CN114552120A - Low-permeability incremental ceramic coating diaphragm and preparation method thereof - Google Patents

Low-permeability incremental ceramic coating diaphragm and preparation method thereof Download PDF

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Publication number
CN114552120A
CN114552120A CN202210272102.3A CN202210272102A CN114552120A CN 114552120 A CN114552120 A CN 114552120A CN 202210272102 A CN202210272102 A CN 202210272102A CN 114552120 A CN114552120 A CN 114552120A
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binder
ceramic
water
stirring
incremental
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张学虎
张立斌
赵海玉
陈朝晖
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Jiangsu Housheng New Energy Technology Co Ltd
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Jiangsu Housheng New Energy Technology Co Ltd
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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • 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
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • 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
    • C09D7/65—Additives macromolecular
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • 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
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
    • 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
    • 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
    • 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 discloses a low-permeability-increment ceramic coating diaphragm and a preparation method thereof, and the coating diaphragm has the advantages of small permeability increment, high peel strength, high heat-resistant temperature, safety, environmental protection and the like, is beneficial to the transmission of lithium ions, and reduces the internal resistance of the diaphragm. The method uses two different binders, namely a water-resistant binder and a solution binder (hydrolysis type binder), and adds a washing process to wash off the solution binder after coating and drying, so that the hole blockage of the binder is reduced, and the air permeability increment is reduced. The invention discloses a low-air-permeability-increment ceramic coating diaphragm and a preparation method thereof, the process design is reasonable, the operation is simple, the prepared ceramic coating diaphragm not only has excellent air permeability, small air permeability increment, but also has excellent heat resistance, the adhesive force between a ceramic coating and the diaphragm is ensured, and the high practicability is realized.

Description

Low-permeability incremental ceramic coating diaphragm and preparation method thereof
Technical Field
The invention relates to the technical field of diaphragms, in particular to a low-permeability incremental ceramic coating diaphragm and a preparation method thereof.
Background
The diaphragm is used for isolating the positive electrode and the negative electrode in the battery, preventing the internal short circuit caused by the contact of the positive electrode and the negative electrode, and providing a channel for the free shuttle of ions in the battery. The separators commercialized at present are mainly ceramic-coated separators because they have better electrochemical reaction inertness, thermal stability, electrolyte wettability, and mechanical strength. Is beneficial to improving the safety performance of the battery. However, the ceramic coating on the base film increases the air permeability of the ceramic film, so that the internal resistance of the battery is increased, and the cycle performance and the rate performance of the battery are seriously influenced. The demand of the current power market cannot be met. Therefore, the development of ceramic-coated separators having excellent thermal stability, electrolyte wettability, mechanical strength, and low air permeation increment has been urgently required.
Disclosure of Invention
The present invention aims to provide a low gas transmission increment ceramic coating diaphragm and a preparation method thereof, so as to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
a low permeability incremental ceramic coated separator comprising a base film, a ceramic coating applied to both sides of the base film;
the ceramic coating raw materials comprise: 0.6-3% of dispersing agent, 30-45% of ceramic powder, 2.5-6.5% of binder, 0.15-0.55% of wetting agent and the balance of ultrapure water.
According to an optimized scheme, the binder comprises a water-resistant binder and a hydrolysis type binder, wherein the water-resistant binder and the hydrolysis type binder are mixed according to a mass ratio of 1: (0.3-1) compounding.
Preferably, the water-resistant binder is any one or mixture of acrylic resin binder and vinyl acetate polymer latex binder. The hydrolysis type binder is any one or more of polyvinyl alcohol binder, polyethylene oxide binder, polyethylene glycol binder, polyacrylamide binder, polyvinylpyrrolidone binder and polyacrylic acid binder.
According to an optimized scheme, the dispersant is any one or more of a water-based polycarboxylate ammonium salt type dispersant, an acrylate copolymer type dispersant and a triethanolamine type dispersant; the ceramic powder is any one or more of aluminum oxide powder, boehmite powder, silicon dioxide powder and titanium dioxide powder; the wetting agent is any one or a plurality of polyether organic silicon copolymer surfactants and alkyne diol modified nonionic surfactants.
In an optimized scheme, the preparation method of the low-permeability incremental ceramic coating membrane comprises the following steps of:
(1) mixing the water-resistant binder and the hydrolysis type binder, and stirring for 20-30min to obtain the binder; placing a dispersing agent in ultrapure water, stirring for 5-10min, adding ceramic powder, stirring for 20-30min, adding a binder, stirring for 1-1.5h, adding a wetting agent, and stirring again for 20-30min to obtain ceramic slurry;
(2) coating the prepared ceramic slurry on two sides of the base film to form a ceramic coating, drying in an oven, washing with water, drying, rolling and slitting after drying to obtain the ceramic coating diaphragm.
In the optimized scheme, in the step (2), an 8-grade water washing tank is adopted during water washing, and the water washing speed is 60-130 m/min.
In a more optimized scheme, the waterproof binder is any one or mixture of acrylic resin binder and vinyl acetate polymer latex binder; the hydrolysis type binder is any one or more of polyvinyl alcohol binder, polyoxyethylene binder, polyethylene glycol binder, polyacrylamide binder, polyvinylpyrrolidone binder and polyacrylic acid binder.
According to an optimized scheme, the preparation method of the water-resistant binder comprises the following steps:
taking methyl methacrylate, butyl acrylate, methacrylic acid, ammonium persulfate, sodium bicarbonate and deionized water, mixing and stirring uniformly, adding 4,4' -dimercaptodiphenyl sulfide dimethyl methacrylate, and stirring for 20-30min to obtain a monomer solution;
mixing and stirring sodium dodecyl sulfate and deionized water for 20-30min, heating to 70-80 ℃, dropwise adding the monomer solution for 1.5-2h, keeping the temperature for 50-60min after dropwise adding, and cooling to obtain the water-resistant binder.
In an optimized scheme, in a monomer solution, the molar ratio of methyl methacrylate, butyl acrylate, methacrylic acid and 4,4' -dimercaptodiphenyl sulfide dimethyl methacrylate is 8: 20: 1: 3.
compared with the prior art, the invention has the following beneficial effects:
the invention solves the problem of high ventilation increment of the existing coated diaphragm, and provides the low-ventilation-increment coated diaphragm and the preparation method thereof. The method uses two different binders, namely a water-resistant binder and a solution binder (hydrolysis type binder), and adds a washing process to wash off the solution binder after coating and drying, so that the hole blockage of the binder is reduced, and the air permeability increment is reduced.
On the basis of the scheme, because this scheme needs pass through the washing workshop section, for guaranteeing ceramic coating and polyolefin base film's adhesion strength, monomers such as methyl methacrylate, butyl acrylate, methacrylic acid are used as raw materials in this application, the preparation obtains the acrylate adhesive, and introduced 4,4' -dimercapto diphenyl sulfide double methyl methacrylate as comonomer, contain sulfydryl and phenyl in this monomer, the high temperature resistance ability of diaphragm not only can be improved in the introduction of this monomer, and flame retardant property obtains promoting, and simultaneously, sulfydryl group can effectively reduce long chain polysulfide shuttle, therefore the electric stability of the diaphragm of preparation is better, the capacity obtains promoting.
The invention discloses a low-air-permeability-increment ceramic coating diaphragm and a preparation method thereof, the process design is reasonable, the operation is simple, the prepared ceramic coating diaphragm not only has excellent air permeability, small air permeability increment, but also has excellent heat resistance, the adhesive force between a ceramic coating and the diaphragm is ensured, and the high practicability is realized.
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, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
a preparation method of a low-permeability incremental ceramic coating diaphragm is characterized by comprising the following steps: the method comprises the following steps:
(1) mixing the water-resistant binder and the hydrolysis type binder, and stirring for 30min to obtain the binder; the water-resistant binder and the hydrolysis type binder are mixed according to a mass ratio of 1: 0.5 compounding. The waterproof binder is an acrylic resin binder (GR506), and the hydrolysis type binder is a polyvinyl alcohol binder.
Placing a dispersing agent in ultrapure water, stirring for 5min, adding ceramic powder, stirring for 30min, adding a binder, stirring for 1h, adding a wetting agent, and stirring again for 30min to obtain ceramic slurry; the ceramic powder comprises, by mass, 0.9% of a dispersing agent, 40% of ceramic powder, 3.5% of a binder, 0.35% of a wetting agent and the balance ultrapure water.
(2) Coating the prepared ceramic slurry on two sides of the base film to form a ceramic coating, drying in an oven, washing with water at a speed of 130m/min in an 8-level water washing tank. Drying, rolling and slitting to obtain the ceramic coated diaphragm. The base film is a polyethylene film.
The dispersant is triethanolamine; the ceramic powder is prepared from aluminum oxide powder, boehmite powder, silicon dioxide powder and titanium dioxide powder in a mass ratio of 1: 1: 1: 1, compounding; the wetting agent is an alkyne diol modified nonionic surfactant.
Example 2:
a preparation method of a low-permeability incremental ceramic coating diaphragm is characterized by comprising the following steps: the method comprises the following steps:
(1) mixing the water-resistant binder and the hydrolysis type binder, and stirring for 20min to obtain a binder; the water-resistant binder and the hydrolysis type binder are mixed according to a mass ratio of 1: 0.3 compounding. The waterproof binder is an acrylic resin binder (GR506), and the hydrolysis type binder is a polyvinyl alcohol binder.
Placing a dispersing agent in ultrapure water, stirring for 10min, adding ceramic powder, stirring for 25min, adding a binder, stirring for 1.5h, adding a wetting agent, and stirring again for 25min to obtain ceramic slurry; the ceramic powder comprises, by mass, 3% of a dispersing agent, 45% of ceramic powder, 6.5% of a binder, 0.55% of a wetting agent and the balance ultrapure water.
(2) Coating the prepared ceramic slurry on two sides of the base film to form a ceramic coating, drying in an oven, washing with water at a speed of 100m/min in an 8-level water washing tank. Drying, rolling and slitting to obtain the ceramic coated diaphragm. The base film is a polyethylene film.
The dispersant is triethanolamine; the ceramic powder is prepared from aluminum oxide powder, boehmite powder, silicon dioxide powder and titanium dioxide powder in a mass ratio of 1: 1: 1: 1, compounding; the wetting agent is an alkyne diol modified nonionic surfactant.
Example 3:
a preparation method of a low-permeability incremental ceramic coating diaphragm is characterized by comprising the following steps: the method comprises the following steps:
(1) mixing the water-resistant binder and the hydrolysis type binder, and stirring for 30min to obtain the binder; the water-resistant binder and the hydrolysis type binder are mixed according to a mass ratio of 1: 1, compounding. The waterproof binder is an acrylic resin binder (GR506), and the hydrolysis type binder is a polyvinyl alcohol binder.
Placing a dispersing agent in ultrapure water, stirring for 10min, adding ceramic powder, stirring for 30min, adding a binder, stirring for 1.5h, adding a wetting agent, and stirring again for 30min to obtain ceramic slurry; the ceramic powder comprises, by mass, 0.6% of a dispersing agent, 30% of ceramic powder, 2.5% of a binder, 0.15% of a wetting agent and the balance ultrapure water.
(2) Coating the prepared ceramic slurry on two sides of the base film to form a ceramic coating, drying in an oven, washing with water at a speed of 60m/min in an 8-level water washing tank. Drying, rolling and slitting to obtain the ceramic coated diaphragm. The base film is a polyethylene film.
The dispersant is triethanolamine; the ceramic powder is prepared from aluminum oxide powder, boehmite powder, silicon dioxide powder and titanium dioxide powder in a mass ratio of 1: 1: 1: 1, compounding; the wetting agent is an alkyne diol modified nonionic surfactant.
Example 4:
a preparation method of a low-permeability incremental ceramic coating diaphragm is characterized by comprising the following steps: the method comprises the following steps:
(1) mixing the water-resistant binder and the hydrolysis type binder, and stirring for 30min to obtain the binder; the water-resistant binder and the hydrolysis type binder are mixed according to a mass ratio of 1: 0.5 compounding. The waterproof binder is an acrylic resin binder, and the hydrolysis type binder is a polyvinyl alcohol binder.
The preparation method of the acrylic resin binder comprises the following steps: taking methyl methacrylate, butyl acrylate, methacrylic acid, ammonium persulfate, sodium bicarbonate and deionized water, mixing and stirring uniformly, adding 4,4' -dimercaptodiphenyl sulfide dimethyl methacrylate, and stirring for 20min to obtain a monomer solution; in the monomer solution, the molar ratio of the methyl methacrylate, the butyl acrylate, the methacrylic acid and the 4,4' -dimercaptodiphenyl sulfide bis-methyl methacrylate is 8: 20: 1: 3. the molar ratio of the methyl methacrylate to the ammonium persulfate to the sodium bicarbonate to the deionized water is 0.8: 0.01: 0.03: 6.
mixing and stirring sodium dodecyl sulfate and deionized water for 20min, wherein the molar ratio of the sodium dodecyl sulfate to the deionized water is 0.02: 22; the mol ratio of the sodium dodecyl sulfate to the methyl methacrylate is 1: 4; heating to 70 ℃, dropwise adding the monomer solution for 2h, keeping the temperature for 50min after dropwise adding, and cooling to obtain the acrylic resin binder.
Placing a dispersing agent in ultrapure water, stirring for 5min, adding ceramic powder, stirring for 30min, adding a binder, stirring for 1h, adding a wetting agent, and stirring again for 30min to obtain ceramic slurry; the ceramic powder comprises, by mass, 0.9% of a dispersing agent, 40% of ceramic powder, 3.5% of a binder, 0.35% of a wetting agent and the balance ultrapure water.
(2) Coating the prepared ceramic slurry on two sides of the base film to form a ceramic coating, drying in an oven, washing with water at a speed of 130m/min in an 8-level water washing tank. Drying, rolling and slitting to obtain the ceramic coated diaphragm. The base film is a polyethylene film.
The dispersant is triethanolamine; the ceramic powder is prepared from aluminum oxide powder, boehmite powder, silicon dioxide powder and titanium dioxide powder in a mass ratio of 1: 1: 1: 1, compounding; the wetting agent is an alkyne diol modified nonionic surfactant.
Example 5:
a preparation method of a low-permeability incremental ceramic coating diaphragm is characterized by comprising the following steps: the method comprises the following steps:
(1) mixing the water-resistant binder and the hydrolysis type binder, and stirring for 30min to obtain the binder; the water-resistant binder and the hydrolysis type binder are mixed according to a mass ratio of 1: 0.5 compounding. The waterproof binder is an acrylic resin binder, and the hydrolysis type binder is a polyvinyl alcohol binder.
The preparation method of the acrylic resin binder comprises the following steps: taking methyl methacrylate, butyl acrylate, methacrylic acid, ammonium persulfate, sodium bicarbonate and deionized water, mixing and stirring uniformly, adding 4,4' -dimercaptodiphenyl sulfide dimethyl methacrylate, and stirring for 20-30min to obtain a monomer solution; in the monomer solution, the molar ratio of methyl methacrylate, butyl acrylate, methacrylic acid and 4,4' -dimercaptodiphenyl sulfide bis-methyl methacrylate is 8: 20: 1: 3. the molar ratio of the methyl methacrylate to the ammonium persulfate to the sodium bicarbonate to the deionized water is 0.8: 0.01: 0.03: 6.
mixing and stirring sodium dodecyl sulfate and deionized water for 30min, wherein the molar ratio of the sodium dodecyl sulfate to the deionized water is 0.02: 22; the mol ratio of the sodium dodecyl sulfate to the methyl methacrylate is 1: 4; heating to 80 ℃, dropwise adding the monomer solution for 1.5h, keeping the temperature for 60min after dropwise adding, and cooling to obtain the acrylic resin binder.
Placing a dispersing agent in ultrapure water, stirring for 5min, adding ceramic powder, stirring for 30min, adding a binder, stirring for 1h, adding a wetting agent, and stirring again for 30min to obtain ceramic slurry; the ceramic powder comprises, by mass, 0.9% of a dispersing agent, 40% of ceramic powder, 3.5% of a binder, 0.35% of a wetting agent and the balance ultrapure water.
(2) Coating the prepared ceramic slurry on two sides of the base film to form a ceramic coating, drying in an oven, washing with water at a speed of 130m/min in an 8-level water washing tank. Drying, rolling and slitting to obtain the ceramic coated diaphragm. The base film is a polyethylene film.
The dispersant is triethanolamine; the ceramic powder is prepared from aluminum oxide powder, boehmite powder, silicon dioxide powder and titanium dioxide powder in a mass ratio of 1: 1: 1: 1, compounding; the wetting agent is an alkyne diol modified nonionic surfactant.
Comparative example 1: in comparison with example 1, no water washing stage was performed.
A preparation method of a low-permeability incremental ceramic coating diaphragm is characterized by comprising the following steps: the method comprises the following steps:
(1) mixing the water-resistant binder and the hydrolysis type binder, and stirring for 30min to obtain the binder; the water-resistant binder and the hydrolysis type binder are mixed according to a mass ratio of 1: 0.5 compounding. The waterproof binder is an acrylic resin binder (GR506), and the hydrolysis type binder is a polyvinyl alcohol binder.
Placing a dispersing agent in ultrapure water, stirring for 5min, adding ceramic powder, stirring for 30min, adding a binder, stirring for 1h, adding a wetting agent, and stirring again for 30min to obtain ceramic slurry; the ceramic powder comprises, by mass, 0.9% of a dispersing agent, 40% of ceramic powder, 3.5% of a binder, 0.35% of a wetting agent and the balance ultrapure water.
(2) And coating the prepared ceramic slurry on two sides of the base film to form a ceramic coating, drying in an oven, rolling and slitting to obtain the ceramic coated diaphragm. The base film is a polyethylene film.
The dispersant is triethanolamine; the ceramic powder is prepared from aluminum oxide powder, boehmite powder, silicon dioxide powder and titanium dioxide powder in a mass ratio of 1: 1: 1: 1, compounding; the wetting agent is an alkyne diol modified nonionic surfactant.
Comparative example 2: in comparison with example 1, a water-resistant binder was used alone.
A preparation method of a low-permeability incremental ceramic coating diaphragm is characterized by comprising the following steps: the method comprises the following steps:
(1) placing a dispersing agent in ultrapure water, stirring for 5min, adding ceramic powder, stirring for 30min, adding a binder, stirring for 1h, adding a wetting agent, and stirring again for 30min to obtain ceramic slurry; the ceramic powder comprises, by mass, 0.9% of a dispersing agent, 40% of ceramic powder, 3.5% of a binder, 0.35% of a wetting agent and the balance ultrapure water. The waterproof binder is acrylic resin binder (GR 506).
(2) Coating the prepared ceramic slurry on two sides of the base film to form a ceramic coating, drying in an oven, washing with water at a speed of 130m/min in an 8-level water washing tank. Drying, rolling and slitting to obtain the ceramic coated diaphragm. The base film is a polyethylene film.
The dispersant is triethanolamine; the ceramic powder is prepared from aluminum oxide powder, boehmite powder, silicon dioxide powder and titanium dioxide powder in a mass ratio of 1: 1: 1: 1, compounding; the wetting agent is an alkyne diol modified nonionic surfactant.
Comparative example 3: compared with example 1, the hydrolysis type binder was used alone.
A preparation method of a low-permeability incremental ceramic coating diaphragm is characterized by comprising the following steps: the method comprises the following steps:
(1) placing a dispersing agent in ultrapure water, stirring for 5min, adding ceramic powder, stirring for 30min, adding a binder, stirring for 1h, adding a wetting agent, and stirring again for 30min to obtain ceramic slurry; the ceramic powder comprises, by mass, 0.9% of a dispersing agent, 40% of ceramic powder, 3.5% of a binder, 0.35% of a wetting agent, and the balance ultrapure water. The binder is polyvinyl alcohol binder.
(2) Coating the prepared ceramic slurry on two sides of the base film to form a ceramic coating, drying in an oven, washing with water at a speed of 130m/min in an 8-level water washing tank. Drying, rolling and slitting to obtain the ceramic coated diaphragm. The base film is a polyethylene film.
The dispersant is triethanolamine; the ceramic powder is prepared from aluminum oxide powder, boehmite powder, silicon dioxide powder and titanium dioxide powder in a mass ratio of 1: 1: 1: 1, compounding; the wetting agent is an alkyne diol modified nonionic surfactant.
Comparative example 4: compared with example 4, the monomer 4,4' -dimercaptodiphenyl sulfide dimethylmethacrylate was not introduced.
A preparation method of a low-permeability incremental ceramic coating diaphragm is characterized by comprising the following steps: the method comprises the following steps:
(1) mixing the water-resistant binder and the hydrolysis type binder, and stirring for 30min to obtain the binder; the water-resistant binder and the hydrolysis type binder are mixed according to a mass ratio of 1: 0.5 compounding. The waterproof binder is an acrylic resin binder, and the hydrolysis type binder is a polyvinyl alcohol binder.
The preparation method of the acrylic resin binder comprises the following steps: taking methyl methacrylate, butyl acrylate, methacrylic acid, ammonium persulfate, sodium bicarbonate and deionized water, and uniformly mixing and stirring to obtain a monomer solution; in the monomer solution, the molar ratio of the methyl methacrylate to the butyl acrylate to the methacrylic acid is 8: 20: 1. the molar ratio of the methyl methacrylate to the ammonium persulfate to the sodium bicarbonate to the deionized water is 0.8: 0.01: 0.03: 6.
mixing and stirring sodium dodecyl sulfate and deionized water for 20min, wherein the molar ratio of the sodium dodecyl sulfate to the deionized water is 0.02: 22; the mol ratio of the sodium dodecyl sulfate to the methyl methacrylate is 1: 4; heating to 70 ℃, dropwise adding the monomer solution for 2h, keeping the temperature for 50min after dropwise adding, and cooling to obtain the acrylic resin binder.
Placing a dispersing agent in ultrapure water, stirring for 5min, adding ceramic powder, stirring for 30min, adding a binder, stirring for 1h, adding a wetting agent, and stirring again for 30min to obtain ceramic slurry; the ceramic powder comprises, by mass, 0.9% of a dispersing agent, 40% of ceramic powder, 3.5% of a binder, 0.35% of a wetting agent and the balance ultrapure water.
(2) Coating the prepared ceramic slurry on two sides of the base film to form a ceramic coating, drying in an oven, washing with water at a speed of 130m/min in an 8-level water washing tank. Drying, rolling and slitting to obtain the ceramic coated diaphragm. The base film is a polyethylene film.
The dispersant is triethanolamine; the ceramic powder is prepared from aluminum oxide powder, boehmite powder, silicon dioxide powder and titanium dioxide powder in a mass ratio of 1: 1: 1: 1, compounding; the wetting agent is an alkyne diol modified nonionic surfactant.
In all of the above examples, the polyvinyl film thickness was 9 microns and the ceramic coating application thickness was 2 microns.
Experiment:
the performance parameters of the separators prepared in examples 1 to 5 and comparative examples 1 to 4 were measured, and the specific data are shown in the following table:
Figure BDA0003553939150000091
Figure BDA0003553939150000101
and (4) conclusion: 1. the invention uses two different binders, namely the water-resistant binder and the solution binder (hydrolysis type binder), and adds a washing process after coating and drying are finished to wash off the solution binder, thereby reducing the hole blockage of the binder and the air permeability increment.
2. This application uses monomers such as methyl methacrylate, butyl acrylate, methacrylic acid as raw materials, the preparation obtains the acrylate adhesive, and introduced 4,4' -dimercapto diphenyl sulfide double methyl methacrylate as comonomer, contain sulfydryl and phenyl in this monomer, the high temperature resistance performance of diaphragm not only can be improved in the introduction of this monomer, and flame retardant property obtains promoting moreover, simultaneously, sulfydryl group can effectively reduce long chain polysulfide shuttle, therefore the electric stability of the diaphragm of preparation is better, the capacity obtains promoting.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A low permeability incremental ceramic coated membrane characterized by: the diaphragm comprises a base film and ceramic coatings coated on two sides of the base film;
the ceramic coating raw materials comprise: 0.6 to 3 percent of dispersant, 30 to 45 percent of ceramic powder, 2.5 to 6.5 percent of binder, 0.15 to 0.55 percent of wetting agent and the balance of ultrapure water by mass percentage.
2. The low permeability incremental ceramic coated membrane of claim 1 wherein: the binder comprises a water-resistant binder and a hydrolysis type binder, wherein the water-resistant binder and the hydrolysis type binder are mixed according to a mass ratio of 1: (0.3-1) compounding.
3. The low permeability incremental ceramic coated membrane of claim 2 wherein: the waterproof binder is any one or mixture of acrylic resin binder and vinyl acetate polymer latex binder.
4. The low permeability incremental ceramic coated membrane of claim 2 wherein: the hydrolysis type binder is any one or more of polyvinyl alcohol binder, polyoxyethylene binder, polyethylene glycol binder, polyacrylamide binder, polyvinylpyrrolidone binder and polyacrylic acid binder.
5. The low permeability incremental ceramic coated membrane of claim 1 wherein: the dispersant is any one or more of a water-based polycarboxylate ammonium salt type dispersant, an acrylate copolymer type dispersant and a triethanolamine type dispersant; the ceramic powder is any one or more of aluminum oxide powder, boehmite powder, silicon dioxide powder and titanium dioxide powder; the wetting agent is any one or a plurality of polyether organic silicon copolymer surfactants and alkyne diol modified nonionic surfactants.
6. A preparation method of a low-permeability incremental ceramic coating diaphragm is characterized by comprising the following steps: the method comprises the following steps:
(1) mixing the water-resistant binder and the hydrolysis type binder, and stirring for 20-30min to obtain the binder; placing a dispersing agent in ultrapure water, stirring for 5-10min, adding ceramic powder, stirring for 20-30min, adding a binder, stirring for 1-1.5h, adding a wetting agent, and stirring again for 20-30min to obtain ceramic slurry;
(2) coating the prepared ceramic slurry on two sides of the base film to form a ceramic coating, drying in an oven, washing with water, drying, rolling and slitting after drying to obtain the ceramic coating diaphragm.
7. The method of making a low permeability incremental ceramic coated membrane of claim 6 wherein: in the step (2), an 8-grade rinsing bath is adopted during rinsing, and the rinsing speed is 60-130 m/min.
8. The method of making a low permeability incremental ceramic coated membrane of claim 6 wherein: the water-resistant binder is any one or mixture of acrylic resin binder and vinyl acetate polymer latex binder; the hydrolysis type binder is any one or more of polyvinyl alcohol binder, polyoxyethylene binder, polyethylene glycol binder, polyacrylamide binder, polyvinylpyrrolidone binder and polyacrylic acid binder.
9. The method of making a low permeability incremental ceramic coated membrane of claim 6 wherein: the preparation method of the water-resistant binder comprises the following steps:
taking methyl methacrylate, butyl acrylate, methacrylic acid, ammonium persulfate, sodium bicarbonate and deionized water, mixing and stirring uniformly, adding 4,4' -dimercaptodiphenyl sulfide dimethyl methacrylate, and stirring for 20-30min to obtain a monomer solution;
mixing and stirring sodium dodecyl sulfate and deionized water for 20-30min, heating to 70-80 ℃, dropwise adding the monomer solution for 1.5-2h, keeping the temperature for 50-60min after dropwise adding, and cooling to obtain the water-resistant binder.
10. The method of making a low permeability incremental ceramic coated membrane of claim 9 wherein: in the monomer solution, the molar ratio of methyl methacrylate, butyl acrylate, methacrylic acid and 4,4' -dimercaptodiphenyl sulfide bis-methyl methacrylate is 8: 20: 1: 3.
CN202210272102.3A 2022-03-18 2022-03-18 Low-permeability incremental ceramic coating diaphragm and preparation method thereof Withdrawn CN114552120A (en)

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Cited By (2)

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CN114696040A (en) * 2022-06-01 2022-07-01 沧州明珠隔膜科技有限公司 Lithium ion battery diaphragm and preparation method and application thereof
CN117253652A (en) * 2023-11-16 2023-12-19 宁德时代新能源科技股份有限公司 Insulating glue solution and preparation method thereof, insulating glue film, positive electrode plate, secondary battery and power utilization device

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114696040A (en) * 2022-06-01 2022-07-01 沧州明珠隔膜科技有限公司 Lithium ion battery diaphragm and preparation method and application thereof
CN114696040B (en) * 2022-06-01 2022-08-30 沧州明珠隔膜科技有限公司 Lithium ion battery diaphragm and preparation method and application thereof
CN117253652A (en) * 2023-11-16 2023-12-19 宁德时代新能源科技股份有限公司 Insulating glue solution and preparation method thereof, insulating glue film, positive electrode plate, secondary battery and power utilization device
CN117253652B (en) * 2023-11-16 2024-04-16 宁德时代新能源科技股份有限公司 Insulating glue solution and preparation method thereof, insulating glue film, positive electrode plate, secondary battery and power utilization device

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