CN117025140A - Water-based adhesive and preparation method thereof - Google Patents

Water-based adhesive and preparation method thereof Download PDF

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Publication number
CN117025140A
CN117025140A CN202311026260.1A CN202311026260A CN117025140A CN 117025140 A CN117025140 A CN 117025140A CN 202311026260 A CN202311026260 A CN 202311026260A CN 117025140 A CN117025140 A CN 117025140A
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China
Prior art keywords
monomer
polymer
aqueous
aqueous solution
aqueous adhesive
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CN202311026260.1A
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Chinese (zh)
Inventor
赵晓东
白丰瑞
黄志杰
罗贺斌
林松日
施燕玲
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Fujian Blue Ocean & Black Stone New Material Technology Co ltd
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Fujian Blue Ocean & Black Stone New Material Technology Co ltd
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Priority to CN202311026260.1A priority Critical patent/CN117025140A/en
Publication of CN117025140A publication Critical patent/CN117025140A/en
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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • 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
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • 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
    • C08F220/42—Nitriles
    • C08F220/44—Acrylonitrile
    • C08F220/46—Acrylonitrile with carboxylic acids, sulfonic acids or salts thereof
    • 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
    • C08F220/42—Nitriles
    • C08F220/44—Acrylonitrile
    • C08F220/48—Acrylonitrile with nitrogen-containing monomers
    • 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
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives 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; Adhesives based on derivatives of such polymers
    • C09J133/18—Homopolymers or copolymers of nitriles
    • C09J133/20—Homopolymers or copolymers of acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives 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; Adhesives based on derivatives of such polymers
    • C09J133/24—Homopolymers or copolymers of amides or imides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • 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 application relates to the field of aqueous adhesives, and particularly provides an aqueous adhesive and a preparation method thereof. An aqueous binder comprising a first polymer and a second polymer, the first polymer providing good adhesion to the copper foil and cohesion between the negative active particles; the second polymer may provide good pole piece flexibility. Therefore, the aqueous adhesive disclosed by the application has good adhesion to polar plates, high cohesive force and better flexibility through compounding of two polymers, and realizes excellent comprehensive performance.

Description

Water-based adhesive and preparation method thereof
Technical Field
The application relates to the technical field of aqueous adhesives, in particular to an aqueous adhesive and a preparation method thereof.
Background
The aqueous binder is one of the indispensable raw material components of the lithium ion battery, can disperse the positive electrode material and/or the negative electrode material, and simultaneously adheres the positive electrode material and/or the negative electrode material to the pole piece. The performance of the aqueous adhesive has an important influence on the performance of the lithium ion battery because the performance of the lithium ion battery is directly related to the dispersibility of the positive electrode material and the negative electrode material, the adhesion to the pole piece, the flexibility of the pole piece and the like. Materials of the common water-based adhesive are polyacrylate PAA, styrene-butadiene emulsion SBR, sodium carboxymethylcellulose CMC and the like. PAA has the characteristics of high bonding strength and better dispersibility, but has the defect of insufficient softness. Blending several aqueous binder materials to improve the performance of aqueous binders is one of the methods commonly used in the industry, such as paa+cmc blending, sbr+paa blending, paa+cmc+sbr blending, etc., but all improve other performance at the expense of some performance. For example, although CMC+PAA has higher adhesive force and cohesive force, the internal resistance of the final battery is low, and the circulation is better, but the pole piece has high hardness and brittleness, and the phenomena of powder falling, cracking and the like are easy to occur in the pole piece manufacturing process, so that the performance of the final battery is influenced.
Disclosure of Invention
The application provides a water-based adhesive and a preparation method thereof, and aims to solve the technical problems of poor comprehensive performance, particularly poor flexibility and the like of different water-based adhesives after mixing and splicing in the prior art.
The application adopts the following technical scheme:
an aqueous adhesive comprising a first polymer and a second polymer;
the first polymer has a structure represented by the following formula (1),
wherein R is 1 、R 2 And R is 3 Independently selected from H or C1-C4 alkyl, R 4 Selected from H, na + 、Li + And K + At least one of R 5 Selected from C2-C18 alkyl, C2-C18 substituted alkyl, amino or substituted amino, R 6 Has the general formula of-R 7 CN，R 7 Is at least one of the non-existence or selected from C1-C4 alkylene, a is more than 0, b is more than or equal to 0, C is more than 0, a: b: c=2-5:0-4:2-5;
the second polymer is prepared as follows: adding a surfactant and/or a protective colloid into water, and then adding a mixed monomer consisting of a first monomer, a second monomer and a third monomer for polymerization reaction to obtain the modified polyurethane foam;
the general formula of the first monomer is CH 2 ＝CR 8 COOM, wherein R 8 Selected from H or C1-C4 alkyl, M is selected from H, na + 、Li + And K + At least one of (a) and (b);
the second monomer is selected from at least one of soft monomers;
the third monomer is selected from R 9 CH＝CHR 10 CN, wherein R 9 Selected from H or methyl, R 10 Is absent or at least one selected from C1-C4 alkylene.
Preferably, the concentration of the aqueous binder is 3-60wt%.
Preferably, the weight ratio of the first polymer to the second polymer is 1:9-9:1.
Preferably, the soft monomer has the general formula CH 2 ＝CHCOOR 11 Wherein R is 11 Selected from C2-C18 alkyl, C2-C18 substituted alkyl or substituted amino.
Preferably, the surfactant is one or more selected from nonionic surfactant and anionic surfactant, and the weight ratio of the surfactant to the mixed monomer is 0-5:100.
Preferably, the protective colloid is at least one selected from the group consisting of polyvinyl alcohol, carboxymethyl cellulose ether, hydroxymethyl cellulose ether, hydroxypropyl cellulose ether, and polyvinylpyrrolidone.
Preferably, the weight ratio of the protective colloid to the mixed monomer is 0-50:100.
Preferably, the mixed monomer is composed of 5 to 50% by weight of the first monomer, 5 to 50% by weight of the second monomer, and 20 to 90% by weight of the third monomer.
The method for producing an aqueous adhesive according to any one of the above embodiments, which comprises mixing a first aqueous solution containing the first polymer and a second aqueous solution containing the second polymer.
The method of preparing an aqueous adhesive according to any one of the above embodiments, wherein the first polymer is added to a third aqueous solution containing the second polymer, and mixed uniformly.
In summary, the application has the following beneficial effects:
1. in the application, the combination of two polyacrylate polymers is adopted, and the first polymer can provide good adhesion capability with copper foil and cohesive capability between anode active particles; the second polymer can provide good adhesion capability with copper foil and cohesive capability among particles, has certain flexibility, and solves the technical problems of good flexibility but low adhesive force and cohesive strength when being mixed with SBR. Therefore, the aqueous adhesive disclosed by the application has the advantages of good adhesive force to the pole piece, high cohesive force, better flexibility and good comprehensive performance.
2. According to the application, through selection of monomers in the synthesis of the polyacrylate polymer, setting of the proportion of the monomers and optimization of the preparation process, the obtained two polyacrylate polymers cooperatively play roles, and have good comprehensive performance.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the technical solutions of the present application will be described in detail below.
Throughout the specification, unless specifically indicated otherwise, the terms used herein should be understood as meaning as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. In case of conflict, the present specification will control.
In one aspect, the present application provides an aqueous adhesive comprising a first polymer and a second polymer; the first polymer and the second polymer are active ingredients of the aqueous binder. The aqueous adhesive of the present application may be obtained by mixing a first aqueous solution containing a first polymer and a second aqueous solution containing a second polymer, or by adding the first polymer to a third aqueous solution containing the second polymer and mixing them uniformly.
The concentration of the aqueous binder may be 3 to 60wt%, and for example, may be 3wt%, 5wt%, 8wt%, 10wt%, 20wt%, 30wt%, 40wt%, 50wt%, 60wt%, etc. For example, the aqueous binder may be formed by mixing a first aqueous solution with a concentration of 20wt% and a second aqueous solution with a concentration of 20wt% at a weight ratio of 1:1, may be formed by mixing a first aqueous solution with a concentration of 40wt% and a second aqueous solution with a concentration of 40wt% at a weight ratio of 1:1, may be formed by mixing a first aqueous solution with a concentration of 8wt% and a second aqueous solution with a concentration of 16wt% at a weight ratio of 1:1, may be formed by mixing a first aqueous solution with a concentration of 10wt% and a second aqueous solution with a concentration of 8wt% at a weight ratio of 1:2, may be formed by mixing a first aqueous solution with a concentration of 50wt% and a second aqueous solution with a concentration of 30wt% at a weight ratio of 1:1, may be formed by mixing a first aqueous solution with a concentration of 20wt% and a second aqueous solution with a concentration of 60wt% at a weight ratio of 1:2, may be formed by mixing a first aqueous solution with a concentration of 50wt% and a second aqueous solution with a concentration of 50wt% at a weight ratio of 1:6, or the like, without particular limitation.
Wherein the weight ratio of the first polymer to the second polymer is 1:9-9:1, or further, may be 1:7-7:1, for example, the weight ratio may be 1:7, 2:7, 3:7, 4:7, 5:7, 6:7, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, etc.
First Polymer
The first polymer has a structure represented by the following formula (1),
wherein R is 1 、R 2 And R is 3 Independently selected from H or C1-C4 alkyl, R 4 Selected from H, na + 、Li + And K + At least one of (a) and (b); r is R 5 Selected from C2-C18 alkyl, C2-C18 substituted alkyl or substituted amino, for example, substituted amino may be N, N-dimethylamino, N-methylamino, N-diethylamino, N-ethylamino, N-methylolamino, N-hydroxyethylamino, etc.; r is R 6 Has the general formula of-R 7 CN，R 7 Is at least one of the non-existence or selected from C1-C4 alkylene, a is more than 0, b is more than or equal to 0, C is more than 0, a: b: c=2-5:0-4:2-5; the first polymer may be composed of three monomers, each of the general formula CH 2 ＝CR 1 COOR 4 、CH 2 ＝CR 2 COOR 5 And CH (CH) 2 ＝CR 3 COOR 6 The three monomers are obtained through free radical polymerization, and can be directly polymerized in an aqueous system to obtain a first aqueous solution, or polymerized in an oily system and removed of an organic solvent to obtain a first polymer, or the obtained first polymer is added into water to prepare the first aqueous solution. By way of example, CH 2 ＝CR 1 COOR 4 The monomer may be methacrylic acid, acrylic acid, sodium acrylate, sodium methacrylate, etc. For example, CH 2 ＝CR 2 COOR 5 The monomer may be acrylic ester monomer, such as butyl acrylate, octyl acrylate, isooctyl acrylate, lauryl acrylate, stearic acid ester, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, etc., or acrylamide monomer, or acrylic ester monomer and acrylamide monomer in a weight ratio of 1The combination of 1-10:1 can be N, N-dimethylacrylamide, N-methylacrylamide, N-ethylacrylamide, N-diethylacrylamide, N-methylolacrylamide, N-hydroxyethyl acrylamide, N-dihydroxyethylacrylamide, etc. By way of example, CH 2 ＝CR 3 COOR 6 The monomer may be acrylonitrile, methacrylonitrile, 3-butenenitrile, and the like.
The first polymer adopts a combination of three monomers, CH 2 ＝CR 1 COOR 4 The monomer can impart good hydrophilicity, CH, to the first polymer 2 ＝CR 2 COOR 5 The monomer can endow the first polymer with better flexibility, certain hydrophilicity or hydrophobicity and CH 2 ＝CR 3 COOR 6 The monomer can impart better hydrophobicity, good coating property and cohesion to the active particles, especially the negative electrode active particles, to the first polymer.
Second Polymer
The second polymer was prepared as follows: adding a surfactant and/or a protective colloid into water, and then adding a mixed monomer consisting of a first monomer, a second monomer and a third monomer for polymerization reaction to obtain the modified polyurethane foam;
the mixed monomer may be composed of 5 to 50% by weight of the first monomer, 5 to 50% by weight of the second monomer, and 20 to 90% by weight of the third monomer. For example, the mixed monomer may be composed of 10% of the first monomer, 10% of the second monomer and 80% of the third monomer, may be composed of 5% of the first monomer, 10% of the second monomer and 85% of the third monomer, may be composed of 10% of the first monomer, 20% of the second monomer and 70% of the third monomer, may be composed of 25% of the first monomer, 10% of the second monomer and 65% of the third monomer, may be composed of 20% of the first monomer, 15% of the second monomer and 65% of the third monomer, may be composed of 30% of the first monomer, 10% of the second monomer and 60% of the third monomer, may be composed of 30% of the first monomer, 40% of the second monomer and 30% of the third monomer, and the like, without particular limitation.
The first monomer has the general formula of CH 2 ＝CR 8 COOM, wherein R 8 Selected from H or C1-C4 alkyl,m is selected from H, na + 、Li + And K + At least one of (a) and (b); for example, the first monomer may be sodium acrylate, sodium methacrylate, acrylic acid, methacrylic acid, and the like.
The second monomer is selected from at least one of soft monomers; the second monomer may be selected from the CH 2 ＝CR 2 COOR 5 One or more than two of the monomers can be acrylate monomers, such as acrylate soft monomers, wherein the soft monomers refer to homopolymers obtained by homopolymerization of the monomers, and the glass transition temperature Tg is not higher than 0 ℃ or further not higher than-10 ℃; for example, the acrylic soft monomer may be butyl acrylate, hydroxypropyl acrylate, ethyl acrylate, hydroxyethyl acrylate, hydroxybutyl acrylate, isooctyl acrylate, octyl acrylate, lauryl acrylate, stearic acrylate, or the like, or may be a combination of acrylic soft monomer and acrylamide monomer according to a weight ratio of 1:1-10:1, wherein the acrylic monomer may be as described above, and the acrylamide monomer may be N, N-dimethylacrylamide, N-methylacrylamide, N-ethylacrylamide, N-diethylacrylamide, N-methylolacrylamide, N-hydroxyethylacrylamide, N-dihydroxyethylacrylamide, or the like.
The third monomer is selected from R 9 CH＝CHR 10 CN, wherein R 9 Selected from H or methyl, R 10 Is absent or at least one selected from C1-C4 alkylene. For example, the third monomer may be acrylonitrile, methacrylonitrile, 3-butenenitrile, and the like.
In the application, the surfactant and/or the protective colloid, such as a single protective colloid or the combination of the protective colloid and the surfactant according to the weight ratio of 1:1-20:1, can realize the dispersion of the polymerized monomer, so that the polymerization reaction is smoother, and the free radical polymerization can also partially occur on the molecular chain of the surfactant and/or the protective colloid, so that the molecular chain of the surfactant and/or the protective colloid is grafted on the side chain of the high molecular main chain of the second polymer as a branched chain, and the second polymer is actually a branched chain polymer, thereby improving the branching degree and flexibility of the second polymer.
The surfactant can be one or more of nonionic surfactant and anionic surfactant, and the weight ratio of the surfactant to the mixed monomer is 0-5:100. For example, the surfactant may be dodecylbenzenesulfonic acid, sodium dodecylbenzenesulfonate, AEO-3, AEO-6, AEO-9, AEO-12, span 20, span 80, tween 20, tween 80, or the like, without particular limitation. Further, the weight ratio of surfactant to mixed monomer may be 0.5-5:100, for example, 0.5:100, 1:100, 1.5:100, 2:100, 2.5:100, 3:100, 3.5:100, 4:100, 4.5:100, 5:100, etc.
The protective colloid may be at least one selected from polyvinyl alcohol PVA, carboxymethyl cellulose ether, hydroxymethyl cellulose ether, hydroxypropyl cellulose ether, and polyvinylpyrrolidone PVP. For example, the protective colloid may be PVA with different molecular weights and degrees of hydrolysis, such as PVA1788, PVA1792, etc. The weight ratio of the protective colloid to the mixed monomer can be 0-50:100. Further, the weight ratio of the protective colloid to the mixed monomer may be 0.5 to 30:100, and for example, may be 1:100, 5:100, 10:100, 12:100, 15:100, 18:100, 20:100, 22:100, 25:100, 27:100, 30:100, etc.
The technical scheme of the application is described in detail below with reference to examples and comparative examples. Unless otherwise indicated, the parts in the following preparations, examples and comparative examples are parts by weight.
PREPARATION EXAMPLES 1-4 preparation of first aqueous solution
Preparation example 1
300 parts of water, 60 parts by weight of methacrylic acid, butyl acrylate, N-dimethylacrylamide and acrylonitrile (the molar ratio of the methacrylic acid, the butyl acrylate, the N, N-dimethylacrylamide and the acrylonitrile is 1:0.5:1:1) are added into a reaction vessel, 5 parts of sodium bicarbonate is added, the temperature is raised to 72 ℃, 20 parts of aqueous solution containing 0.3 part of ammonium persulfate is dropwise added within 30 minutes, the constant temperature reaction is continued for 210 minutes after the dropwise addition, the temperature is reduced to below 40 ℃, the sodium bicarbonate and the water are added, the pH value is regulated to 7.5-8.0, the solid content is 10wt%, and the first aqueous solution is obtained.
Preparation example 2
The differences between preparation 2 and preparation 1 are: the molar ratio of methacrylic acid, butyl acrylate, N-dimethylacrylamide and acrylonitrile in preparation example 1 was adjusted to 1:0.5:1:1, and the molar ratio of acrylic acid, isooctyl acrylate, N-dimethylacrylamide and acrylonitrile was adjusted to 2:0.5:1:1. The remaining steps remain unchanged.
Preparation example 3
300 parts of water, 50 parts by weight of acrylic acid, butyl acrylate, N-dimethylacrylamide and acrylonitrile (the molar ratio of the acrylic acid to the butyl acrylate to the N, N-dimethylacrylamide to the acrylonitrile is 1:0:2:1) are added into a reaction vessel, 5 parts of sodium bicarbonate is added, the temperature is raised to 72 ℃, 20 parts of aqueous solution containing 0.3 part of ammonium persulfate is dropwise added within 30min, the dropwise addition is continued to perform constant temperature reaction for 210min, the temperature is reduced to below 40 ℃, the sodium bicarbonate and the water are added, the pH value is regulated to 7.5-8.0, the solid content is 12wt%, and the first aqueous solution is obtained.
Preparation example 4
300 parts of water, 50 parts by weight of acrylic acid, N-dimethylacrylamide, butyl acrylate and methacrylonitrile (the molar ratio of the acrylic acid to the N, N-dimethylacrylamide to the butyl acrylate to the methacrylonitrile is 1:0.5:0.5:2), 5 parts of sodium bicarbonate, heating to 72 ℃, dropwise adding 20 parts of aqueous solution containing 0.3 part of ammonium persulfate within 30 minutes, continuing to perform constant temperature reaction for 210 minutes after dropwise adding, cooling to below 40 ℃, adding sodium bicarbonate and water, adjusting the pH to 7.5-8.0 and the solid content to 12wt%, and obtaining a first aqueous solution.
PREPARATION EXAMPLES 5-8 preparation of second aqueous solution
Preparation example 5
Adding 8 parts of PVA BP-05 and 350 parts of water into a reaction vessel, heating to 90 ℃, stirring until BP-05 is completely dissolved, cooling to below 40 ℃, sequentially adding 20 parts of acrylic acid, 15 parts of n-butyl acrylate, 5 parts of ethyl acrylate and 60 parts of acrylonitrile, raising the temperature to 76 ℃, dropwise adding 50 parts of aqueous solution containing 0.3 part of ammonium persulfate within 120min, continuing to perform heat preservation reaction for 100min after dropwise adding, cooling to below 40 ℃, adding sodium bicarbonate and water, regulating the pH to 7.0-7.5, and obtaining a second aqueous solution with the solid content of 16 wt%.
Preparation example 6
The differences between preparation 6 and preparation 5 are: in preparation example 5, 5 parts of ethyl acrylate was adjusted to 5 parts of N, N-dimethylacrylamide. The remaining steps remain unchanged.
Preparation example 7
Adding 5 parts of PVA BP-05 and 350 parts of water into a reaction vessel, heating to 90 ℃, stirring until BP-05 is completely dissolved, cooling to below 40 ℃, sequentially adding 15 parts of acrylic acid, 10 parts of n-butyl acrylate and 75 parts of acrylonitrile, heating to 73 ℃, dropwise adding 50 parts of aqueous solution containing 0.3 part of ammonium persulfate within 120min, continuing to perform heat preservation reaction for 100min after dropwise adding, cooling to below 40 ℃, adding sodium bicarbonate and water, regulating pH to 7.0-7.5, and obtaining a second aqueous solution with a solid content of 16 wt%.
Preparation example 8
The differences between preparation 8 and preparation 7 are: in preparation example 7, 5 parts of PVA BP-05 was adjusted to 3.5 parts of PVA BP-05 and 1.5 parts of surfactant AEO-9. The remaining steps remain unchanged.
Example 1
The first aqueous solution of preparation example 1 and the second aqueous solution of preparation example 5 were mixed in a weight ratio of 10:1 and stirred uniformly to obtain an aqueous adhesive.
Example 2
The first aqueous solution of preparation example 1 and the second aqueous solution of preparation example 5 are mixed according to a weight ratio of 1:1, and stirred uniformly to obtain an aqueous adhesive.
Example 3
The first aqueous solution of preparation example 1 and the second aqueous solution of preparation example 5 are mixed according to a weight ratio of 1:4 and stirred uniformly to obtain an aqueous adhesive.
Example 4
The first aqueous solution of preparation example 1 and the second aqueous solution of preparation example 5 are mixed according to a weight ratio of 1:6 and stirred uniformly to obtain an aqueous adhesive.
Example 5
The first aqueous solution of preparation example 1 and the second aqueous solution of preparation example 7 are mixed according to a weight ratio of 1:1, and stirred uniformly to obtain an aqueous adhesive.
Example 6
The first aqueous solution of preparation example 2 and the second aqueous solution of preparation example 6 were mixed in a weight ratio of 3:1 and stirred uniformly to obtain an aqueous adhesive.
Example 7
The first aqueous solution of preparation example 3 and the second aqueous solution of preparation example 6 were mixed in a weight ratio of 3:1 and stirred uniformly to obtain an aqueous adhesive.
Example 8
The first aqueous solution of preparation example 3 and the second aqueous solution of preparation example 7 were mixed in a weight ratio of 6:1 and stirred uniformly to obtain an aqueous adhesive.
Example 9
The first aqueous solution of preparation example 3 and the second aqueous solution of preparation example 8 were mixed in a weight ratio of 6:1 and stirred uniformly to obtain an aqueous adhesive.
Example 10
The first aqueous solution of preparation example 4 and the second aqueous solution of preparation example 7 are mixed according to a weight ratio of 1:2 and stirred uniformly to obtain an aqueous adhesive.
Comparative example 1
The first aqueous solution of preparation example 1.
Comparative example 2
The second aqueous solution of preparation 5.
Comparative example 3
The second aqueous solution of preparation 7.
Performance testing
The preparation process of the graphite negative electrode plate comprises the following steps: dispersing the water-based adhesive to be tested and 50% of water for 15 minutes at 1000rpm, adding the conductive agent SP conductive carbon black to wet for 12 minutes, and stirring at a high speed of 1600rpm for 120 minutes; the negative electrode material S360-L2-H and the remaining 50% of water were added and stirring was continued at 1600rpm for 120 minutes at high speed. After the dispersion is finished, the viscosity (23 ℃) is regulated to be 2500-2700 mPa.s, and the mixture is filtered by a 150-mesh filter screen to finish discharging. Placing copper foil on a coater, adjusting the scale of a scraper of a wet film preparation device, uniformly pouring the filtered slurry, sending into 100 ℃ environment, blowing and baking until the slurry is dried, cutting the slurry into a specification of 12.5cm multiplied by 5cm, and enabling the single-sided surface density to be 100-110g/m 2 Is a pole piece.
The pole piece stripping force testing method comprises the following steps: will be cut wellThe pole pieces are sent into a 35 percent RH constant temperature chamber for 30 minutes, the coating surface faces outwards, the copper foil surface faces inwards to attach the two pole pieces, and the pole pieces are sent into an electric roller press to be rolled to 1.6g/cm 3 Placing for 30 minutes after rolling, selecting five stainless steel plates with the specification of 12.5 multiplied by 5cm, attaching double-sided adhesive tapes with corresponding specifications on the steel plates, attaching a pole piece on the double-sided adhesive tapes in a way that a coating faces downwards, attaching a piece of masking paper tape with the width of 2.5cm on a copper foil, rolling the pole piece steel plates back and forth for one circle by an electric rolling roller with certain pressure, using an electronic stripper, and testing the adhesive force of the pole piece; in the same way, the cohesive force of the pole piece can be tested by only changing the way that the pole piece is attached to the double-sided adhesive tape in an upward coating way.
The pole piece flexibility test method comprises the following steps: the softness tester, model ITM-RRD01, was used for testing.
The method for testing the swelling rate of the adhesive film electrolyte comprises the following steps: cutting edge part of bubble-free adhesive film, cutting into 1×4cm, oven drying in 105 deg.C air drying oven for 4 hr, and taking out weighing record M 1 Is put into a container filled with electrolyte (1M LiPF 6 in EC: DMC: EMC=1:1:1), soaking in the vial at constant temperature for 48 hr, taking out, wiping the surface electrolyte with filter paper, controlling wiping and weighing process within 1min, and weighing M 2 The swelling ratio of the adhesive film is (M 2 -M 1 )/M 1 ×100％。
The buckling assembly sequence is from bottom to top: negative electrode shell-elastic sheet-gasket-lithium sheet-electrolyte-diaphragm-electrolyte-pole piece-positive electrode shell; the first coulombic efficiency and impedance test is as follows:
first effect test 0.1C,0.005-1.5V charge and discharge; the impedance sweep was from 100kHz to 0.1Hz.
The results are shown in Table 1 below.
TABLE 1 Performance test results
As is clear from the data in table 1, the aqueous binder of the present application has suitable adhesive force, cohesive force, softness, interfacial resistance, swelling rate of the adhesive film, and the like, and has good overall properties, and is suitable as an aqueous binder of active particles of positive electrode material/negative electrode material of lithium ion batteries.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.

Claims (10)

1. An aqueous adhesive comprising a first polymer and a second polymer;
the first polymer has a structure represented by the following formula (1),
wherein R is 1 、R 2 And R is 3 Independently selected from H or C1-C4 alkyl, R 4 Selected from H, na + 、Li + And K + At least one of R 5 Selected from C2-C18 alkyl, C2-C18 substituted alkyl, amino or substituted amino, R 6 Has the general formula of-R 7 CN，R 7 Is at least one of the non-existence or selected from C1-C4 alkylene, a is more than 0, b is more than or equal to 0, C is more than 0, a: b: c=2-5:0-4:2-5;
the second polymer is prepared as follows: adding a surfactant and/or a protective colloid into water, and then adding a mixed monomer consisting of a first monomer, a second monomer and a third monomer for polymerization reaction to obtain the modified polyurethane foam;
the general formula of the first monomer is CH 2 ＝CR 8 COOM, wherein R 8 Selected from H or C1-C4 alkyl, M is selected from H, na + 、Li + And K + At least one of (a) and (b);
the second monomer is selected from at least one of soft monomers;
the third monomer is selected from R 9 CH＝CHR 10 CN, wherein R 9 Selected from H or methyl, R 10 Is absent or at least one selected from C1-C4 alkylene.
2. The aqueous binder of claim 1 wherein the concentration of the aqueous binder is 3-60wt%.
3. The aqueous adhesive of claim 1, wherein the weight ratio of the first polymer to the second polymer is 1:9-9:1.
4. The aqueous adhesive of claim 1, wherein the soft monomer has the formula CH 2 ＝CHCOOR 11 Wherein R is 11 Selected from C2-C18 alkyl, C2-C18 substituted alkyl or substituted amino.
5. The aqueous adhesive according to claim 1, wherein the surfactant is one or more selected from nonionic surfactant and anionic surfactant, and the weight ratio of the surfactant to the mixed monomer is 0-5:100.
6. The aqueous adhesive according to claim 1, wherein the protective colloid is at least one selected from the group consisting of polyvinyl alcohol, carboxymethyl cellulose ether, hydroxymethyl cellulose ether, hydroxypropyl cellulose ether, and polyvinylpyrrolidone.
7. The aqueous adhesive according to claim 1, wherein the weight ratio of the protective colloid to the mixed monomer is 0-50:100.
8. The aqueous binder of claim 1 wherein said mixed monomer consists of 5-50% by weight of said first monomer, 5-50% by weight of said second monomer and 20-90% by weight of said third monomer.
9. The method of producing an aqueous adhesive according to any one of claims 1 to 8, wherein the aqueous adhesive is obtained by mixing a first aqueous solution containing the first polymer and a second aqueous solution containing the second polymer.
10. The method of preparing an aqueous adhesive according to any one of claims 1 to 8, wherein the first polymer is added to a third aqueous solution containing the second polymer and mixed uniformly.
CN202311026260.1A 2023-08-15 2023-08-15 Water-based adhesive and preparation method thereof Pending CN117025140A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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 (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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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