CN110172124B - Special adhesive for lithium battery ceramic diaphragm and preparation method and application thereof - Google Patents
Special adhesive for lithium battery ceramic diaphragm and preparation method and application thereof Download PDFInfo
- Publication number
- CN110172124B CN110172124B CN201910515614.6A CN201910515614A CN110172124B CN 110172124 B CN110172124 B CN 110172124B CN 201910515614 A CN201910515614 A CN 201910515614A CN 110172124 B CN110172124 B CN 110172124B
- Authority
- CN
- China
- Prior art keywords
- water
- parts
- adhesive
- soluble
- organic solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
-
- 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
- C08F222/00—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 carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/02—Acids; Metal salts or ammonium salts thereof, e.g. maleic acid or itaconic acid
-
- 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
- H01M50/431—Inorganic material
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Cell Separators (AREA)
Abstract
The invention discloses a special adhesive for a ceramic diaphragm of a lithium battery, and a preparation method and application thereof. The adhesive can be used for a water-based system and an organic solvent system, is a homogeneous clear solution, can be diluted by water or an organic solvent, and the diluted product is still the homogeneous clear solution, and comprises the following components in parts by mass: 10-60 parts of water-soluble unsaturated carboxylic acid; 10-60 parts of water-soluble unsaturated carboxylic ester; 0.1-15 parts of water-soluble functional monomer; 0.1-15 parts of water-insoluble functional monomer; 0.01-3 parts of an initiator; 50-200 parts of a water-soluble organic solvent; 0-20 parts of pure water. The adhesive is used for preparing ceramic diaphragm slurry and diaphragms, so that very good performance can be obtained, and the obtained ceramic diaphragm slurry has low water absorption; after the obtained diaphragm is treated at 160 ℃ for 30-60 min, the transverse and longitudinal heat shrinkage rates are not more than 3%.
Description
Technical Field
The invention relates to a lithium battery ceramic diaphragm material, in particular to a lithium battery ceramic diaphragm adhesive and a preparation method and application thereof.
Background
Various new energy batteries represented by lithium ion batteries are widely applied in the fields of daily life and advanced science and technology at present. With the increasing demand of new energy batteries in the market, how to increase the production efficiency and expand the capacity while ensuring the safety and effectiveness of the batteries becomes a problem to be solved by various new energy battery manufacturers and their upstream suppliers. The main components of the battery comprise a shell, electrolyte, a positive electrode, a negative electrode, a diaphragm and the like, wherein the diaphragm serving as a core component of the battery is mainly coated with powder ceramic at present, and the production relates to a process of preparing a slurry from the powder ceramic material and then coating the slurry on the surface of a base material. The binder is one of indispensable components in the preparation of the slurry, and the quality thereof has a direct influence on the quality of the finished battery.
The mainstream adhesive special for the ceramic diaphragm of the lithium battery at present is an aqueous emulsion adhesive of an acrylate system, and the adhesive and the production process thereof tend to be mature and have wide application. However, the emulsion system is a thermodynamically unstable system, and is easily broken due to mechanical shearing, electrolytes, temperature change, long-time storage and the like, and the emulsion type adhesive needs to be added with various additives in the preparation process, so that the components and the process flow are complex, and various additives may cause unpredictable influence on the performance of the adhesive product. Thus, there is increasing interest in solution-type adhesives that are thermodynamically stable systems, have relatively simple components, and have a relatively simple process flow. In addition, due to the requirements on environmental protection, personnel health and the like, the market is concerned about the water solution type adhesive which is prepared by taking water as a solvent.
On the other hand, however, the aqueous emulsion type adhesives are limited by the critical factor of water solubility of the monomers, resulting in a much smaller number of monomers being available in the manufacturing process than the aqueous emulsion adhesives. The limitation of the water solubility of the monomers also results in that various monomers capable of imparting specific properties to the adhesive cannot be applied to the aqueous solution polymerization process, thus resulting in that the modification space of the aqueous solution type adhesive is greatly limited. For example, aromatic monomers (e.g., styrene) or epoxy structural monomers (e.g., glycidyl acrylate) that can impart heat resistance and low water absorption to the adhesive are mostly insoluble in water. Therefore, how to expand the modification space of the aqueous solution type adhesive without affecting the water solubility of the product is a potential research direction of the adhesive.
Disclosure of Invention
The invention aims to provide a special adhesive for a lithium battery ceramic diaphragm, which can be used for a water-soluble system and an organic solvent system, and a preparation method and application thereof. The invention selects proper organic solvent as the solvent in the solution polymerization process, the organic solvent has good solubility corresponding to each synthetic raw material, and the solvent has good solubility in water; a small amount of water-insoluble monomer is used as a functional monomer to be copolymerized with a water-soluble monomer used as a main monomer, and the obtained polymer still has good water solubility; the characteristics can effectively avoid the influence of the water solubility limit of the monomer on the polymerization process of the adhesive, and the adhesive can keep good water solubility, and can be applied to the preparation of aqueous slurry. Meanwhile, the adhesive can also be applied to the preparation of organic solvent-based sizing agent.
The technical scheme of the invention is as follows:
the adhesive can be used in an aqueous system and an organic solvent system, is a homogeneous clear solution, can be diluted by water or an organic solvent, and the diluted product is still the homogeneous clear solution, and comprises the following components in parts by mass:
10-60 parts of water-soluble unsaturated carboxylic acid;
10-60 parts of water-soluble unsaturated carboxylic ester;
0.1-15 parts of water-soluble functional monomer;
0.1-15 parts of water-insoluble functional monomer;
0.01-3 parts of an initiator;
50-200 parts of a water-soluble organic solvent;
0-20 parts of pure water.
Further, the water-soluble unsaturated carboxylic acid is one or more than two of the following substances: acrylic acid, methacrylic acid, maleic acid (commonly known as maleic acid), fumaric acid (commonly known as fumaric acid), 2-methylenesuccinic acid (commonly known as itaconic acid), propylene-1, 2, 3-carboxylic acid (commonly known as aconitic acid); one or more of acrylic acid, methacrylic acid and 2-methylenesuccinic acid are preferable.
Further, the water-soluble unsaturated carboxylic acid ester is one or more than two of the following substances: 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and 3-hydroxypropyl methacrylate; 2-hydroxyethyl acrylate is preferred.
Further, the water-soluble functional monomer is one or more than two of the following substances: acrylamide, N-methylolacrylamide, N-methylenebisacrylamide, N-dimethylacrylamide; one or two of N-methylolacrylamide and N, N-methylene-bisacrylamide are preferable.
Further, the water-insoluble functional monomer is one or more than two of the following substances: styrene, methyl methacrylate, n-butyl acrylate, isooctyl acrylate, n-octyl acrylate, glycidyl methacrylate, epoxy acrylate, gamma-methacryloxypropyltrimethoxysilane (commonly known as KH-570), diallyl phthalate; one or more of styrene, glycidyl methacrylate, epoxy acrylate and gamma-methacryloxypropyltrimethoxysilane are preferable.
Further, the initiator is one or more than two of the following substances: azobisisobutyronitrile, azobisisoheptonitrile, dibenzoyl peroxide, persulfate; preferably a persulfate salt, more preferably ammonium persulfate.
Further, the water-soluble organic solvent is one or more than two of the following substances: ethanol, isopropanol, N-propanol, N-butanol, ethylene glycol, propylene glycol, glycerol, cyclohexanol, 1, 4-dioxane, butanone, 3-pentanone, N-dimethylformamide, N-dimethylacetamide, 1-methyl-2-pyrrolidone, dimethyl sulfoxide, methyl glycolate, ethyl glycolate, propylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, glycerol monoacetate, glycerol diacetate, and ethylene glycol monoacetate; ethanol, dimethyl sulfoxide or 1, 4-dioxane are preferred.
The preparation method of the adhesive comprises the following steps:
(1) adding a solvent, a monomer and an initiator into a reaction device, keeping the temperature in the reaction device below 40 ℃, and stirring until the monomer and the initiator are completely dissolved;
(2) keeping stirring, and raising the temperature in the reaction device to 60-80 ℃;
(3) and after reacting for 2-5 h, cooling and collecting the materials to obtain a finished adhesive product.
Further, the method also comprises the dilution of the adhesive, specifically: dissolving the adhesive product in diluent, and dissolving measured neutralizer in the diluent in advance to make active hydrogen concentration in the diluted adhesive be 10-5~10-8And (5) mol/L to obtain a binder diluent.
Further, the diluent is pure water or the above-mentioned water-soluble organic solvent, and preferably pure water.
Further, the neutralizing agent is one or more than two of the following substances: ammonia water, organic amine and alkali metal hydroxide; preferably organic amine or alkali metal hydroxide, more preferably triethanolamine, diethylenetriamine, sodium hydroxide or lithium hydroxide.
The adhesive is applied to lithium battery ceramic diaphragm slurry and ceramic diaphragms.
The experiment proves that:
(1) the adhesive is colorless, light yellow or orange homogeneous clear solution, and does not precipitate or gel after being placed for a long time at room temperature;
(2) the adhesive can be dissolved in pure water or aqueous solution of a neutralizing agent with the weight more than 1 time of the adhesive, is still clear homogeneous solution after being dissolved, and can still be kept for a long time at room temperature without precipitation and gel; meanwhile, the adhesive can also be dissolved in various organic solvents;
(3) the adhesive has good thermal performance, and TGA test shows that the initial thermal decomposition temperature is not lower than 300 ℃, and DSC test shows that the glass transition temperature is not lower than 120 ℃;
(4) the adhesive has wide mechanical property parameters due to different solvents selected in the synthesis process, and a high-modulus and high-hardness adhesive film is obtained after the adhesive synthesized by using a low-boiling-point solvent is dried and shows rigid mechanical properties; the adhesive synthesized by using the high-boiling point solvent plays a role in plasticization due to partial solvent residue after drying, so that the adhesive film with low modulus and low hardness is obtained and shows flexible mechanical characteristics;
(5) the adhesive meets the requirements of the existing general preparation method of the ceramic diaphragm slurry of the lithium battery on the adhesive, the slurry prepared by the adhesive is uniform suspension, and does not settle obviously after standing for 2 hours at room temperature;
(6) the ceramic diaphragm slurry prepared by using the adhesive has low water absorption after being dried, and the weight increase of a dried solid is not more than 1.5% after the dried solid is kept stand for 24 hours in a room temperature environment with the relative humidity of 75%;
(7) the ceramic diaphragm slurry prepared by using the adhesive can endow a diaphragm with good heat resistance, and when the thickness of a base film is 9-12 mu m and the thickness of a ceramic coating is 3-4 mu m, the transverse and longitudinal heat shrinkage rates of the diaphragm are not more than 3% after the diaphragm is treated at 160 ℃ for 30-60 min.
Compared with the prior art, the invention has the beneficial effects that:
(1) the special adhesive for the ceramic diaphragm of the lithium battery is suitable for a water-based system and an organic solvent system, and the application range of the adhesive is expanded;
(2) the water-soluble organic solvent is used as the solvent in the solution polymerization process, so that the product has good water solubility, and the selection range of the raw materials for synthesizing the adhesive is expanded, so that more water-insoluble monomers can be used as functional monomers to participate in copolymerization;
(3) a small amount of water-insoluble monomer is used as a functional monomer to be copolymerized with a water-soluble monomer used as a main monomer, and the obtained product still has good water solubility, can be dissolved in water to form a homogeneous solution, and meets the requirements of environmental protection.
Drawings
FIG. 1 is a thermogravimetric analysis (TGA) curve of the adhesive described in example 1, showing an initial thermal decomposition temperature of 376.0 deg.C.
FIG. 2 is a Differential Scanning Calorimetry (DSC) curve of the adhesive of example 1, showing that the glass transition temperature of the adhesive is 133.8 ℃.
Fig. 3 is a comparison of the state of the separator of example 5 before and after heat treatment, the left diagram showing the state before heat treatment and the right diagram showing the state after heat treatment. The results show that no significant shrinkage was observed after heat treatment of the separator.
Detailed Description
The present invention will be described in more detail by way of examples for the sake of understanding, but the scope of the present invention is not limited to these examples.
Example 1
110g of ethanol, 30g of itaconic acid and 0.3g of N, N' -methylenebisacrylamide were put into a three-necked flask equipped with a stirrer and a condenser, and stirred at room temperature until all solid materials were dissolved, and then 30g of 2-hydroxyethyl acrylate and 6g of glycidyl methacrylate were put into the flask and stirred uniformly. 0.6g of ammonium persulfate is taken, dissolved by 10g of pure water and then put into a flask; keeping stirring, raising the reaction temperature to 70 ℃, reacting for 4 hours, cooling and collecting the materials, wherein the product is an orange-yellow homogeneous transparent solution.
Example 2
Adding 120g of dimethyl sulfoxide, 30g of itaconic acid, 0.3g of N, N' -methylene bisacrylamide and 0.6g of ammonium persulfate into a three-necked flask provided with a stirring device and a condensation pipe, stirring at room temperature until all solid materials are dissolved, adding 30g of acrylic acid-2-hydroxyethyl ester and 1.5g of epoxy acrylate into the flask, stirring uniformly, keeping stirring, raising the reaction temperature to 70 ℃, reacting for 4 hours, cooling and collecting materials; the product was a pale yellow homogeneous clear solution.
Example 3
An appropriate amount of the binder as described in example 1 or 2 was dissolved in pure water 2 times the mass of the binder to obtain a diluted solution of the binder. The pure water is dissolved with metered sodium hydroxide in advance, so that the pH value of the diluent is 5.5-6.5.
The diluent of the adhesive is a light yellow homogeneous clear solution, and the adverse phenomena of layering, precipitation, gelation and the like are not seen.
Example 4
An alumina ceramic separator slurry was prepared using the binder diluent described in example 3. The total amount of the slurry is 500 parts, and the solid content is 40% +/-2% (mass fraction). The solid content composition of the slurry comprises (by dry weight): 185-195 parts of alumina powder ceramic; 1-2 parts of a dispersant; 0.15-0.2 parts of a thickening agent; 0.7-0.9 part of adhesive; 0.7-0.8 part of wetting agent; the preparation process comprises the following steps:
(1) adding the alumina ceramic powder, the dispersing agent and the metered pure water into a pulping device, and dispersing for 60-90 min at the rotating speed of 1200-1500 rpm;
(2) adding the thickener, and dispersing for 30-60 min at the rotating speed of 800-1000 rpm;
(3) adding the adhesive diluent, and dispersing for 30-60 min at the rotating speed of 500-700 rpm;
(4) adding the wetting agent, dispersing for 30-60 min at the rotating speed of 200-300 rpm, and collecting slurry.
Example 5
The slurry as described in example 4 was uniformly applied to the surface of a base film having a thickness of 12 μm using a wire bar coater having a size of 10 μm, and the thickness of the dried coating was 3 μm, and the obtained separator was allowed to stand in an electrothermal blowing dry oven at 160 ℃ for 30 minutes.
The results show that the transverse and longitudinal shrinkage does not exceed 2%.
Claims (8)
1. The special adhesive for the ceramic diaphragm of the lithium battery is characterized by being capable of being used in a water-based system and an organic solvent system, being a homogeneous clear solution and being diluted by water or an organic solvent, wherein the diluted product is still the homogeneous clear solution and comprises the following components in parts by mass:
10-60 parts of water-soluble unsaturated carboxylic acid;
10-60 parts of water-soluble unsaturated carboxylic ester;
0.1-15 parts of water-soluble functional monomer;
0.1-15 parts of water-insoluble functional monomer;
0.01-3 parts of an initiator;
50-200 parts of a water-soluble organic solvent;
0-20 parts of pure water;
the water-soluble unsaturated carboxylic acid is one or more than two of the following substances: acrylic acid, methacrylic acid, maleic acid, fumaric acid, 2-itaconic acid, propylene-1, 2, 3-carboxylic acid;
the water-soluble unsaturated carboxylic ester is one or more than two of the following substances: 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and 3-hydroxypropyl methacrylate;
the water-soluble functional monomer is one or more than two of the following substances: acrylamide, N-methylolacrylamide, N-methylenebisacrylamide, N-dimethylacrylamide;
the water-insoluble functional monomer is one or more than two of the following substances: styrene, methyl methacrylate, n-butyl acrylate, isooctyl acrylate, n-octyl acrylate, glycidyl methacrylate, epoxy acrylate, gamma-methacryloxypropyltrimethoxysilane, diallyl phthalate.
2. The binder for a ceramic separator of a lithium battery as claimed in claim 1, wherein the initiator is one or more than two of the following substances: azobisisobutyronitrile, azobisisoheptonitrile, dibenzoyl peroxide, persulfate.
3. The binder of claim 1, wherein the water-soluble organic solvent is one or more of the following substances: ethanol, isopropanol, N-propanol, N-butanol, ethylene glycol, propylene glycol, glycerol, cyclohexanol, 1, 4-dioxane, butanone, 3-pentanone, N-dimethylformamide, N-dimethylacetamide, 1-methyl-2-pyrrolidone, dimethyl sulfoxide, methyl glycolate, ethyl glycolate, propylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, glycerol monoacetate, glycerol diacetate, and ethylene glycol monoacetate.
4. A method for preparing the adhesive according to any one of claims 1 to 3, comprising the steps of:
(1) adding a solvent, a monomer and an initiator into a reaction device, keeping the temperature in the reaction device below 40 ℃, and stirring until the monomer and the initiator are completely dissolved;
(2) keeping stirring, and raising the temperature in the reaction device to 60-80 ℃;
(3) and after reacting for 2-5 h, cooling and collecting the materials to obtain a finished adhesive product.
5. The method for preparing the adhesive according to claim 4, further comprising the step of diluting the adhesive, specifically: dissolving the adhesive product in diluent, and dissolving measured neutralizer in the diluent in advance to make active hydrogen concentration in the diluted adhesive be 10-5~10-8And (5) mol/L to obtain a binder diluent.
6. The method for preparing an adhesive according to claim 5, wherein the diluent is pure water or the water-soluble organic solvent according to claim 3.
7. The method of claim 5, wherein the neutralizing agent is one or more of the following substances: ammonia water, organic amine and alkali metal hydroxide.
8. Use of the binder of any one of claims 1 to 3 in a ceramic separator slurry for lithium batteries and in a ceramic separator.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910515614.6A CN110172124B (en) | 2019-06-14 | 2019-06-14 | Special adhesive for lithium battery ceramic diaphragm and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910515614.6A CN110172124B (en) | 2019-06-14 | 2019-06-14 | Special adhesive for lithium battery ceramic diaphragm and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110172124A CN110172124A (en) | 2019-08-27 |
| CN110172124B true CN110172124B (en) | 2021-07-02 |
Family
ID=67698513
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910515614.6A Active CN110172124B (en) | 2019-06-14 | 2019-06-14 | Special adhesive for lithium battery ceramic diaphragm and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110172124B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112467142A (en) * | 2020-11-25 | 2021-03-09 | 湖南高瑞电源材料有限公司 | Aqueous solution type lithium iron phosphate anode adhesive, preparation method and application thereof |
| CN112952297B (en) * | 2021-04-26 | 2023-03-21 | 乐凯胶片股份有限公司 | Ceramic diaphragm, preparation method thereof and lithium battery |
| CN115404029A (en) * | 2022-10-19 | 2022-11-29 | 苏州德比电子材料科技有限公司 | High-temperature-resistant low-moisture-content diaphragm binder and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0546640A1 (en) * | 1991-12-13 | 1993-06-16 | Shell Internationale Researchmaatschappij B.V. | Interpolymer-based binders |
| US5322897A (en) * | 1988-07-07 | 1994-06-21 | Basf Lacke | Copolymers containing hydroxyl groups, based on vinyl ester monomers, vinylaromatic monomers and hydroxylalkyl ester monomers, process for the preparation thereof and use thereof in coating compositions |
| CN105131875A (en) * | 2015-08-26 | 2015-12-09 | 深圳市贝特瑞新能源材料股份有限公司 | Aqueous binder for lithium ion battery as well as preparation method and application thereof |
| CN105315927A (en) * | 2015-11-01 | 2016-02-10 | 华南理工大学 | Special adhesive for polyvinyl alcohol/polyolefine composite film and preparation method of special adhesive |
| CN105440988A (en) * | 2014-09-10 | 2016-03-30 | 藤森工业株式会社 | Adhesive composition and surface protective film |
-
2019
- 2019-06-14 CN CN201910515614.6A patent/CN110172124B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5322897A (en) * | 1988-07-07 | 1994-06-21 | Basf Lacke | Copolymers containing hydroxyl groups, based on vinyl ester monomers, vinylaromatic monomers and hydroxylalkyl ester monomers, process for the preparation thereof and use thereof in coating compositions |
| EP0546640A1 (en) * | 1991-12-13 | 1993-06-16 | Shell Internationale Researchmaatschappij B.V. | Interpolymer-based binders |
| CN105440988A (en) * | 2014-09-10 | 2016-03-30 | 藤森工业株式会社 | Adhesive composition and surface protective film |
| CN105131875A (en) * | 2015-08-26 | 2015-12-09 | 深圳市贝特瑞新能源材料股份有限公司 | Aqueous binder for lithium ion battery as well as preparation method and application thereof |
| CN105315927A (en) * | 2015-11-01 | 2016-02-10 | 华南理工大学 | Special adhesive for polyvinyl alcohol/polyolefine composite film and preparation method of special adhesive |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110172124A (en) | 2019-08-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110172124B (en) | Special adhesive for lithium battery ceramic diaphragm and preparation method and application thereof | |
| CN102533177B (en) | High water resistance emulsion polyacrylate pressure-sensitive adhesive and preparation method and application thereof | |
| CN110003382B (en) | Special aqueous solution type adhesive for lithium battery ceramic diaphragm and preparation method and application thereof | |
| CN101974194B (en) | Epoxy modified styrene-acrylate emulsion and preparation method thereof | |
| CN101168584B (en) | Redispersable latex powder emulsion, redispersable latex powder and preparation method thereof | |
| CN104877058B (en) | A kind of polyacrylate resins 3D printing material and preparation method thereof | |
| CN103613702A (en) | Aqueous multi-functional crylic acid extinction resin and preparation method thereof | |
| CN109054570B (en) | Environment-friendly high-strength elastic coating and preparation method thereof | |
| WO2019242318A1 (en) | Waterborne binder, preparation method therefor and use thereof | |
| CN104151584B (en) | Preparation method and product of ultrathin high strength hydrogel membrane | |
| JP2015018776A (en) | Binder for aqueous electrode composition for battery | |
| CN103214629A (en) | Antistatic agent for dacron textile and preparation method of antistatic agent | |
| CN110190235A (en) | A kind of aqueous solution type lithium battery ceramic diaphragm adhesive specially and its preparation method and application | |
| CN110627945B (en) | Acrylate adhesive modified by long-chain unsaturated carboxylic acid or derivative thereof, and preparation method and application thereof | |
| CN103224625A (en) | Preparation method for poly(2,5-dihydroxyl-1,4-phenylene pyridobisimidazole) | |
| CN105440931B (en) | Ultraviolet light solidifies hydrophilic aluminum foil paint composition | |
| CN104761673A (en) | Carbomer and preparation method thereof | |
| CN113528041A (en) | Flame-retardant antistatic protective film and preparation method thereof | |
| CN114456318B (en) | Chitosan-bentonite-acrylic acid water-absorbent resin and preparation method thereof | |
| CN109929371B (en) | Water-based graphene conductive coating and application thereof | |
| CN108878781A (en) | Lithium an- ode and preparation method thereof and lithium ion battery | |
| CN112142917B (en) | Modified chitosan water-based binder and preparation method thereof | |
| CN105441010B (en) | A kind of compound adhesive of optical Response | |
| CN112877012A (en) | Preparation method and application of water-soluble low-modulus acrylic resin adhesive | |
| CN110776863B (en) | Special adhesive for modified lithium battery ceramic diaphragm and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |