CN109054068B - Method for modifying polymer coating film by using polymethyl methacrylate as modifier - Google Patents

Method for modifying polymer coating film by using polymethyl methacrylate as modifier Download PDF

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CN109054068B
CN109054068B CN201810753413.5A CN201810753413A CN109054068B CN 109054068 B CN109054068 B CN 109054068B CN 201810753413 A CN201810753413 A CN 201810753413A CN 109054068 B CN109054068 B CN 109054068B
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polymethyl methacrylate
film
mixed solution
coating film
accounting
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CN109054068A (en
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童庆松
马莎莎
余欣瑞
胡志刚
廖洁
李颖
席强
祖国晶
童君开
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Fujian Normal University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • 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
    • C09D133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/10—Homopolymers or copolymers of methacrylic acid esters
    • C09D133/12—Homopolymers or copolymers of methyl methacrylate
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2427/00—Characterised by the use of 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; Derivatives of such polymers
    • C08J2427/02—Characterised by the use of 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; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2427/12—Characterised by the use of 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; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2427/16—Homopolymers or copolymers of vinylidene fluoride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2433/10—Homopolymers or copolymers of methacrylic acid esters
    • C08J2433/12—Homopolymers or copolymers of methyl methacrylate
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/327—Aluminium phosphate
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/328—Phosphates of heavy metals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to a method for modifying a polymer film by polymethyl methacrylate, which comprises the following preparation steps: according to the volume ratio of 0.05-12: mixing acetone and dimethylformamide according to a proportion of 1 to prepare a mixed solution, adding a coating agent accounting for 1 to 5 weight percent of the mixed solution, carrying out ultrasonic oscillation, and then adding polyvinylidene fluoride-hexafluoropropylene accounting for 1 to 5 weight percent and polymethyl methacrylate accounting for 0.5 to 2.5 weight percent to obtain viscous liquid. Coating the viscous liquid on the surface of a base film, and drying in vacuum or by blowing to obtain the polymer coating film taking polymethyl methacrylate as a modifier. The invention has low cost, simple process and less time consumption, and the prepared coating film applied to a battery system can obviously reduce the internal resistance of the battery, obviously improve the matching property with materials such as a positive electrode, a negative electrode, electrolyte and the like, improve the discharge capacity and the cycle performance of the battery and lay a good foundation for industrialization.

Description

Method for modifying polymer coating film by using polymethyl methacrylate as modifier
Technical Field
The invention relates to a method for modifying a polymer coating film by taking polymethyl methacrylate as a modifier, in particular to a method for preparing a coating film which can be used for lithium batteries, lithium ion batteries, polymer batteries and super capacitors. Belonging to the technical field of battery diaphragm preparation.
Technical Field
The lithium ion battery has the advantages of high voltage, large capacity, no memory effect, long service life and the like, and is widely applied to digital products such as mobile phones, digital cameras, notebook computers and the like and power tools such as electric vehicles, hybrid electric vehicles and the like. In the battery system, the separator functions to prevent electron communication between the positive electrode and the negative electrode and to conduct ions. The separator plays an important role in battery performance and safe use. Battery separators can be classified into dry-process membranes, wet-process membranes, and composite membranes, depending on the production process.
Under abuse conditions, the lithium ion battery may be in a high temperature range of 100-300 ℃, and the lithium ion battery using the polyolefin film has potential safety hazards due to the fact that Polyethylene (PE), polypropylene (PP) and polyolefin composite films (such as PP/PE/PP and PE/PP) can shrink and deform at high temperature. Therefore, the polyolefin film is coated with alumina and other nanometer materials at home and abroad to prepare the coating film. The organic material in the coating film enables the diaphragm to have flexibility and meet the requirements of battery assembly. At high temperature, organic components in the coating film can be melted to block the holes of the diaphragm, so that the reaction of the battery is slowed or prevented, and the safety of the battery is guaranteed. In the coating film, the inorganic material is distributed on the outer layer of the diaphragm, and plays the role of a rigid framework, thereby ensuring the safety of the lithium ion battery. The coating film generally comprises a base film, a binder and an inorganic nano material.
From the binder point of view, current coating films generally use PVDF resins [ Hennige v., et al, US 7790321, 2010.7.9.]And polymethyl methacrylate (PMMA) [ zhao jin bao et al, chinese patent invention, CN 103035866 a, 2013.4.10.]Styrene Butadiene Rubber (SBR) [ Park J.H., et al. J. Power Sources, 2010, 195(24): 8306-.]Silica sol [ Lee j.r., et al. j. Power Sources, 2012, 216: 42-47.]And polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) [ Jeong H.S., et al. electrochim. Acta, 2012, 86: 317-.]And (3) a binder. Sohn et al (R) methyl Polymethacrylate (PM)MA), polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) and nano Al2O3As coating agent [ Sohn J. Y., et al., J. Solid State electrochem., 2012, 16, 551-Asn 556 ].]And preparing a coating layer on the PE film. Researches prove that the PVDF has larger structural regularity, closely arranged polymer chains, stronger hydrogen bonds of fluorine atoms and hydrogen atoms in the molecular chains, and larger tensile strength, compressive strength and impact toughness.
The coating film is easy to have powder falling phenomenon in the long-term charge-discharge cycle process. To ameliorate this phenomenon, Chen et al [ Chen H., et al2 on polypropylene membranes for improved performances of lithium-ion batteries， J. Membr. Sci.， 2014， 458， 217-224.]Firstly, the surface of the PP film is treated by the plasma technology, and then TiO is coated2And obtaining the coating film. Research shows that the plasma treatment can generate polar groups on the surface of the PP film, which is beneficial to TiO2Dispersion over the surface of the membrane. The prepared diaphragm has higher liquid absorption rate, higher ionic conductivity and lower thermal shrinkage. The lithium ion battery assembled by the diaphragm has higher discharge capacity and better rate discharge performance.
Through the modification research, the coating film prepared at present still has problems in a battery system. For example, the coating film increases the internal resistance of the battery, making it difficult to develop the discharge capacity of the battery. The dusting may affect the safety performance of the battery. The matching of the coating with the positive electrode, the negative electrode and the electrolyte has a problem.
In order to solve the problems in the application of the coating film, the compound containing the P-O bond is added into the coating layer, and the compound containing the P-O bond reacts with the polyolefin base film to form the coating layer connected with the base film through the valuable bond, so that the bonding force between the coating layer and the base film in the coating film can be obviously improved, the internal resistance of the battery is reduced, and the discharge capacity of the battery is fully exerted. In addition, the compound having a P — O bond has high wettability and high affinity for an electrolyte. The compatibility with the anode, the cathode and the electrolyte is good, and the performance of the coating film is obviously improved.
Disclosure of Invention
The technical scheme adopted by the invention comprises the following steps:
in a reaction kettle, according to the volume ratio (0.05-12): 1 ratio acetone and dimethylformamide were mixed to prepare a mixed solution. Adding a coating agent accounting for 1-5% of the weight of the mixed solution, and carrying out ultrasonic oscillation for 5-30 min to obtain a uniformly mixed suspension. And adding polyvinylidene fluoride-hexafluoropropylene accounting for 1-5 wt% of the mixed solution into the suspension, and then adding polymethyl methacrylate accounting for 0.5-2.5 wt% of the mixed solution. And (4) carrying out ultrasonic oscillation for 10-50 min. Stirring for 8-12 h at 60-95 ℃ to convert the solution in the reaction kettle into viscous liquid. Spreading a base film on an aluminum plate, coating the viscous liquid on the surface of the base film, and performing vacuum drying or forced air drying at any temperature in a temperature range of 70-120 ℃ to obtain the polymer coating film taking polymethyl methacrylate as a modifier.
The coating agent is zinc aluminum phosphate with the particle size ranging from 1nm to 5 mu m, zinc phosphate tetrahydrate or zinc phosphate containing zinc in the range of 50.5 to 52wt percent.
The polyvinylidene fluoride-hexafluoropropylene is polyvinylidene fluoride-hexafluoropropylene with the average molecular weight of 100-300 ten thousand.
The polymethyl methacrylate is polymethyl methacrylate with the average molecular weight of 60-160 ten thousand.
The base film is a single-layer film or a multi-layer film containing a polypropylene or polyethylene layer.
The multilayer film is a diaphragm composed of single-layer films with the number of layers within the range of 2-10.
The raw material cost of the invention is lower, the preparation process is simple, the operation is simple and convenient, the time consumption is less, the prepared coating film is applied to a battery system, the internal resistance of the battery can be obviously reduced, the matching performance with materials such as a positive electrode, a negative electrode, electrolyte and the like is obviously improved, the exertion of the discharge capacity of the battery is increased, the cycle performance of the battery is improved, and a good foundation is laid for industrialization.
Drawings
FIG. 1 is an infrared image of the interface of the base film and the coating layer of the coating film of example 1 of the present invention.
Fig. 2 is an impedance plot of an acyclic sample and a sample charged and discharged through 40 cycles of a button cell prepared in example 1 of the invention.
Detailed Description
The present invention will be further described with reference to the following examples. The examples are merely further additions and illustrations of the present invention, and are not intended to limit the invention.
Example 1
In a reaction kettle, according to a volume ratio of 4: 1 mixing acetone and dimethylformamide to obtain a mixed solution. Adding zinc aluminum phosphate with the weight of 1.25% of the weight of the mixed solution and the particle size of 5 mu m, and performing ultrasonic oscillation for 20min to obtain a uniformly mixed suspension. Polyvinylidene fluoride-hexafluoropropylene having a weight of 2% by weight and an average molecular weight of 150 ten thousand based on the weight of the mixed solution was added to the suspension, and polymethyl methacrylate having a weight of 1% by weight and an average molecular weight of 80 ten thousand based on the weight of the mixed solution was added thereto, and the mixture was ultrasonically oscillated for 25 min. The reaction kettle was stirred at 80 ℃ for 9 h to convert the solution to a viscous liquid. After a polypropylene single-layer film (with the thickness of 10 mu m) is tiled, single-side coating is carried out on the viscous liquid on the surface of the polypropylene single-layer film, the coating thickness is 5 mu m, and vacuum drying is carried out at 80 ℃ to obtain the polymer coating film taking polymethyl methacrylate as a modifier.
Will form Li1.05Ni0.5Co0.2Mn0.3O2The type ternary positive electrode material, the acetylene black and the PVDF binder are weighed according to the weight ratio of 85:10:5, N-methyl pyrrolidone is used as a grinding aid, and ball milling and mixing are carried out for 3 hours to prepare uniform slurry. And coating the uniform slurry on an aluminum foil current collector, and drying to obtain the positive plate. And placing the metal lithium, the prepared coating film, the positive plate, the battery shell and the electrolyte into a glove box filled with argon atmosphere to assemble the CR2025 button battery. And (3) carrying out charge-discharge and cycle performance test on the prepared button cell on a new Will cell test system. The test temperature was normal temperature (25. + -. 1 ℃). The charging and discharging interval is 2.5-4.3V. The charge-discharge cycle experiment was performed at a current of 1C rate. The charge and discharge experiments show that the discharge capacity of the prepared sample at the 1 st cycle is 165 mAh/g.
Example 2
In a reaction kettle, according to the volume ratio of 0.05: 1 mixing acetone and dimethylformamide to obtain a mixed solution. Adding 1 wt% of the mixed solution and 1nm zinc aluminum phosphate, and ultrasonically oscillating for 5min to obtain uniformly mixed suspension. Polyvinylidene fluoride-hexafluoropropylene having an average molecular weight of 100 ten thousand in an amount of 1% by weight based on the weight of the mixed solution was added to the suspension. Then, polymethyl methacrylate with an average molecular weight of 60 ten thousand and a weight of 0.5% of the weight of the mixed solution was added thereto, and the mixture was ultrasonically vibrated for 10 min. The reaction kettle was stirred at 60 ℃ for 8h to convert the solution to a viscous liquid. After the polyethylene single-layer film is laid flatly, viscous liquid is coated on the outer surface of the polyethylene single-layer film, and vacuum drying is carried out at 70 ℃ to obtain the polymer coating film taking polymethyl methacrylate as a modifier.
Example 3
In a reaction kettle, according to the volume ratio of 12: 1 mixing acetone and dimethylformamide to prepare a mixed solution. Zinc phosphate tetrahydrate with the particle size of 1 mu m and the weight accounting for 5 percent of the weight of the mixed solution is added, and the mixture is ultrasonically oscillated for 30min to prepare a uniformly mixed suspension. Polyvinylidene fluoride-hexafluoropropylene having a weight of 5% by weight and an average molecular weight of 300 ten thousand based on the weight of the mixed solution was added to the suspension, and polymethyl methacrylate having a weight of 2.5% by weight and an average molecular weight of 160 ten thousand based on the weight of the mixed solution was added thereto, and the mixture was ultrasonically oscillated for 50 min. The reaction kettle was stirred at 95 ℃ for 12 h to convert the solution to a viscous liquid. And after the PP/PE/PP multilayer film is laid flatly, coating viscous liquid on two surfaces of the multilayer film, and drying in vacuum at 120 ℃ to obtain the polymer coating film taking polymethyl methacrylate as a modifier.
Example 4
In a reaction kettle, mixing the raw materials in a volume ratio of 1: 1 mixing acetone and dimethylformamide to obtain a mixed solution. Adding 0.83 wt% of the mixed solution and zinc phosphate tetrahydrate with particle size of 10nm, and ultrasonically oscillating for 5min to obtain uniformly mixed suspension. Polyvinylidene fluoride-hexafluoropropylene having an average molecular weight of 200 ten thousand in an amount of 1% by weight of the mixed solution was added to the suspension, and polymethyl methacrylate having an average molecular weight of 80 ten thousand in an amount of 1% by weight of the mixed solution was added thereto, followed by ultrasonic oscillation for 20 min. The reaction kettle was stirred at 60 ℃ for 10 h to convert the solution to a viscous liquid. And after the PP/PE multilayer film is laid flatly, coating the viscous liquid on the PP surface of the multilayer film, and drying by blowing at 90 ℃ to obtain the polymer coating film taking polymethyl methacrylate as a modifier.
Example 5
In a reaction kettle, according to the volume ratio of 0.1: 1 mixing acetone and dimethylformamide to obtain a mixed solution. Adding zinc phosphate containing zinc 50.5wt% with particle size of 10nm and 2wt% of the mixed solution, and ultrasonically oscillating for 15min to obtain uniformly mixed suspension. Polyvinylidene fluoride-hexafluoropropylene having an average molecular weight of 300 ten thousand in an amount of 5% by weight of the mixed solution was added to the suspension, and polymethyl methacrylate having an average molecular weight of 100 ten thousand in an amount of 1.4% by weight of the mixed solution was added thereto, followed by ultrasonic oscillation for 15 min. The reaction kettle was stirred at 95 ℃ for 9 h to convert the solution to a viscous liquid. And after the PP/PP multilayer film is laid flatly, coating viscous liquid on two surfaces of the multilayer film, and drying by blowing at 60 ℃ to obtain the polymer coating film taking polymethyl methacrylate as a modifier.
Example 6
In a reaction kettle, according to the volume ratio of 12: 1 mixing acetone and dimethylformamide to obtain a mixed solution. Adding 2wt% of the mixed solution and zinc phosphate tetrahydrate with particle size of 50nm, and ultrasonically oscillating for 5min to obtain uniformly mixed suspension. Polyvinylidene fluoride-hexafluoropropylene having an average molecular weight of 100 ten thousand in an amount of 2.5% by weight based on the weight of the mixed solution was added to the suspension, and polymethyl methacrylate having an average molecular weight of 60 ten thousand in an amount of 2.5% by weight based on the weight of the mixed solution was added thereto, followed by ultrasonic oscillation for 50 min. The reaction kettle was stirred at 80 ℃ for 8h to convert the solution to a viscous liquid. After the single-layer film of the polypropylene film is laid flatly, viscous liquid is coated on two surfaces of the single-layer film, and vacuum drying is carried out at 120 ℃ to prepare the polymer coating film taking polymethyl methacrylate as a modifier.
Example 7
In a reaction kettle, according to a volume ratio of 5:1 mixing acetone and dimethylformamide to obtain a mixed solution. Adding zinc phosphate containing 52wt% of zinc and with the weight of 1.25% of the weight of the mixed solution and the particle size of 3 mu nm, and carrying out ultrasonic oscillation for 30min to obtain a uniformly mixed suspension. Polyvinylidene fluoride-hexafluoropropylene having an average molecular weight of 280 ten thousand in an amount of 1% by weight of the mixed solution was added to the suspension, and polymethyl methacrylate having an average molecular weight of 160 ten thousand in an amount of 2% by weight of the mixed solution was added thereto, followed by ultrasonic oscillation for 50 min. The reaction kettle was stirred at 80 ℃ for 12 h to convert the solution to a viscous liquid. And after the PP/PE multilayer film is laid flatly, coating the viscous liquid on the PE surface of the multilayer film, and drying by blowing at 100 ℃ to obtain the polymer coating film taking polymethyl methacrylate as a modifier.

Claims (5)

1. A method for modifying a polymer coating film by taking polymethyl methacrylate as a modifier is characterized by comprising the following preparation steps:
in a reaction kettle, according to the volume ratio (0.05-12): 1, mixing acetone and dimethylformamide to prepare a mixed solution; adding a coating agent accounting for 1-5% of the weight of the mixed solution, and carrying out ultrasonic oscillation for 5-30 min to obtain a uniformly mixed suspension; adding polyvinylidene fluoride-hexafluoropropylene accounting for 1-5 wt% of the mixed solution into the suspension; adding polymethyl methacrylate accounting for 0.5-2.5 wt% of the mixed solution; carrying out ultrasonic oscillation for 10-50 min; stirring for 8-12 h at 60-95 ℃ to convert the solution in the reaction kettle into viscous liquid; spreading a base film on an aluminum plate, coating viscous liquid on one surface or two surfaces of the base film, and drying in vacuum or by air blast at any temperature in a temperature range of 70-120 ℃ to prepare a polymer coating film taking polymethyl methacrylate as a modifier; the coating agent is zinc aluminum phosphate with the particle size ranging from 1nm to 5 mu m, zinc phosphate tetrahydrate or zinc phosphate containing zinc in the range of 50.5 to 52wt percent.
2. The method of claim 1, wherein the polyvinylidene fluoride-hexafluoropropylene has an average molecular weight of 100 to 300 ten thousand.
3. The method of claim 1, wherein the polymethyl methacrylate is a polymethyl methacrylate having an average molecular weight of 60 to 160 ten thousand.
4. The method of claim 1, wherein the base film is a monolayer film or a multilayer film comprising a polypropylene or polyethylene layer.
5. The method of claim 1, wherein the multilayer film is a separator comprising a single layer of film having a number of layers within a range of 2 to 10.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104112833A (en) * 2014-06-06 2014-10-22 珠海光宇电池有限公司 Lithium ion battery separating membrane, preparing method thereof and applications of the separating membrane
CN107293753A (en) * 2017-06-01 2017-10-24 桂林理工大学 A kind of preparation and application of new zinc-nickel battery anode material
CN108112275A (en) * 2015-02-25 2018-06-01 赛尔格有限责任公司 For the improved partition plate and correlation technique of high voltage rechargeable lithium battery

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150000118A1 (en) * 2013-06-26 2015-01-01 Xin Zhao Method for manufacturing graphene-incorporated rechargeable li-ion battery
WO2017197406A1 (en) * 2016-05-13 2017-11-16 Quantumscape Corporation Solid electrolyte separator bonding agent

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104112833A (en) * 2014-06-06 2014-10-22 珠海光宇电池有限公司 Lithium ion battery separating membrane, preparing method thereof and applications of the separating membrane
CN108112275A (en) * 2015-02-25 2018-06-01 赛尔格有限责任公司 For the improved partition plate and correlation technique of high voltage rechargeable lithium battery
CN107293753A (en) * 2017-06-01 2017-10-24 桂林理工大学 A kind of preparation and application of new zinc-nickel battery anode material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Poly(vinylidene fluoride-co-hexafluoropropylene)/;Yongguang Zhang;《J Solid State Electrochem》;20140103;1111-1116 *

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