claims abstract description 13
- 239000002562 thickening agent Substances 0.000 claims abstract description 13
- 239000000080 wetting agent Substances 0.000 claims abstract description 12
- 239000011230 binding agent Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 41
- 239000011247 coating layer Substances 0.000 claims description 22
- 238000000576 coating method Methods 0.000 claims description 18
- 239000011248 coating agent Substances 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 17
- 229920000098 polyolefin Polymers 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 15
- 239000006185 dispersion Substances 0.000 claims description 14
- 235000012239 silicon dioxide Nutrition 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 238000003760 magnetic stirring Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 238000007761 roller coating Methods 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- 150000008431 aliphatic amides Chemical group 0.000 claims description 3
- 150000008051 alkyl sulfates Chemical group 0.000 claims description 3
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims description 3
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 239000013530 defoamer Substances 0.000 claims 2
- 238000005119 centrifugation Methods 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 7
- 239000003792 electrolyte Substances 0.000 abstract description 7
- 229910052744 lithium Inorganic materials 0.000 abstract description 7
- 230000035699 permeability Effects 0.000 abstract description 3
- 239000007888 film coating Substances 0.000 abstract 1
- 238000009501 film coating Methods 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 11
- 238000005096 rolling process Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C09D127/16—Homopolymers or copolymers of vinylidene fluoride
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- 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
- H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
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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
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/491—Porosity
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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
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Abstract
The invention relates to the technical field of lithium battery diaphragms, in particular to PVDF hollow porous nanoparticle coating slurry which is prepared from the following raw materials in percentage by weight: 6 to 20 percent of PVDF hollow porous nano particles, 0.5 to 2 percent of dispersing agent, 5 to 10 percent of thickening agent, 5 to 15 percent of binding agent, 0.1 to 1 percent of wetting agent, 0.1 to 1 percent of defoaming agent and the balance of ultrapure water; the PVDF hollow porous nanoparticle is prepared from the following raw materials in parts by weight: silica nanoparticles 1.226g, ultra pure water 315mL, polyvinylidene fluoride 0.965g, N-dimethylformamide 11.553g, and sodium hydroxide solution of 5.0mol/L in balance. The invention provides a lithium ion battery diaphragm with low cost, high electrolyte wettability and high adhesion, which has excellent pole piece adhesion performance, electrolyte wettability and air permeability, and meanwhile, compared with the traditional PVDF film coating, the cost is greatly reduced.
Description
Technical Field
The invention relates to the technical field of lithium battery diaphragms, in particular to PVDF hollow porous nanoparticle coating slurry, a preparation method and a modified composite diaphragm thereof.
Background
The lithium battery is used as a novel secondary battery, has the advantages of high energy density, long cycle life and the like, is continuously expanded in application range, is widely applied to portable electronic devices, energy storage and power automobiles, and is increasingly applied to the power automobiles along with the rapid development of new energy industries. The diaphragm is used as an important component of the lithium battery, can effectively prevent the contact of the positive electrode and the negative electrode from generating short circuit, has very important influence on the safety of the lithium battery, and therefore, the improvement of the performance of the lithium battery and the safety requirement have higher requirements on the performance of the diaphragm.
Polyolefin separators are the most widely used lithium battery separators at present. However, polyolefin separators in the market have some disadvantages, such as poor adhesion performance to the polar plate and insufficient electrolyte-philic performance, so that a series of problems of poor cycle performance, low thermal stability, unstable interface between the polar plate and the separator, poor hardness of the battery, adverse processing and transportation and the like occur in the battery, the improvement of the energy density of the battery is greatly limited, and the development of high-performance ultrathin batteries is hindered.
Aiming at the problem that the adhesion of the polyolefin diaphragm to the pole piece and the electrolyte wettability are poor, the main solution is to coat a water-based PVDF adhesive layer on one side or two sides of the polyolefin diaphragm at present, and the adhesive coating layer can effectively improve the adhesion of the diaphragm and has good wettability with the electrolyte. However, PVDF in the current market has higher selling price (about 900 yuan/kg), so that the cost of a coating film is greatly increased, and the profit margin of a diaphragm is greatly reduced. And the traditional PVDF particle glue coating layer has poor air permeability, so that the air permeability of the PVDF glue coating film is poor.
Thus, developing a PVDF rubberized separator with high electrolyte wettability, high adhesion, and low cost is a common goal in the industry.
Disclosure of Invention
The invention aims to solve the defects in the prior art, and provides PVDF hollow porous nanoparticle coating slurry, a preparation method and a modified composite membrane thereof.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the PVDF hollow porous nanoparticle coating slurry is prepared from the following raw materials in percentage by weight:
6 to 20 percent of PVDF hollow porous nano particles, 0.5 to 2 percent of dispersing agent, 5 to 10 percent of thickening agent, 5 to 15 percent of binding agent, 0.1 to 1 percent of wetting agent, 0.1 to 1 percent of defoaming agent and the balance of ultrapure water;
the PVDF hollow porous nanoparticle is prepared from the following raw materials in parts by weight:
silica nanoparticles 1.226g, ultra pure water 315mL, polyvinylidene fluoride 0.965g, N-dimethylformamide 11.553g, and sodium hydroxide solution of 5.0mol/L in balance.
Preferably, the dispersing agent is aliphatic amide, the thickening agent is hydroxymethyl cellulose sodium, the binder is polyacrylic acid, the wetting agent is alkyl sulfate, and the defoaming agent is polyether type defoaming agent.
The preparation method of the PVDF hollow porous nanoparticle coating slurry comprises the following steps:
s1, preparing a silicon dioxide nanoparticle dispersion liquid: under the condition of continuous stirring, adding the silicon dioxide nano particles into ultrapure water, continuing magnetic stirring for 90-130 minutes, and then performing ultrasonic dispersion to obtain uniformly dispersed silicon dioxide nano particle dispersion liquid;
s2, slowly adding polyvinylidene fluoride into N, N-dimethylformamide, sealing the mixed solution, then slowly heating the mixed solution in a water bath kettle to 60-80 ℃, and stirring the mixed solution by using a magnetic stirring device for 4-8 hours;
s3, preparing PVDF hollow porous nano particles: dripping PVDF solution into the uniformly dispersed silicon dioxide nano particle dispersion liquid under the condition of continuously stirring at the rotating speed of 300-400 rpm, continuing to magnetically stir for 100-200 minutes at the rotating speed of 400-500 rpm, carrying out ultrasonic treatment, centrifuging, fully washing and vacuum drying precipitate obtained by centrifuging, and coating SiO with porous PVDF 2 A nanoparticle composite;
s4, coating the obtained porous PVDF with SiO 2 Adding the nano particle composite material into 5.0mol/L sodium hydroxide solution, keeping for 10-12 hours, and then filtering, washing and drying to obtain PVDF hollow porous nano particles;
s5, premixing the dispersant and PVDF hollow porous nanoparticle powder in ultrapure water according to the mass ratio for 80-120 min, adding the dispersant and the PVDF hollow porous nanoparticle powder at the rotating speed of 600-800 rpm, continuously stirring the thickener for 50-70 min at the rotating speed of 600-800 rpm, and continuously stirring the thickener for 150-250 min at the rotating speed of 800-1000 rpm; adding a wetting agent and a defoaming agent, stirring for 50-60 min at the rotating speed of 400-500 rpm, and filtering to remove iron to obtain PVDF hollow porous nanoparticle coating slurry.
Preferably, the stirring speed in the step S1 is 600-700 rpm, and the ultrasonic dispersion condition is 33KHZ, 400W and 10-14 hours.
Preferably, the stirring speed in step S2 is 400-500 rpm.
Preferably, in step S3, the PVDF solution is slowly added dropwise to the homogeneously dispersed silica nanoparticle dispersion at a flow rate of 1.15 ml/min.
Preferably, in the step S3, the conditions of ultrasonic treatment are 35KHZ, 340W and 8-12 hours, the conditions of centrifugal treatment are 8000-8400 rpm and 10-30 minutes, and the conditions of vacuum drying are 0.08Mpa, 80 ℃ and 16-20 hours.
Preferably, in the step S4, the drying condition is 60 to 80 ℃ for 16 to 24 hours.
The PVDF hollow porous nanoparticle modified composite membrane comprises a base membrane and a coating layer, wherein the base membrane is a polyolefin membrane; the coating layer is a coating layer of PVDF hollow porous nano particle coating slurry coated on the base film.
Preferably, the coating layer adopts a micro-gravure roll coating process, the coating slurry is uniformly coated on the polyolefin diaphragm by a coating machine, and the polyolefin diaphragm is baked and formed by an oven at 60-80 ℃.
The beneficial effects of the invention are as follows:
1. the PVDF hollow porous nano particles have the specific surface area far larger than that of the traditional PVDF particles and the mass far smaller than that of the traditional PVDF particles, so that the same pole piece bonding effect, electrolyte infiltration effect and the like as those of the traditional PVDF particles can be achieved by only needing fewer PVDF hollow porous nano particles, and the cost can be greatly reduced.
2. The PVDF hollow porous nanoparticle modified composite membrane has the advantages that the hollow porous structure greatly increases the specific surface area of the material, so that the liquid absorption and retention capacity of the membrane and the bonding performance of the pole piece are greatly improved.
3. The composite membrane modified by the PVDF hollow porous nano particles benefits from the hollow structure of the PVDF nano particles and the porous structure of the surface, and compared with the traditional PVDF particle coating layer, the ventilation increment of the PVDF coating layer is greatly reduced, so that the ventilation performance of the PVDF coating film is remarkably improved.
Drawings
Fig. 1 is a schematic diagram of a hollow PVDF particle formation process in a method for preparing a low cost, high electrolyte wettability and high adhesion lithium ion battery separator according to the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments.
Embodiment one:
the preparation method of the PVDF hollow porous nanoparticle coating slurry comprises the following steps:
preparation of PVDF hollow porous nanoparticles:
firstly, adding 1.226g of silicon dioxide nano particles into 315mL of ultrapure water under the condition of continuous stirring (650 rpm), continuing to magnetically stir for 110 minutes (600 rpm), and then performing ultrasonic dispersion for 12 hours (treatment under 33KHZ and 400w ultrasonic power) to obtain a uniformly dispersed silicon dioxide nano particle dispersion liquid;
then, 0.965g of polyvinylidene fluoride (PVDF) is slowly added into 11.553g of N, N-Dimethylformamide (DMF), the mixed solution is subjected to sealing treatment, then the mixed solution is placed into a water bath kettle to be slowly heated to 70 ℃, and then stirred by a magnetic stirring device (the rotating speed of 450 rpm) for 6 hours;
finally, slowly dripping PVDF solution into the uniformly dispersed silica nanoparticle dispersion liquid at a flow rate of 1.15ml/min under the condition of continuous stirring (330 rpm), continuing magnetic stirring for 150 minutes (450 rpm), and then performing ultrasonic treatment (10 hours under ultrasonic power of 35KHZ and 340 w); then the obtained mixed solution is subjected to centrifugal treatment (20 minutes at 8200 rpm), the precipitate obtained by the centrifugal treatment is fully washed and dried in vacuum (0.08 Mpa vacuum degree, 80 ℃ for 18 hours), and the porous PVDF coated SiO is obtained 2 A nanoparticle composite; finally coating the obtained porous PVDF with SiO 2 The nanoparticle composite was added to 5.0mol/L sodium hydroxide solution and maintained for 11 hours, thenFiltering, washing and drying at 70 ℃ for 20 hours, and obtaining the PVDF hollow porous nano particles after drying.
Preparing PVDF hollow porous nanoparticle coating slurry:
premixing 0.95% of dispersing agent and 7.5% of PVDF hollow porous nano particle powder in ultrapure water for 105min according to the mass ratio, wherein the rotating speed is 670rpm; adding 7.3% of thickener, and stirring for 60min at 680rpm; adding 10.5% of binder, and continuously stirring for 200min at 930rpm; adding 0.35% of wetting agent, and 0.3% of defoaming agent, stirring for 55min at the rotating speed of 450rpm; finally, filtering and removing iron to obtain PVDF hollow porous nano particle coating slurry.
The dispersing agent is aliphatic amide, the thickening agent is hydroxymethyl cellulose sodium, the binder is polyacrylic acid, the wetting agent is alkyl sulfate, and the defoaming agent is polyether type defoaming agent.
Preparing a PVDF hollow porous nanoparticle modified composite membrane:
and uniformly rolling the prepared coating slurry on a polyolefin diaphragm by a coating machine by adopting a micro-gravure roller coating process, baking in an oven at 70 ℃ and rolling for standby, thus obtaining the PVDF hollow porous nanoparticle modified composite diaphragm for the lithium ion battery to be prepared.
The lithium ion battery diaphragm comprises a base film and a coating layer, wherein the base film is a polyolefin diaphragm; the coating layer is a coating layer of PVDF hollow porous nano particle coating slurry coated on the base film.
Embodiment two:
the preparation method of the PVDF hollow porous nanoparticle coating slurry comprises the following steps:
preparation of PVDF hollow porous nanoparticles:
firstly, adding 1.226g of silicon dioxide nano particles into 315mL of ultrapure water under the condition of continuous stirring (650 rpm), continuing to magnetically stir for 110 minutes (600 rpm), and then performing ultrasonic dispersion for 12 hours (treatment under 33KHZ and 400w ultrasonic power) to obtain a uniformly dispersed silicon dioxide nano particle dispersion liquid;
secondly, slowly adding 0.965g of polyvinylidene fluoride (PVDF) into 11.553g of N, N-Dimethylformamide (DMF), then sealing the mixed solution, then slowly heating the mixed solution to 70 ℃ in a water bath, and then stirring the mixed solution for 6 hours by using a magnetic stirring device (rotating speed of 450 rpm);
finally, slowly dripping PVDF solution into the uniformly dispersed silica nanoparticle dispersion liquid at a flow rate of 1.15ml/min under the condition of continuous stirring (330 rpm), continuing magnetic stirring for 150 minutes (450 rpm), and then performing ultrasonic treatment (10 hours under ultrasonic power of 35KHZ and 340 w); then the obtained mixed solution is subjected to centrifugal treatment (20 minutes at 8200 rpm), the precipitate obtained by the centrifugal treatment is fully washed and dried in vacuum (0.08 Mpa vacuum degree, 80 ℃ for 18 hours), and the porous PVDF coated SiO is obtained 2 A nanoparticle composite; finally coating the obtained porous PVDF with SiO 2 The nano particle composite material is added into 5.0mol/L sodium hydroxide solution and kept for 11 hours, then filtered, washed and dried for 20 hours at 70 ℃, and the PVDF hollow porous nano particles are obtained after drying.
Preparing PVDF hollow porous nanoparticle coating slurry:
premixing 0.95% of dispersing agent and 13.5% of PVDF hollow porous nano particle powder in ultrapure water for 105min according to the mass ratio, wherein the rotating speed is 670rpm; adding 7.3% of thickener, and stirring for 60min at 680rpm; adding 10.5% of binder, and continuously stirring for 200min at 930rpm; adding 0.35% of wetting agent, and 0.3% of defoaming agent, stirring for 55min at the rotating speed of 450rpm; finally, filtering and removing iron to obtain PVDF hollow porous nano particle coating slurry.
Preparing a PVDF hollow porous nanoparticle modified composite membrane:
and uniformly rolling the prepared coating slurry on a polyolefin diaphragm by a coating machine by adopting a micro-gravure roller coating process, baking in an oven at 70 ℃ and rolling for standby, thus obtaining the PVDF hollow porous nanoparticle modified composite diaphragm for the lithium ion battery to be prepared.
The lithium ion battery diaphragm comprises a base film and a coating layer, wherein the base film is a polyolefin diaphragm; the coating layer is a coating layer of PVDF hollow porous nano particle coating slurry coated on the base film.
Embodiment III:
the preparation method of the PVDF hollow porous nanoparticle coating slurry comprises the following steps:
preparation of PVDF hollow porous nanoparticles:
firstly, adding 1.226g of silicon dioxide nano particles into 315mL of ultrapure water under the condition of continuous stirring (650 rpm), continuing to magnetically stir for 110 minutes (600 rpm), and then performing ultrasonic dispersion for 12 hours (treatment under 33KHZ and 400w ultrasonic power) to obtain a uniformly dispersed silicon dioxide nano particle dispersion liquid;
secondly, slowly adding 0.965g of polyvinylidene fluoride (PVDF) into 11.553g of N, N-Dimethylformamide (DMF), then sealing the mixed solution, then slowly heating the mixed solution to 70 ℃ in a water bath, and then stirring the mixed solution for 6 hours by using a magnetic stirring device (rotating speed of 450 rpm);
finally, slowly dripping PVDF solution into the uniformly dispersed silica nanoparticle dispersion liquid at a flow rate of 1.15ml/min under the condition of continuous stirring (330 rpm), continuing magnetic stirring for 150 minutes (450 rpm), and then performing ultrasonic treatment (10 hours under ultrasonic power of 35KHZ and 340 w); then the obtained mixed solution is subjected to centrifugal treatment (20 minutes at 8200 rpm), the precipitate obtained by the centrifugal treatment is fully washed and dried in vacuum (0.08 Mpa vacuum degree, 80 ℃ for 18 hours), and the porous PVDF coated SiO is obtained 2 A nanoparticle composite; finally coating the obtained porous PVDF with SiO 2 The nano particle composite material is added into 5.0mol/L sodium hydroxide solution and kept for 11 hours, then filtered, washed and dried for 20 hours at 70 ℃, and the PVDF hollow porous nano particles are obtained after drying.
Preparing PVDF hollow porous nanoparticle coating slurry:
premixing 0.95% of dispersing agent and 19.5% of PVDF hollow porous nano particle powder in ultrapure water for 105min at the rotating speed of 670rpm; adding 7.3% of thickener, and stirring for 60min at 680rpm; adding 10.5% of binder, and continuously stirring for 200min at 930rpm; adding 0.35% of wetting agent, and 0.3% of defoaming agent, stirring for 55min at the rotating speed of 450rpm; finally, filtering and removing iron to obtain PVDF hollow porous nano particle coating slurry.
Preparing a PVDF hollow porous nanoparticle modified composite membrane:
and uniformly rolling the prepared coating slurry on a polyolefin diaphragm by a coating machine by adopting a micro-gravure roller coating process, baking in an oven at 70 ℃ and rolling for standby, thus obtaining the PVDF hollow porous nanoparticle modified composite diaphragm for the lithium ion battery to be prepared.
The lithium ion battery diaphragm comprises a base film and a coating layer, wherein the base film is a polyolefin diaphragm; the coating layer is a coating layer of PVDF hollow porous nano particle coating slurry coated on the base film.
Comparative example one:
s1, preparing a traditional PVDF particle coating slurry:
premixing 0.95% of dispersing agent and 7.5% of PVDF particles (model LBG POWDER) in ultrapure water for 105min at 670rpm; adding 7.3% of thickener, and stirring for 60min at 680rpm; adding 10.5% of binder, and continuously stirring for 200min at 930rpm; adding 0.35% of wetting agent, and 0.3% of defoaming agent, stirring for 55min at the rotating speed of 450rpm; and finally, filtering to remove iron to obtain PVDF particle coating slurry.
Preparation of a traditional PVDF particle modified composite membrane:
and uniformly rolling the prepared coating slurry on a polyolefin diaphragm by a coating machine by adopting a micro-gravure roller coating process, baking in an oven at 70 ℃ and rolling for standby, thus obtaining the composite diaphragm of the lithium ion battery modified by the traditional PVDF particles.
Comparative example two:
the same polyolefin separator as in the above examples and comparative examples was not coated with a coating layer.
Experimental results:
the properties of the composite separators prepared in examples 1 to 3 and comparative examples 1 to 2 were compared as follows:
the foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (10)
- The PVDF hollow porous nanoparticle coating slurry is characterized by being prepared from the following raw materials in percentage by weight:6 to 20 percent of PVDF hollow porous nano particles, 0.5 to 2 percent of dispersing agent, 5 to 10 percent of thickening agent, 5 to 15 percent of binding agent, 0.1 to 1 percent of wetting agent, 0.1 to 1 percent of defoaming agent and the balance of ultrapure water;the PVDF hollow porous nanoparticle is prepared from the following raw materials in parts by weight:silica nanoparticles 1.226g, ultra pure water 315mL, polyvinylidene fluoride 0.965g, N-dimethylformamide 11.553g, and sodium hydroxide solution of 5.0mol/L in balance.
- 2. The PVDF hollow porous nanoparticle coating slurry of claim 1, wherein the dispersant is an aliphatic amide, the thickener is sodium hydroxymethyl cellulose, the binder is polyacrylic, the wetting agent is alkyl sulfate, and the defoamer is a polyether defoamer.
- The preparation method of the PVDF hollow porous nanoparticle coating slurry is characterized by comprising the following steps:s1, preparing a silicon dioxide nanoparticle dispersion liquid: under the condition of continuous stirring, adding the silicon dioxide nano particles into ultrapure water, continuing magnetic stirring for 90-130 minutes, and then performing ultrasonic dispersion to obtain uniformly dispersed silicon dioxide nano particle dispersion liquid;s2, slowly adding polyvinylidene fluoride into N, N-dimethylformamide, sealing the mixed solution, then slowly heating the mixed solution in a water bath kettle to 60-80 ℃, and stirring the mixed solution by using a magnetic stirring device for 4-8 hours;s3, preparing PVDF hollow porous nano particles: dripping PVDF solution into the uniformly dispersed silicon dioxide nano particle dispersion liquid under the condition of continuously stirring at the rotating speed of 300-400 rpm, continuing to magnetically stir for 100-200 minutes at the rotating speed of 400-500 rpm, carrying out ultrasonic treatment, centrifuging, fully washing and vacuum drying precipitate obtained by centrifuging, and coating SiO with porous PVDF 2 A nanoparticle composite;s4, coating the obtained porous PVDF with SiO 2 Adding the nano particle composite material into 5.0mol/L sodium hydroxide solution, keeping for 10-12 hours, and then filtering, washing and drying to obtain PVDF hollow porous nano particles;s5, premixing the dispersing agent and PVDF hollow porous nano particle powder in ultrapure water for 80-120 min at 600-800 rpm, adding the thickening agent, continuously stirring for 50-70 min at 600-800 rpm, adding the binding agent, continuously stirring for 150-250 min at 800-1000 rpm; adding a wetting agent and a defoaming agent, stirring for 50-60 min at the rotating speed of 400-500 rpm, and filtering to remove iron to obtain PVDF hollow porous nanoparticle coating slurry.
- 4. The method for preparing a PVDF hollow porous nanoparticle coating slurry according to claim 3, wherein the stirring speed in the step S1 is 600-700 rpm, and the ultrasonic dispersion conditions are 33KHz, 400W, and 10-14 hours.
- 5. The method for preparing a PVDF hollow porous nanoparticle coating slurry according to claim 3, wherein the stirring speed in step S2 is 400 to 500rpm.
- 6. The method for preparing a PVDF hollow porous nanoparticle coating slurry according to claim 3, wherein in step S3, the PVDF solution is slowly dropped into the uniformly dispersed silica nanoparticle dispersion at a flow rate of 1.15 ml/min.
- 7. The method for preparing a PVDF hollow porous nanoparticle coating slurry according to claim 3, wherein in the step S3, the conditions of ultrasonic treatment are 35KHZ, 340W, 8-12 hours, the conditions of centrifugation treatment are 8000-8400 rpm, 10-30 minutes, and the conditions of vacuum drying are 0.08Mpa, 80 ℃ and 16-20 hours.
- 8. The method for preparing a hollow porous nanoparticle coating slurry for PVDF according to claim 3, wherein in the S4 step, the drying condition is 60 to 80 ℃ for 16 to 24 hours.
- The PVDF hollow porous nanoparticle modified composite membrane is characterized by comprising a base membrane and a coating layer, wherein the base membrane is a polyolefin membrane; the coating layer is a coating layer of the PVDF hollow porous nanoparticle coating slurry of one of claims 1-2 coated on a base film.
- 10. The PVDF hollow porous nanoparticle modified composite membrane according to claim 9, wherein the coating layer is prepared by uniformly coating the coating slurry on the polyolefin membrane by a coating machine through a micro gravure roller coating process, and baking and forming the membrane by a baking oven at 60-80 ℃.
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