CN115044331B - Water-dispersible polymer microparticle emulsion binder for lithium ion battery and preparation method thereof - Google Patents

Water-dispersible polymer microparticle emulsion binder for lithium ion battery and preparation method thereof Download PDF

Info

Publication number
CN115044331B
CN115044331B CN202110254669.3A CN202110254669A CN115044331B CN 115044331 B CN115044331 B CN 115044331B CN 202110254669 A CN202110254669 A CN 202110254669A CN 115044331 B CN115044331 B CN 115044331B
Authority
CN
China
Prior art keywords
water
monomer
dispersible polymer
polymer microparticle
lithium ion
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
Application number
CN202110254669.3A
Other languages
Chinese (zh)
Other versions
CN115044331A (en
Inventor
刘祥
汪舟鹭
张翼
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nanjing Tech University
Original Assignee
Nanjing Tech University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nanjing Tech University filed Critical Nanjing Tech University
Priority to CN202110254669.3A priority Critical patent/CN115044331B/en
Publication of CN115044331A publication Critical patent/CN115044331A/en
Application granted granted Critical
Publication of CN115044331B publication Critical patent/CN115044331B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/003—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • 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
    • C08F212/00—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 an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • 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
    • C08F212/00—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 an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/12—Monomers containing a branched unsaturated aliphatic radical or a ring substituted by an alkyl radical
    • 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
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic 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
    • C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
    • C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
    • 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
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to a water-dispersible polymer microparticle emulsion binder for lithium ion batteries and a preparation method thereof, wherein the binder is water-dispersible polymer microparticle emulsion, a dispersion medium is water, the emulsion dispersion is specifically polymer microparticles with a core-shell structure, the total of conjugated diene monomer and aromatic vinyl monomer in the core part of the emulsion is more than 80 percent (weight) of the total of the monomer mixture in the core part, and the total of acrylate monomer and acrylonitrile and/or methacrylonitrile monomer in the shell part of the emulsion is more than 15 percent (weight) of the total of the monomer mixture in the shell part. The binder can be used for manufacturing a negative electrode of a lithium ion secondary battery and is used for binding an electrode active material, a conductive agent and a current collector.

Description

Water-dispersible polymer microparticle emulsion binder for lithium ion battery and preparation method thereof
Technical Field
The invention relates to a water-dispersible polymer microparticle emulsion binder for a lithium ion battery and a preparation method thereof.
Background
A lithium ion secondary battery generally consists of a positive electrode, a negative electrode, a separator, and an electrolyte. The negative electrode is composed of an active material, a conductive agent, a binder and a current collector, wherein the active material, the conductive agent and the binder are mixed into liquid slurry, coated on the current collector, and dried and rolled to prepare the negative electrode of the lithium ion battery. The binder, which is one of the internal components of the battery, is capable of connecting the active material and the conductive agent and adhering them to the current collector to form a complete electrode structure. In general, the binder is used in an amount of only 1.5% -5% of the total electrode mass, but it has an important effect on maintaining the stability of the electrode structure and improving the electrochemical properties of the electrode.
The binder for the negative electrode should have the following characteristics: (1) The binder can have enough interaction force with the active substance and the current collector, so that the active substance is always in a conductive network; (2) Through proper swelling electrolyte, the lithium ion conduction in the electrode can be promoted while the electrode structure is kept stable; (3) possess good mechanical properties; (4) Electrochemical stability is maintained over a charge/discharge voltage range.
Polyvinylidene fluoride (PVDF) has long been the binder mainly used in the anode and cathode of lithium ion secondary batteries, has good electrochemical, chemical and thermal stability and high mechanical strength, meets the basic requirement of serving as an electrode binder and is widely used. However, PVDF and an active material are only combined by simple van der waals force, so that the adhesion is poor, and when the PVDF is used as a negative electrode binder, the volume expansion of the active material cannot be well adapted, and the negative electrode particles are easily separated from a conductive network, so that the battery capacity is excessively fast attenuated. The sodium carboxymethylcellulose/styrene-butadiene latex (CMC/SBR) mixed bonding system has the advantages of small elastic modulus, high elongation at break and high bonding strength, and the cycle capacity retention rate of the negative electrode adopting the CMC/SBR composite bonding agent is remarkably improved compared with that of the negative electrode adopting the PVDF bonding agent. However, the conventional SBR binder has poor ability to swell an electrolyte, and electrolyte/electrode interfacial film resistance and charge transfer resistance are increased, resulting in poor low-temperature performance of the lithium ion battery.
International publication WO2012/128182 reports that an SBR composite binder containing dicarboxylic acid, although it shows excellent processability and good binding property during the electrode preparation process, shows poor low temperature performance of a lithium ion battery due to poor compatibility with an electrolyte.
CN 101457131B discloses a water-based adhesive for electrode material of inside-lining ion battery and its preparation method, the material is acrylic ester, the low-polarity polymer is used as core, the high-polarity polymer is used as shell layer, so as to form the water-based adhesive with core-shell structure, the inside of which is soft and the outside of which is hard. The adhesive shows good low-temperature performance of the lithium ion battery, but has poor adhesive strength.
Disclosure of Invention
Aiming at the problems that the existing PVDF resin binder has low binding force, and the polyacrylate binder is easy to expand or slowly dissolve in electrolyte and has unstable performance; the polyacrylic acid adhesive is easy to peel off from the electrode plate in the rolling and winding processes, and absorbs water and moisture; the CMC/SBR composite binder has poor capability of swelling electrolyte, and increases electrolyte/electrode interface film impedance and charge transfer impedance, so that the lithium ion battery has poor low-temperature performance. Through repeated research and demonstration, the invention provides a water-dispersible polymer microparticle emulsion binder for a lithium ion battery and a preparation method thereof, which solve the application problems, and particularly have excellent low-temperature performance.
The adhesive has excellent adhesive property and good processing property. The ester group with a certain proportion is introduced into the shell part, so that a complete lithium ion transportation channel is formed inside the electrode, the lithium ion transfer impedance is reduced, the lithium ion conduction rate is improved, and the low-temperature performance and the excellent low-temperature performance of the lithium ion battery are improved.
The invention relates to a water-dispersible polymer microparticle emulsion binder for lithium ion batteries and a preparation method thereof, wherein the binder is water-dispersible polymer microparticle emulsion, in particular to polymer microparticles with a core-shell structure, the total content of conjugated diene monomer and aromatic vinyl monomer in the core part of the binder is more than 80 percent (weight) of the total content of monomer mixture in the core part, and the total content of acrylate monomer and acrylonitrile and/or methacrylonitrile monomer in the shell part of the binder is more than 15 percent (weight) of the total content of monomer mixture in the shell part. The water-dispersible polymer microparticle emulsion binder is dried to form a film, wherein the film forming condition is 25 ℃ and the relative humidity is 75%, and the conductivity of the film is 10 after being immersed in electrolyte solution at 60 ℃ for 72 hours -5 s/cm to 10 3 s/cm. The particle diameter of the water-dispersible polymer microparticle is 120-450nm, the glass transition temperature of the water-dispersible polymer is-20-40 ℃, the gel content of the water-dispersible polymer is 60-90%, and the pH of the water-dispersible polymer microparticle emulsion binder is 7.5-8.5.
The invention relates to a water-dispersible polymer microparticle emulsion binder for a lithium ion battery and a preparation method thereof, comprising the following steps:
a water-dispersed polymer microparticle emulsion binder for lithium ion battery is characterized by that it is a water-dispersed polymer microparticle emulsion whose dispersion medium is water, and the emulsion dispersion is specifically polymer microparticles with core-shell structure, and its inner core portion contains conjugated diene monomer and aromatic vinyl monomer and total is more than 80% by weight of total core portion monomer mixture, and its outer shell portion contains acrylate monomer and acrylonitrile and/or methacrylonitrile monomer and total is more than 15% by weight of total shell portion monomer mixture.
The water-dispersible polymer microparticle emulsion binder for the lithium ion battery is characterized in that the particle size of the water-dispersible polymer microparticles is 120-450nm, the glass transition temperature of the water-dispersible polymer is-20-40 ℃, and the gel content of the water-dispersible polymer is 60-90%.
The water-dispersible polymer microparticle emulsion binder for lithium ion batteries is characterized in that the binder is dried to form a film, wherein the film forming condition is 25 ℃ and the relative humidity is 75%, and the tensile strength of the film is 1000-5000N/cm 2 After immersing in an electrolyte at 60℃for 72 hours, the film had a conductivity of 10 -5 s/cm to 10 3 s/cm。
The preparation method of the water-dispersible polymer microparticle emulsion binder for the lithium ion battery is characterized in that the core part adopts conjugated diene monomer, aromatic vinyl monomer and unsaturated monomer containing acid functional group, or adopts conjugated diene monomer, aromatic vinyl monomer, unsaturated monomer containing acid functional group and more than one other unsaturated monomer which can be copolymerized with the monomers; wherein the total of the conjugated diene monomer and the aromatic vinyl monomer is 80% or more of the total amount of the core monomer mixture; preparing core polymer microparticle emulsion by batch emulsion polymerization or/and stepwise dropwise addition semi-continuous emulsion polymerization method in the presence of alkyl sulfate emulsifier or/and sulfonate emulsifier water solution and water-soluble peroxidation initiator or initiator and reducer, wherein the polymerization temperature is 30-85deg.C; the shell part adopts conjugated diene monomer, aromatic vinyl monomer, unsaturated monomer containing acid functional group, acrylic ester monomer and acrylonitrile and/or methyl acrylonitrile monomer, and the total content of acrylic ester monomer and acrylonitrile and/or methyl acrylonitrile monomer is 15% of the total content of shell part monomer, under the existence of core part polymer microparticle emulsion, all the above-mentioned monomers are mixed and emulsified by utilizing alkyl sulfate emulsifier or/and sulfonate emulsifier, and under the existence of water-soluble peroxidation initiator or initiator and reducing agent, the water-dispersed polymer microparticle emulsion adhesive is prepared by means of intermittent emulsion polymerization or semi-continuous emulsion polymerization method of gradual dropwise addition, and its polymerization temperature is 35-85 deg.C.
The preparation method of the water-dispersible polymer microparticle emulsion binder for the lithium ion battery is characterized in that the conjugated diene monomer is one of 1, 3-butadiene, isoprene, methylpentadiene, phenylbutadiene, 3, 4-dimethyl-1, 3-hexadiene and 4, 5-diethyl-1, 3-octadiene and a mixture of more than one of any proportion; the aromatic vinyl monomer is styrene, alpha-methylstyrene, 4-tert-butylstyrene, chlorovinylbenzene, vinyltoluene, divinylbenzene, p-chloromethylstyrene, methyl 4-vinylbenzoate, 2-vinylnaphthalene, 4-vinylbenzoic acid, methyl 4-vinylbenzoate, 2-vinylpyridine, 4-vinylpyridine; the unsaturated monomer containing acid functional groups is one or more than one of acrylic acid, methacrylic acid, 2-acrylamide-2-methylpropanesulfonic acid, crotonic acid, fumaric acid, maleic acid, 2-methyl maleic acid and itaconic acid and a mixture of more than one of the above components in any proportion; the alkyl sulfate emulsifier is one or more of sodium dodecyl sulfate, sodium dodecyl ether sulfate and ammonium dodecyl ether sulfate and a mixture of more than one of the sodium dodecyl sulfate, the sodium dodecyl ether sulfate and the ammonium dodecyl ether sulfate in any proportion; the sulfonate emulsifier is one or more of sodium dodecyl benzene sulfonate, sodium hexadecyl sulfonate, sodium dodecyl diphenyl ether disulfonate and sodium diisobutyl naphthalene sulfonate and a mixture of more than one of the sodium dodecyl benzene sulfonate, the sodium hexadecyl sulfonate, the sodium dodecyl diphenyl ether disulfonate and the sodium diisobutyl naphthalene sulfonate in any proportion; the water-soluble peroxide initiator is one or more of potassium persulfate, sodium persulfate, ammonium persulfate, tert-butyl hydroperoxide and hydrogen peroxide and a mixture of more than one of the potassium persulfate, the sodium persulfate, the ammonium persulfate, the tert-butyl hydroperoxide and the hydrogen peroxide in any proportion; the reducing agent is one of glucose, sodium bisulphite and sodium sulfite and a mixture of more than one of the above components in any proportion.
The preparation method of the water-dispersible polymer microparticle emulsion binder for the lithium ion battery is characterized in that in the process of preparing the core polymer microparticle emulsion, other unsaturated monomers with copolymerization possibility are one or more of methyl acrylate, ethyl acrylate, butyl methacrylate, isooctyl acrylate, methyl methacrylate, glycidyl acrylate, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide and N-tertiary butyl acrylamide and a mixture of more than one of the above components in any proportion.
The preparation method of the water-dispersible polymer microparticle emulsion binder for the lithium ion battery is characterized in that the usage amount of the conjugated diene monomer and aromatic vinyl monomer mixture is 99.5-80 percent (weight) of the total amount of the core monomer mixture in the process of preparing the core polymer microparticle emulsion; the amount of the unsaturated monomer containing acid functional groups is 0.5-9.0% by weight of the total amount of the core monomer mixture; the amount of the other unsaturated monomers which are possibly copolymerized is 0 to 11.0% by weight based on the total amount of the core monomer mixture; the usage amount of the alkyl sulfate emulsifier or/and the sulfonate emulsifier is 0.05-3.0 percent (weight) of the total amount of the core monomer mixture; the water-soluble peroxidation initiator is used in an amount of 0.05-3.0% by weight based on the total amount of the core monomer mixture; the reducing agent is used in an amount of 0 to 0.5% by weight based on the total amount of the core monomer mixture.
The preparation method of the water-dispersible polymer microparticle emulsion binder for the lithium ion battery is characterized in that in the process of preparing the water-dispersible polymer microparticle emulsion binder for the shell, the acrylic ester monomer is one or more of methyl acrylate, ethyl acrylate, butyl methacrylate, isooctyl acrylate, methyl methacrylate and glycidyl acrylate and a mixture of more than one of the methyl acrylate, the ethyl acrylate, the butyl methacrylate, the isooctyl acrylate, the methyl methacrylate and the glycidyl acrylate in any proportion.
The preparation method of the water-dispersible polymer microparticle emulsion binder for the lithium ion battery is characterized in that in the process of preparing the water-dispersible polymer microparticle emulsion binder for the shell, the usage amount of the conjugated diene monomer and aromatic vinyl monomer mixture is 84.95-60 percent (weight) of the total shell monomer mixture; the usage amount of the unsaturated monomer containing acid functional groups is 0.05-10 percent (weight) of the total amount of the shell part monomer mixture; the usage amount of the acrylic monomer and the acrylonitrile and/or methacrylonitrile monomer mixture is 15-30 percent (weight) of the total shell monomer mixture; the usage amount of the alkyl sulfate emulsifier or/and the sulfonate emulsifier is 0.05-3.0 percent (weight) of the total shell monomer mixture; the usage amount of the water-soluble peroxidation initiator is 0.05-3.0 percent (weight) of the total shell monomer mixture; the reducing agent is used in an amount of 0 to 0.5% by weight based on the total amount of the shell monomer mixture.
The preparation method of the water-dispersible polymer microparticle emulsion binder for the lithium ion battery is characterized in that the weight ratio of the shell monomer mixture to the core monomer mixture is 90:10-20:80.
The invention also discloses application of the water-dispersible polymer microparticle emulsion binder for the lithium ion battery in preparing a negative electrode of the lithium ion secondary battery, which is used for binding an electrode active material, a conductive agent and a current collector.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are only for the purpose of the present invention and are not intended to limit the scope of the present invention. It is to be understood that various changes and modifications may be made by one skilled in the art after reading the disclosure herein, and that such equivalents are intended to fall within the scope of the claims appended hereto.
In the examples below, the core monomer mixture includes monomers of conjugated dienes, aromatic vinyl monomers, unsaturated monomers containing acid functionality, and one or more other unsaturated monomers that may have a possibility of copolymerization with the above monomers; the shell monomer mixture is conjugated diene monomer, aromatic vinyl monomer, unsaturated monomer containing acid functional group, acrylic monomer and acrylonitrile and/or methacrylonitrile monomer. The low-temperature test evaluation method comprises the following steps: the dispersion type polymer microparticle emulsion binder prepared in the example was assembled into a 800mAh cylindrical lithium battery, and after standing at 25℃for 24 hours, charged to 4.3V at 1℃to measure the charging capacity W at that time 0 After that, discharge was performed to 3.0V at 1C. Then charging to 4.3V at-10deg.C, measuring the charging timeCapacitance W 1 . Low temperature performance Δw=w1/w0×100%, the greater the value of Δw, the better the low temperature performance.
Example 1
(1) Preparation of core polymer microparticle emulsion:
100g of deionized water, 0.025g of sodium dodecyl sulfate, 40g of styrene, 9g of acrylic acid and 11g of methyl acrylate were respectively charged into a pressure-resistant emulsification vessel equipped with a stirring paddle and a nitrogen inlet valve. After the oxygen was removed by nitrogen exchange, 40g of 1, 3-butadiene was taken in and stirred to obtain a monomer mixture for use.
To a pressure-resistant reaction vessel equipped with a stirring paddle, a thermometer, a nitrogen inlet valve and a reflux condenser, 80g of deionized water and 0.025g of sodium dodecyl sulfate were added, and the temperature was raised to 30℃with stirring, and an aqueous potassium persulfate solution (0.04 g of potassium persulfate dissolved in 10g of deionized water) was added to the reaction vessel. Simultaneously, continuously dripping the monomer mixture for 300 minutes, then adding 0.01g of potassium persulfate and 10g of deionized water after dripping, heating to 65 ℃, keeping the temperature until the conversion rate is 97%, stopping the reaction, and cooling to obtain the core polymer microparticle emulsion for later use.
(2) Preparation of water-dispersible polymer microparticle emulsion binder
Into a pressure-resistant emulsification vessel equipped with a stirring paddle and a nitrogen inlet valve, 1100g of deionized water, 0.45g of sodium dodecyl ether sulfate, 364.55g of alpha-methylstyrene, 0.45g of acrylic acid, 35g of methyl acrylate and 100g of acrylonitrile were respectively charged. After the oxygen was removed by nitrogen exchange, 400g of 1, 3-butadiene was taken in and stirred to obtain a monomer mixture for use.
The core polymer microparticle emulsion prepared above was charged into a pressure-resistant reaction vessel equipped with a stirring paddle, a thermometer, a nitrogen inlet valve and a reflux condenser, and the temperature was raised to 35℃to charge an aqueous potassium persulfate solution (0.40 g of potassium persulfate dissolved in 150g of deionized water) into the reaction vessel. Meanwhile, continuously dripping the monomer mixture for 300 minutes, then adding 0.05g of potassium persulfate and 50g of deionized water after finishing dripping, heating to 75 ℃, keeping the temperature until the conversion rate is 97%, stopping the reaction, cooling, finally removing residual monomers, and adjusting the pH value to 7.5 to obtain the water-dispersible polymer microparticle emulsion binder, wherein the particle size of the water-dispersible polymer microparticles is 450nm, the glass transition temperature of the water-dispersible polymer is 9 ℃, and the gel content of the water-dispersible polymer is 60%.
(3) Aqueous dispersion type polymer microparticle emulsion binder performance
The prepared water-dispersible polymer microparticle emulsion binder is dried to form a film, wherein the film forming condition is 25 ℃ and the relative humidity is 75%, and the tensile strength of the film is 1650N/cm 2 After immersion in an electrolyte at 60℃for 72 hours, the film had a conductivity of 2X 10 -2 s/cm。
And (3) performing battery test by using the prepared water-dispersible polymer microparticle emulsion binder, wherein the delta W is 77% according to the low-temperature test at-10 ℃.
Example 2
(1) Preparation of core polymer microparticle emulsion:
100g of deionized water, 1.5g of sodium dodecyl ether sulfate, 48g of alpha-methylstyrene, 0.5g of methacrylic acid and 0.5g of ethyl acrylate were respectively charged into a pressure-resistant emulsification vessel equipped with a stirring paddle and a nitrogen inlet valve. After oxygen was removed by nitrogen exchange, 41g of isoprene was taken in, and the resultant monomer mixture was stirred for use.
To a pressure-resistant reaction vessel equipped with a stirring paddle, a thermometer, a nitrogen inlet valve and a reflux condenser, 80g of deionized water and 1.5g of sodium dodecyl ether sulfate were added, and the temperature was raised to 50℃with stirring, and an aqueous sodium persulfate solution (2.5 g of sodium persulfate dissolved in 10g of deionized water) was added to the reaction vessel. Simultaneously, continuously dripping the monomer mixture for 300 minutes, then adding 0.5g of sodium persulfate and 10g of deionized water after dripping, heating to 75 ℃, keeping the temperature until the conversion rate is 97%, stopping the reaction, and cooling to obtain the core polymer microparticle emulsion for later use.
(2) Preparation of water-dispersible polymer microparticle emulsion binder
Into a pressure-resistant emulsification vessel equipped with a stirring paddle and a nitrogen inlet valve, 0.05g of deionized water, 0.75g of sodium dodecyl ether sulfate, 7.5g of alpha-methylstyrene, 2.5g of methacrylic acid, 2.5g of ethyl acrylate and 5g of methacrylonitrile were respectively added. After oxygen was removed by nitrogen exchange, 7.5g of isoprene was taken in, and the resulting monomer mixture was stirred for use.
The core polymer microparticle emulsion prepared above was charged into a pressure-resistant reaction vessel equipped with a stirring paddle, a thermometer, a nitrogen inlet valve and a reflux condenser, and heated to 55℃to charge an aqueous sodium persulfate solution (0.6 g of sodium persulfate dissolved in 3g of deionized water) into the reaction vessel. Meanwhile, continuously dripping the monomer mixture for 300 minutes, then adding 0.15g of sodium persulfate and 1g of deionized water after dripping, heating to 85 ℃, keeping the temperature until the conversion rate is 97%, stopping the reaction, cooling, finally removing residual monomers, and adjusting the pH value to 8.0 to obtain the water-dispersible polymer microparticle emulsion binder, wherein the particle size of the water-dispersible polymer microparticles is 120nm, the glass transition temperature of the water-dispersible polymer is 13 ℃, and the gel content of the water-dispersible polymer is 90%.
(3) Aqueous dispersion type polymer microparticle emulsion binder performance
The prepared water-dispersible polymer microparticle emulsion binder is dried to form a film, wherein the film forming condition is 25 ℃ and the relative humidity is 75%, and the tensile strength of the film is 1020N/cm 2 After immersion in an electrolyte at 60℃for 72 hours, the film had a conductivity of 1.2X10 -1 s/cm。
The battery test was carried out using the prepared water-dispersible polymer microparticle emulsion binder, and the low-temperature test at-10 ℃ gave a Δw of 79%.
Example 3
(1) Preparation of core polymer microparticle emulsion:
100g of deionized water, 0.5g of ammonium dodecyl ether sulfate, 0.5g of sodium dodecyl benzene sulfonate, 30g of 4-tert-butylstyrene, 3g of 2-acrylamido-2-methylpropanesulfonic acid and 2g of butyl acrylate are respectively added into a pressure-resistant emulsification vessel equipped with a stirring paddle and a nitrogen inlet valve. After exchange with nitrogen to remove oxygen, 65g of methylpentadiene was taken in and stirred to obtain a monomer mixture for use.
To a pressure-resistant reaction vessel equipped with a stirring paddle, a thermometer, a nitrogen inlet valve and a reflux condenser, 80g of deionized water, 0.5g of ammonium dodecyl ether sulfate and 0.5g of sodium dodecyl benzene sulfonate were added, and the temperature was raised to 55℃with stirring, and an aqueous t-butyl hydroperoxide solution (1.0 g of t-butyl hydroperoxide was dissolved in 10g of deionized water) was added to the reaction vessel. Simultaneously, continuously dripping the monomer mixture for 300 minutes, then adding 0.3g of tert-butyl hydroperoxide and 10g of deionized water after dripping, heating to 85 ℃, keeping the temperature until the conversion rate is 97%, stopping the reaction, and cooling to obtain the core polymer microparticle emulsion for later use.
(2) Preparation of water-dispersible polymer microparticle emulsion binder
400g of deionized water, 2.0g of ammonium dodecyl ether sulfate, 2.0g of sodium dodecyl benzene sulfonate, 180g of 4-tert-butylstyrene, 8g of 2-acrylamido-2-methylpropanesulfonic acid, 47g of butyl methacrylate, 10g of acrylonitrile and 15g of methacrylonitrile are respectively added into a pressure-resistant emulsification vessel provided with a stirring paddle and a nitrogen inlet valve. After the oxygen was removed by nitrogen exchange, 140g of methylpentadiene was taken in and stirred to obtain a monomer mixture for use.
The core polymer microparticle emulsion prepared above was charged into a pressure-resistant reaction vessel equipped with a stirring paddle, a thermometer, a nitrogen inlet valve and a reflux condenser, and heated to 65℃to charge an aqueous t-butyl hydroperoxide solution (3 g of t-butyl hydroperoxide was dissolved in 100g of deionized water). And simultaneously, continuously dripping the monomer mixture for 300 minutes, then adding 1g of tert-butyl hydroperoxide and 50g of deionized water after dripping, heating to 80 ℃, keeping the temperature until the conversion rate is 97%, stopping the reaction, cooling, finally removing residual monomers, and adjusting the pH value to 8.5 to obtain the water-dispersible polymer microparticle emulsion binder, wherein the particle size of the water-dispersible polymer microparticles is 150nm, the glass transition temperature of the water-dispersible polymer is 20 ℃, and the gel content of the water-dispersible polymer is 75%.
(3) Aqueous dispersion type polymer microparticle emulsion binder performance
The prepared water-dispersible polymer microparticle emulsion binder is dried to form a film, wherein the film forming condition is 25 ℃ and the relative humidity is 75%, and the tensile strength of the film is 1730N/cm 2 After immersion in an electrolyte at 60℃for 72 hours, the film had a conductivity of 2.3X10 0 s/cm。
And (3) performing battery test by using the prepared water-dispersible polymer microparticle emulsion binder, wherein the delta W is 80% according to the low-temperature test at-10 ℃.
Example 4
(1) Preparation of core polymer microparticle emulsion:
100g of deionized water, 0.6g of sodium dodecyl sulfate, 0.5g of sodium hexadecylsulfonate, 41g of chlorovinylbenzene and 5g of crotonic acid were respectively charged into a pressure-resistant emulsification vessel equipped with a stirring paddle and a nitrogen inlet valve. After the oxygen was removed by nitrogen exchange, 54g of phenylbutadiene was taken in and stirred to obtain a monomer mixture for use.
To a pressure-resistant reaction vessel equipped with a stirring paddle, a thermometer, a nitrogen inlet valve and a reflux condenser, 80g of deionized water and 0.6g of sodium dodecyl sulfate were added, and the temperature was raised to 43℃with stirring, and an aqueous ammonium persulfate solution (ammonium persulfate 1.2g dissolved in 10g of deionized water) was added to the reaction vessel. Simultaneously, continuously dripping the monomer mixture for 300 minutes, then adding 0.7g of ammonium persulfate and 10g of deionized water after dripping, simultaneously heating to 77 ℃, keeping the temperature until the conversion rate is 97%, stopping the reaction, and cooling to obtain the core polymer microparticle emulsion for later use.
(2) Preparation of water-dispersible polymer microparticle emulsion binder
150g of deionized water, 1.2g of sodium dodecyl sulfate, 0.5g of hexadecyl sodium sulfonate, 42g of chlorovinylbenzene, 8g of crotonic acid, 20g of butyl acrylate, 12g of acrylonitrile and 18g of methacrylonitrile are respectively added into a pressure-resistant emulsification vessel provided with a stirring paddle and a nitrogen inlet valve. After oxygen was removed by nitrogen exchange, 100g of phenylbutadiene was taken in and stirred to obtain a monomer mixture for use.
The core polymer microparticle emulsion prepared above was charged into a pressure-resistant reaction vessel equipped with a stirring paddle, a thermometer, a nitrogen inlet valve and a reflux condenser, heated to 58℃and an aqueous ammonium persulfate solution (ammonium persulfate 1.3g dissolved in 80g deionized water) was added to the reaction vessel. Meanwhile, continuously dripping the monomer mixture for 300 minutes, then adding 0.6g of ammonium persulfate and 20g of deionized water after dripping, heating to 83 ℃ at the same time, keeping the temperature until the conversion rate is 97%, stopping the reaction, cooling, finally removing residual monomers, and adjusting the pH value to 8.4 to obtain the water-dispersible polymer microparticle emulsion binder, wherein the particle size of the water-dispersible polymer microparticles is 180nm, the glass transition temperature of the water-dispersible polymer is-20 ℃, and the gel content of the water-dispersible polymer is 65%.
(3) Aqueous dispersion type polymer microparticle emulsion binder performance
The prepared water-dispersible polymer microparticle emulsion binder is dried to form a film, wherein the film forming condition is 25 ℃, the relative humidity is 75%, and the tensile strength of the film is 3300N/cm 2 After immersion in an electrolyte at 60℃for 72 hours, the film had a conductivity of 3.3X10 2 s/cm。
The battery test was carried out using the prepared water-dispersible polymer microparticle emulsion binder, and the Δw was evaluated to be 84% by a low temperature test at-10 ℃.
Example 5
(1) Preparation of core polymer microparticle emulsion:
100g of deionized water, 1.2g of sodium dodecyl diphenyl ether disulfonate, 30g of vinyl toluene, 7g of fumaric acid and 1g of isooctyl acrylate are respectively added into a pressure-resistant emulsification vessel equipped with a stirring paddle and a nitrogen inlet valve. After the oxygen was removed by nitrogen exchange, 62g of 3, 4-dimethyl-1, 3-hexadiene was taken in and stirred to obtain a monomer mixture for use.
To a pressure-resistant reaction vessel equipped with a stirring paddle, a thermometer, a nitrogen inlet valve and a reflux condenser, 80g of deionized water and 0.2g of sodium dodecyl diphenyl ether disulfonate were added, and the temperature was raised to 39℃with stirring, and an aqueous solution of potassium persulfate and sodium persulfate (0.3 g of potassium persulfate and 0.1g of sodium persulfate were dissolved in 10g of deionized water) was added to the reaction vessel. Simultaneously, continuously dripping the monomer mixture for 300 minutes, after dripping, adding 0.1g of potassium persulfate, 0.1g of sodium persulfate and 10g of deionized water, heating to 70 ℃, keeping the temperature until the conversion rate is 97%, stopping the reaction, and cooling to obtain the core polymer microparticle emulsion for later use.
(2) Preparation of water-dispersible polymer microparticle emulsion binder
10g of deionized water, 0.8g of sodium dodecyl diphenyl ether disulfonate, 12g of vinyl toluene, 7g of fumaric acid, 8g of isooctyl acrylate, 5g of acrylonitrile and 18g of methacrylonitrile are respectively added into a pressure-resistant emulsification vessel provided with a stirring paddle and a nitrogen inlet valve. After the oxygen was removed by nitrogen exchange, 50g of 3, 4-dimethyl-1, 3-hexadiene was taken in and stirred to obtain a monomer mixture for use.
The core polymer microparticle emulsion prepared above was charged into a pressure-resistant reaction vessel equipped with a stirring paddle, a thermometer, a nitrogen inlet valve and a reflux condenser, and heated to 54℃to add potassium persulfate and an aqueous sodium persulfate solution (0.5 g of potassium persulfate and 0.8g of sodium persulfate dissolved in 60g of deionized water) to the reaction vessel. Meanwhile, continuously dripping the monomer mixture for 300 minutes, then adding 0.2g of potassium persulfate, 0.3g of sodium persulfate and 30g of deionized water after dripping, heating to 82 ℃ at the same time, keeping the temperature until the conversion rate is 97%, stopping the reaction, cooling, finally removing residual monomers, adjusting the pH value to 7.6, and obtaining the water-dispersible polymer microparticle emulsion binder, wherein the particle size of the water-dispersible polymer microparticles is 235nm, the glass transition temperature of the water-dispersible polymer is-18 ℃, and the gel content of the water-dispersible polymer is 66%.
(3) Aqueous dispersion type polymer microparticle emulsion binder performance
The prepared water-dispersible polymer microparticle emulsion binder is dried to form a film, wherein the film forming condition is 25 ℃ and the relative humidity is 75%, and the tensile strength of the film is1450N/cm 2 After immersion in an electrolyte at 60℃for 72 hours, the film had a conductivity of 6.8X10 1 s/cm。
The battery test was carried out using the prepared water-dispersible polymer microparticle emulsion binder, and the low-temperature test at-10 ℃ gave an evaluation of Δw of 83%.
Example 6
(1) Preparation of core polymer microparticle emulsion:
100g of deionized water, 0.9g of diisobutylnaphthalene sulfonate, 41g of divinylbenzene, 4g of maleic acid and 10g of methyl methacrylate were respectively charged into a pressure-resistant emulsification vessel equipped with a stirring paddle and a nitrogen inlet valve. After the oxygen was removed by nitrogen exchange, 45g of 4, 5-diethyl-1, 3-octadiene was taken in and stirred to obtain a monomer mixture for use.
To a pressure-resistant reaction vessel equipped with a stirring paddle, a thermometer, a nitrogen inlet valve and a reflux condenser, 80g of deionized water and 0.5g of sodium diisobutylnaphthalene sulfonate were added, and the temperature was raised to 57℃with stirring, and an aqueous hydrogen peroxide solution (0.8 g of hydrogen peroxide was dissolved in 10g of deionized water) was added to the reaction vessel. Simultaneously, continuously dripping the monomer mixture for 300 minutes, then adding 0.4g of hydrogen peroxide and 10g of deionized water after dripping, simultaneously heating to 77 ℃, keeping the temperature until the conversion rate is 97%, stopping the reaction, and cooling to obtain the core polymer microparticle emulsion for later use.
(2) Preparation of water-dispersible polymer microparticle emulsion binder
Into a pressure-resistant emulsification vessel equipped with a stirring paddle and a nitrogen inlet valve, 1g of deionized water, 0.75g of sodium diisobutylnaphthalene sulfonate, 20g of divinylbenzene, 4g of maleic acid, 1g of methyl methacrylate and 13g of methacrylonitrile were respectively charged. After the oxygen was removed by nitrogen exchange, 21g of 4, 5-diethyl-1, 3-octadiene was taken in and stirred to obtain a monomer mixture for use.
The core polymer microparticle emulsion prepared above was charged into a pressure-resistant reaction vessel equipped with a stirring paddle, a thermometer, a nitrogen inlet valve and a reflux condenser, and heated to 53℃to charge an aqueous hydrogen peroxide solution (0.8 g of hydrogen peroxide was dissolved in 40g of deionized water). Meanwhile, continuously dripping the monomer mixture for 300 minutes, then adding 0.7g of hydrogen peroxide and 14g of deionized water after dripping, heating to 80 ℃, keeping the temperature until the conversion rate is 97%, stopping the reaction, cooling, finally removing residual monomers, and adjusting the pH value to 7.7 to obtain the water-dispersible polymer microparticle emulsion binder, wherein the particle size of the water-dispersible polymer microparticles is 350nm, the glass transition temperature of the water-dispersible polymer is-15 ℃, and the gel content of the water-dispersible polymer is 72%.
(3) Aqueous dispersion type polymer microparticle emulsion binder performance
The prepared water-dispersible polymer microparticle emulsion binder is dried to form a film, wherein the film forming condition is 25 ℃ and the relative humidity is 75%, and the tensile strength of the film is 1010N/cm 2 After immersing in an electrolyte at 60℃for 72 hours, the film had a conductivity of 3.8X10 -3 s/cm。
The battery test was carried out using the prepared water-dispersible polymer microparticle emulsion binder, and the low-temperature test at-10 ℃ gave a Δw of 76%.
Example 7
(1) Preparation of core polymer microparticle emulsion:
100g of deionized water, 0.2g of sodium dodecyl sulfate, 0.3g of sodium diisobutylnaphthalene sulfonate, 30g of p-chloromethylstyrene, 8g of 2-methyl maleic acid and 4g of glycidyl acrylate were respectively added into a pressure-resistant emulsification vessel equipped with a stirring paddle and a nitrogen inlet valve. After the oxygen was removed by nitrogen exchange, 58g of 1, 3-butadiene was taken in and stirred to obtain a monomer mixture for use.
To a pressure-resistant reaction vessel equipped with a stirring paddle, a thermometer, a nitrogen inlet valve and a reflux condenser, 80g of deionized water, 0.2g of sodium dodecyl sulfate and 0.3g of sodium diisobutylnaphthalene sulfonate were added, and an aqueous solution of potassium persulfate and glucose (potassium persulfate 2.0g and glucose 0.1g were dissolved in 10g of deionized water) was added while heating to 60℃with stirring. Simultaneously, continuously dripping the monomer mixture for 300 minutes, after dripping, adding 0.1g of potassium persulfate, 0.05g of glucose and 10g of deionized water, heating to 82 ℃, keeping the temperature until the conversion rate is 97%, stopping the reaction, and cooling to obtain the core polymer microparticle emulsion for later use.
(2) Preparation of water-dispersible polymer microparticle emulsion binder
Into a pressure-resistant emulsification vessel equipped with a stirring paddle and a nitrogen inlet valve, 1g of deionized water, 0.5g of sodium dodecyl sulfate, 0.8g of sodium diisobutylnaphthalene sulfonate, 27g of p-chloromethylstyrene, 3g of 2-methyl maleic acid, 5g of glycidyl acrylate and 5g of acrylonitrile were respectively added. After oxygen was removed by nitrogen exchange, 10g of 4, 5-diethyl-1, 3-octadiene was taken in and stirred to obtain a monomer mixture for use.
The core polymer microparticle emulsion prepared above was charged into a pressure-resistant reaction vessel equipped with a stirring paddle, a thermometer, a nitrogen inlet valve and a reflux condenser, and heated to 53℃to an aqueous solution of potassium persulfate and glucose (1.0 g of potassium persulfate and 0.05g of glucose dissolved in 15g of deionized water) in the reaction vessel. Meanwhile, continuously dripping the monomer mixture for 300 minutes, then adding 0.1g of potassium persulfate, 0.05g of glucose and 9g of deionized water after dripping, heating to 80 ℃ at the same time, keeping the temperature until the conversion rate is 97%, stopping the reaction, cooling, finally removing residual monomers, adjusting the pH value to 7.9, and obtaining the water-dispersible polymer microparticle emulsion binder, wherein the particle size of the water-dispersible polymer microparticles is 400nm, the glass transition temperature of the water-dispersible polymer is 15 ℃, and the gel content of the water-dispersible polymer is 74%.
(3) Aqueous dispersion type polymer microparticle emulsion binder performance
The prepared water-dispersible polymer microparticle emulsion binder is dried to form a film, wherein the film forming condition is 25 ℃ and the relative humidity is 75%, and the tensile strength of the film is 2400N/cm 2 After immersion in an electrolyte at 60℃for 72 hours, the film had a conductivity of 1.3X10 1 s/cm。
The battery test was carried out using the prepared water-dispersible polymer microparticle emulsion binder, and the low-temperature test at-10 ℃ gave an evaluation of Δw of 82%.
Example 8
(1) Preparation of core polymer microparticle emulsion:
100g of deionized water, 0.1g of sodium dodecyl ether sulfate, 1.2g of sodium hexadecyl sulfonate, 40g of 4-vinyl methyl benzoate, 2.5g of itaconic acid and 1g of acrylonitrile are respectively added into a pressure-resistant emulsification vessel provided with a stirring paddle and a nitrogen inlet valve. After oxygen was removed by nitrogen exchange, 55g of 1, 3-butadiene and 1.5g of isoprene were taken in, and the resulting monomer mixture was stirred for use.
To a pressure-resistant reaction vessel equipped with a stirring paddle, a thermometer, a nitrogen inlet valve and a reflux condenser, 80g of deionized water, 0.1g of sodium dodecyl ether sulfate, 1.2g of sodium hexadecylsulfonate salt were added, and the temperature was raised to 56℃with stirring, and an aqueous solution of ammonium persulfate and sodium bisulfite (ammonium persulfate 0.8g and sodium bisulfite 0.09g were dissolved in 10g of deionized water) was added to the reaction vessel. Simultaneously, continuously dripping the monomer mixture for 300 minutes, then adding 0.5g of ammonium persulfate, 0.01g of sodium bisulphite and 10g of deionized water after dripping, simultaneously heating to 84 ℃, keeping the temperature until the conversion rate is 97%, stopping the reaction, and cooling to obtain the core polymer microparticle emulsion for later use.
(2) Preparation of water-dispersible polymer microparticle emulsion binder
100g of deionized water, 0.8g of sodium dodecyl ether sulfate, 2.2g of sodium hexadecyl sulfonate, 59g of methyl 4-vinylbenzoate, 6g of itaconic acid, 5g of methyl acrylate, 10g of glycidyl acrylate and 20g of acrylonitrile are respectively added into a pressure-resistant emulsification vessel provided with a stirring paddle and a nitrogen inlet valve. After oxygen was removed by nitrogen exchange, 80g of 1, 3-butadiene and 20g of isoprene were taken in, and the mixture was stirred to obtain a monomer mixture for use.
The core polymer microparticle emulsion prepared above was charged into a pressure-resistant reaction vessel equipped with a stirring paddle, a thermometer, a nitrogen inlet valve and a reflux condenser, and heated to 61℃to an aqueous solution of ammonium persulfate and sodium bisulfite (ammonium persulfate 1.5g and sodium bisulfite 0.03g were dissolved in 100g of deionized water) in the reaction vessel. Meanwhile, continuously dripping the monomer mixture for 300 minutes, then adding 0.4g of ammonium persulfate, 0.01g of sodium bisulphite and 50g of deionized water after dripping, heating to 84 ℃, keeping the temperature until the conversion rate is 97%, stopping the reaction, cooling, finally removing residual monomers, adjusting the pH value to 8.1, and obtaining the water-dispersible polymer microparticle emulsion binder, wherein the particle size of the water-dispersible polymer microparticles is 220nm, the glass transition temperature of the water-dispersible polymer is-5 ℃, and the gel content of the water-dispersible polymer is 81%. (3) Aqueous dispersion type polymer microparticle emulsion binder performance
The prepared water-dispersible polymer microparticle emulsion binder is dried to form a film, wherein the film forming condition is 25 ℃ and the relative humidity is 75%, and the tensile strength of the film is 2800N/cm 2 After immersing in an electrolyte at 60℃for 72 hours, the film had a conductivity of 1.6X10 1 s/cm。
The battery test was carried out using the prepared water-dispersible polymer microparticle emulsion binder, and the low-temperature test at-10 ℃ gave an evaluation of Δw of 83%.
Example 9
(1) Preparation of core polymer microparticle emulsion:
100g of deionized water, 1.3g of ammonium dodecyl ether sulfate, 0.1g of sodium dodecyl diphenyl ether disulfonate, 53g of 2-vinylnaphthalene, 5g of acrylic acid, 1g of itaconic acid and 2g of methacrylonitrile are respectively added into a pressure-resistant emulsification vessel equipped with stirring paddles and a nitrogen inlet valve. After oxygen was removed by nitrogen exchange, 20g of isoprene and 20g of methylpentadiene were taken in, and the mixture was stirred to obtain a monomer mixture for use.
To a pressure-resistant reaction vessel equipped with a stirring paddle, a thermometer, a nitrogen inlet valve and a reflux condenser, 80g of deionized water, 1.3g of ammonium dodecyl ether sulfate and 0.1g of sodium dodecyl diphenyl ether disulfonate were added, and the temperature was raised to 63℃with stirring, and an aqueous solution of sodium persulfate and sodium sulfite (1.5 g of sodium persulfate and 0.08g of sodium sulfite were dissolved in 10g of deionized water) was added to the reaction vessel. Simultaneously, continuously dripping the monomer mixture for 300 minutes, after dripping, adding 0.1g of sodium persulfate, 0.05g of sodium sulfite and 10g of deionized water, heating to 75 ℃, keeping the temperature until the conversion rate is 97%, stopping the reaction, and cooling to obtain the core polymer microparticle emulsion for later use.
(2) Preparation of water-dispersible polymer microparticle emulsion binder
150g of deionized water, 3.0g of ammonium dodecyl ether sulfate, 2.0g of sodium dodecyl diphenyl ether disulfonate, 87g of 2-vinyl naphthalene, 15g of acrylic acid, 3g of itaconic acid, 10g of ethyl acrylate, 5g of butyl acrylate and 50g of acrylonitrile are respectively added into a pressure-resistant emulsification vessel provided with a stirring paddle and a nitrogen inlet valve. After oxygen was removed by nitrogen exchange, 30g of isoprene and 50g of methylpentadiene were taken in, and the mixture was stirred to obtain a monomer mixture for use.
The core polymer microparticle emulsion prepared above was charged into a pressure-resistant reaction vessel equipped with a stirring paddle, a thermometer, a nitrogen inlet valve and a reflux condenser, and heated to 68℃to give an aqueous solution of sodium persulfate and sodium sulfite (sodium persulfate 2.0g and sodium sulfite 0.2g were dissolved in 150g of deionized water) in the reaction vessel. Meanwhile, the monomer mixture is continuously added dropwise at 300 minutes, 0.2g of sodium persulfate, 0.1g of sodium sulfite and 25g of deionized water are added after the completion of the dropwise addition, the temperature is raised to 79 ℃ at the same time, the reaction is stopped until the conversion rate is 97%, the temperature is reduced, the residual monomers are finally removed, the pH value is regulated to 8.3, and the water-dispersible polymer microparticle emulsion binder is obtained, wherein the particle size of the water-dispersible polymer microparticles is 380nm, the glass transition temperature of the water-dispersible polymer is 2 ℃, and the gel content of the water-dispersible polymer is 83%.
(3) Aqueous dispersion type polymer microparticle emulsion binder performance
The prepared water-dispersible polymer microparticle emulsion binder is dried to form a film, wherein the film forming condition is 25 ℃, the relative humidity is 75%, and the tensile strength of the film is 3300N/cm 2 After immersion in an electrolyte at 60℃for 72 hours, the film had a conductivity of 1.3X10 -1 s/cm。
And (3) performing battery test by using the prepared water-dispersible polymer microparticle emulsion binder, wherein the delta W is 80% according to the low-temperature test at-10 ℃.
Example 10
(1) Preparation of core polymer microparticle emulsion:
100g of deionized water, 0.5g of sodium dodecyl ether sulfate, 0.4g of sodium dodecyl benzene sulfonate, 75g of 4-vinylpyridine, 2g of crotonic acid, 3g of fumaric acid and 5g of acrylamide are respectively added into a pressure-resistant emulsification vessel equipped with a stirring paddle and a nitrogen inlet valve. After oxygen was removed by nitrogen exchange, 10g of methylpentadiene and 5g of phenylbutadiene were taken in and stirred to obtain a monomer mixture for use.
To a pressure-resistant reaction vessel equipped with a stirring paddle, a thermometer, a nitrogen inlet valve and a reflux condenser, 80g of deionized water, 0.5g of sodium dodecyl ether sulfate and 0.4g of sodium dodecyl benzene sulfonate were added, and the temperature was raised to 51℃with stirring, and an aqueous solution of hydrogen peroxide and sodium hydrogen sulfite (1.6 g of hydrogen peroxide and 0.01g of sodium hydrogen sulfite were dissolved in 10g of deionized water) was added to the reaction vessel. Simultaneously, continuously dripping the monomer mixture for 300 minutes, then adding 0.5g of hydrogen peroxide, 0.05g of sodium bisulphite and 10g of deionized water after dripping, heating to 80 ℃, keeping the temperature until the conversion rate is 97%, stopping the reaction, and cooling to obtain the core polymer microparticle emulsion for later use.
(2) Preparation of water-dispersible polymer microparticle emulsion binder
200g of deionized water, 3.5g of sodium dodecyl ether sulfate, 2.4g of sodium dodecyl benzene sulfonate, 229g of 4-vinyl pyridine, 10g of crotonic acid, 13g of fumaric acid, 10g of ethyl acrylate, 8g of butyl acrylate and 50g of acrylonitrile are respectively added into a pressure-resistant emulsification vessel provided with a stirring paddle and a nitrogen inlet valve. After oxygen was removed by nitrogen exchange, 20g of methylpentadiene and 10g of phenylbutadiene were taken in and stirred to obtain a monomer mixture for use.
The core polymer microparticle emulsion prepared above was charged into a pressure-resistant reaction vessel equipped with a stirring paddle, a thermometer, a nitrogen inlet valve and a reflux condenser, and heated to 52℃to give an aqueous solution of hydrogen peroxide and sodium hydrogen sulfite (hydrogen peroxide 4.0g and sodium hydrogen sulfite 0.1g were dissolved in 200g deionized water). Simultaneously, continuously dripping the monomer mixture for 300 minutes, then adding 1.5g of hydrogen peroxide, 0.05g of sodium bisulphite and 75g of deionized water after dripping, heating to 81 ℃, keeping the temperature until the conversion rate is 97%, stopping the reaction, cooling, finally removing residual monomers, adjusting the pH value to 8.2, and obtaining the water-dispersible polymer microparticle emulsion binder, wherein the particle size of the water-dispersible polymer microparticles is 270nm, the glass transition temperature of the water-dispersible polymer is 40 ℃, and the gel content of the water-dispersible polymer is 88%. (3) Aqueous dispersion type polymer microparticle emulsion binder performance
The prepared water-dispersible polymer microparticle emulsion binder is dried to form a film, wherein the film forming condition is 25 ℃ and the relative humidity is 75%, and the tensile strength of the film is 3800N/cm 2 After immersing in an electrolyte at 60℃for 72 hours, the film had a conductivity of 2.0X10 -1 s/cm。
And (3) performing battery test by using the prepared water-dispersible polymer microparticle emulsion binder, wherein the delta W is 80% according to the low-temperature test at-10 ℃.

Claims (8)

1. The application of the water-dispersible polymer microparticle emulsion binder for the lithium ion battery in preparing the lithium ion secondary battery cathode is characterized in that the binder is water-dispersible polymer microparticle emulsion, a dispersion medium is water, the emulsion dispersion is specifically polymer microparticles with a core-shell structure, the total of monomers and aromatic vinyl monomers of conjugated diene in the core part of the emulsion is more than 80% by weight of the total of the monomer mixture of the core part, and the total of acrylate monomers and acrylonitrile and/or methacrylonitrile monomers in the shell part of the emulsion is more than 15% by weight of the total of the monomer mixture of the shell part; drying to form a film, wherein the film forming condition is 25deg.C, the relative humidity is 75%, and the tensile strength of the film is 1000-5000N/cm 2 After immersing in an electrolyte at 60℃for 72 hours, the film had a conductivity of 10 -5 s/cm to 10 3 s/cm；
The adhesive is prepared by the following steps: the core part adopts conjugated diene monomer, aromatic vinyl monomer, unsaturated monomer containing acid functional group, or adopts conjugated diene monomer, aromatic vinyl monomer, unsaturated monomer containing acid functional group and more than one other unsaturated monomer which can be copolymerized with the above monomers; wherein the total of the conjugated diene monomer and the aromatic vinyl monomer is 80% or more of the total amount of the core monomer mixture; preparing core polymer microparticle emulsion by batch emulsion polymerization or/and stepwise dropwise addition semi-continuous emulsion polymerization method in the presence of alkyl sulfate emulsifier or/and sulfonate emulsifier water solution and water-soluble peroxidation initiator or initiator and reducer, wherein the polymerization temperature is 30-85deg.C; the shell part adopts conjugated diene monomer, aromatic vinyl monomer, unsaturated monomer containing acid functional group, acrylic ester monomer and acrylonitrile and/or methyl acrylonitrile monomer, and the total content of acrylic ester monomer and acrylonitrile and/or methyl acrylonitrile monomer is 15% of the total weight of the shell part monomer, under the existence of core part polymer microparticle emulsion, all the above monomers are mixed and emulsified by utilizing alkyl sulfate emulsifier or/and sulfonate emulsifier, and under the existence of water-soluble peroxidation initiator or initiator and reducer, the water-dispersible polymer microparticle emulsion adhesive is prepared by using a semi-continuous emulsion polymerization method of intermittent emulsion polymerization or gradual dropwise addition, and the polymerization temperature is 35-85 ℃.
2. The application of the water-dispersible polymer microparticle emulsion binder for the lithium ion battery in preparing the negative electrode of the lithium ion secondary battery according to claim 1, wherein the particle size of the water-dispersible polymer microparticles is 120-450nm, the glass transition temperature of the water-dispersible polymer is-20-40 ℃, the gel content of the water-dispersible polymer is 60-90%, and the pH of the water-dispersible polymer microparticle emulsion binder is 7.5-8.5.
3. The application of the water-dispersible polymer microparticle emulsion binder for the lithium ion battery in preparing the negative electrode of the lithium ion secondary battery according to claim 1, wherein the conjugated diene monomer is one of 1, 3-butadiene, isoprene, methylpentadiene, phenylbutadiene, 3, 4-dimethyl-1, 3-hexadiene and 4, 5-diethyl-1, 3-octadiene and a mixture of more than one of the conjugated diene monomers in any proportion; the aromatic vinyl monomer is styrene, alpha-methylstyrene, 4-tert-butylstyrene, chlorovinylbenzene, vinyltoluene, divinylbenzene, p-chloromethylstyrene, methyl 4-vinylbenzoate, 2-vinylnaphthalene, 4-vinylbenzoic acid and methyl 4-vinylbenzoate; the unsaturated monomer containing acid functional groups is one or more than one of acrylic acid, methacrylic acid, 2-acrylamide-2-methylpropanesulfonic acid, crotonic acid, fumaric acid, maleic acid, 2-methyl maleic acid and itaconic acid and a mixture of more than one of the above components in any proportion; the alkyl sulfate emulsifier is one or more of sodium dodecyl sulfate, sodium dodecyl ether sulfate and ammonium dodecyl ether sulfate and a mixture of more than one of the sodium dodecyl sulfate, the sodium dodecyl ether sulfate and the ammonium dodecyl ether sulfate in any proportion; the sulfonate emulsifier is one or more of sodium dodecyl benzene sulfonate, sodium hexadecyl sulfonate, sodium dodecyl diphenyl ether disulfonate and sodium diisobutyl naphthalene sulfonate and a mixture of more than one of the sodium dodecyl benzene sulfonate, the sodium hexadecyl sulfonate, the sodium dodecyl diphenyl ether disulfonate and the sodium diisobutyl naphthalene sulfonate in any proportion; the water-soluble peroxide initiator is one or more of potassium persulfate, sodium persulfate, ammonium persulfate, tert-butyl hydroperoxide and hydrogen peroxide and a mixture of more than one of the potassium persulfate, the sodium persulfate, the ammonium persulfate, the tert-butyl hydroperoxide and the hydrogen peroxide in any proportion; the reducing agent is one of glucose, sodium bisulphite and sodium sulfite and a mixture of more than one of the above components in any proportion.
4. The application of the water-dispersible polymer microparticle emulsion binder for lithium ion batteries in preparing the negative electrode of the lithium ion secondary battery according to claim 1, wherein in the process of preparing the polymer microparticle emulsion for the core part, the other unsaturated monomers with copolymerization possibility are one or more of methyl acrylate, ethyl acrylate, butyl methacrylate, isooctyl acrylate, methyl methacrylate, glycidyl acrylate, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide and N-tert-butyl acrylamide and a mixture of more than one of the above components in any proportion.
5. The use of a water-dispersible polymer microparticle emulsion binder for lithium ion batteries according to claim 1 for preparing a negative electrode of a lithium ion secondary battery, wherein the monomer and aromatic vinyl monomer mixture of the conjugated diene is used in an amount of 99.5 to 80% by weight based on the total amount of the monomer mixture of the core part in the preparation of the polymer microparticle emulsion of the core part; the usage amount of the unsaturated monomer containing acid functional groups is 0.5-9.0% by weight of the total amount of the core monomer mixture; the other unsaturated monomers which are possibly copolymerized are used in an amount of 0 to 11.0% by weight based on the total amount of the core monomer mixture; the usage amount of the alkyl sulfate emulsifier and/or the sulfonate emulsifier is 0.05-3.0% of the total weight of the core monomer mixture; the water-soluble peroxidation initiator is used in an amount of 0.05-3.0% by weight of the total amount of the core monomer mixture; the reducing agent is used in an amount of 0 to 0.5% by weight based on the total amount of the core monomer mixture.
6. The application of the water-dispersible polymer microparticle emulsion binder for the lithium ion battery in preparing the negative electrode of the lithium ion secondary battery according to claim 1, wherein in the process of preparing the water-dispersible polymer microparticle emulsion binder for the shell, the acrylic monomer is one or more of methyl acrylate, ethyl acrylate, butyl methacrylate, isooctyl acrylate, methyl methacrylate and glycidyl acrylate and a mixture of more than one of the methyl acrylate, the ethyl acrylate, the butyl methacrylate, the isooctyl acrylate, the methyl methacrylate and the glycidyl acrylate in any proportion.
7. The use of a water-dispersible polymer microparticle emulsion binder for lithium ion batteries according to claim 1 for preparing a negative electrode of a lithium ion secondary battery, wherein the monomer and aromatic vinyl monomer mixture of conjugated diene is used in an amount of 84.95 to 60% by weight based on the total amount of the shell monomer mixture in preparing the shell water-dispersible polymer microparticle emulsion binder; the usage amount of the unsaturated monomer containing acid functional groups is 0.05-10% by weight of the total amount of the shell part monomer mixture; the usage amount of the acrylic monomer and the acrylonitrile and/or methacrylonitrile monomer mixture is 15-30% by weight of the total shell monomer mixture; the usage amount of the alkyl sulfate type emulsifier or/and the sulfonate type emulsifier is 0.05-3.0% by weight of the total shell part monomer mixture; the usage amount of the water-soluble peroxidation initiator is 0.05-3.0% by weight of the total shell monomer mixture; the reducing agent is used in an amount of 0 to 0.5% by weight based on the total amount of the shell monomer mixture.
8. The use of the water-dispersible polymer microparticle emulsion binder for lithium ion batteries according to claim 1 for preparing a negative electrode of a lithium ion secondary battery, wherein the weight ratio of the shell monomer mixture to the core monomer mixture is 90:10-20:80.
CN202110254669.3A 2021-03-09 2021-03-09 Water-dispersible polymer microparticle emulsion binder for lithium ion battery and preparation method thereof Active CN115044331B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110254669.3A CN115044331B (en) 2021-03-09 2021-03-09 Water-dispersible polymer microparticle emulsion binder for lithium ion battery and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110254669.3A CN115044331B (en) 2021-03-09 2021-03-09 Water-dispersible polymer microparticle emulsion binder for lithium ion battery and preparation method thereof

Publications (2)

Publication Number Publication Date
CN115044331A CN115044331A (en) 2022-09-13
CN115044331B true CN115044331B (en) 2023-05-09

Family

ID=83156891

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110254669.3A Active CN115044331B (en) 2021-03-09 2021-03-09 Water-dispersible polymer microparticle emulsion binder for lithium ion battery and preparation method thereof

Country Status (1)

Country Link
CN (1) CN115044331B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115332540B (en) * 2022-10-18 2023-01-31 江苏道赢科技有限公司 Negative electrode binder for secondary battery and preparation method thereof
CN115842132B (en) * 2022-12-29 2023-09-22 江苏道赢科技有限公司 Lithium battery composite binder and preparation method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07157736A (en) * 1993-12-03 1995-06-20 Mitsui Toatsu Chem Inc Pressure-sensitive adhesive for information-carrying sheet
CN1788039A (en) * 2003-06-27 2006-06-14 Lg化学株式会社 Method of manufacture of styrene-butadiene latexes
CN107338011A (en) * 2016-08-16 2017-11-10 南京工业大学 A kind of water-dispersed polymer particulate emulsion binder and preparation method thereof
CN108929401A (en) * 2018-06-25 2018-12-04 重庆云天化瀚恩新材料开发有限公司 A kind of lithium battery silicium cathode adhesive and preparation method thereof
CN110183584A (en) * 2019-05-05 2019-08-30 欣旺达惠州动力新能源有限公司 A kind of acrylonitrile polymer emulsion binder and preparation method thereof
CN112437996A (en) * 2018-08-29 2021-03-02 日本瑞翁株式会社 Composition for non-aqueous secondary battery adhesive layer, battery member for non-aqueous secondary battery and method for producing same, method for producing laminate for non-aqueous secondary battery, and method for producing non-aqueous secondary battery

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07157736A (en) * 1993-12-03 1995-06-20 Mitsui Toatsu Chem Inc Pressure-sensitive adhesive for information-carrying sheet
CN1788039A (en) * 2003-06-27 2006-06-14 Lg化学株式会社 Method of manufacture of styrene-butadiene latexes
CN107338011A (en) * 2016-08-16 2017-11-10 南京工业大学 A kind of water-dispersed polymer particulate emulsion binder and preparation method thereof
CN108929401A (en) * 2018-06-25 2018-12-04 重庆云天化瀚恩新材料开发有限公司 A kind of lithium battery silicium cathode adhesive and preparation method thereof
CN112437996A (en) * 2018-08-29 2021-03-02 日本瑞翁株式会社 Composition for non-aqueous secondary battery adhesive layer, battery member for non-aqueous secondary battery and method for producing same, method for producing laminate for non-aqueous secondary battery, and method for producing non-aqueous secondary battery
CN110183584A (en) * 2019-05-05 2019-08-30 欣旺达惠州动力新能源有限公司 A kind of acrylonitrile polymer emulsion binder and preparation method thereof

Also Published As

Publication number Publication date
CN115044331A (en) 2022-09-13

Similar Documents

Publication Publication Date Title
CN105131875B (en) A kind of water adhesive for lithium ion battery, preparation method and its usage
CN115044331B (en) Water-dispersible polymer microparticle emulsion binder for lithium ion battery and preparation method thereof
CN107868160B (en) Composition of binder for lithium ion secondary battery cathode and preparation method thereof
CN110183584B (en) Acrylonitrile polymer emulsion binder and preparation method thereof
JP4461659B2 (en) Binder composition for lithium ion secondary battery electrode and use thereof
WO2019242318A1 (en) Waterborne binder, preparation method therefor and use thereof
CN107338011B (en) A kind of water-dispersed polymer particulate emulsion binder and preparation method thereof
CN111139002A (en) Water-soluble adhesive for lithium ion battery, preparation method of water-soluble adhesive, electrode plate and battery
CN106207184A (en) A kind of water adhesive for lithium ion battery and its production and use
CN115332540B (en) Negative electrode binder for secondary battery and preparation method thereof
WO2022111580A1 (en) Dispersant for lithium ion battery, preparation method therefor, positive electrode slurry and lithium ion battery
JPH09199135A (en) Binder composition for battery, electrode and battery
JPH09213337A (en) Binder for battery, binder composition, electrode and battery
CN113644266A (en) Binder material for improving low-temperature performance of lithium battery and preparation method thereof
CN112151802A (en) Negative electrode binder for lithium ion battery, preparation method of negative electrode binder and lithium ion battery containing negative electrode binder
CN113480695A (en) Core-shell binder material and preparation method thereof
TW202039605A (en) Energy storage device including two electrodes and an isolation layer which is arranged between the electrodes
CN112909252B (en) Polymer binder, its preparation and use
CN111082062A (en) Water-soluble binder for lithium ion battery and preparation method thereof
CN113736002A (en) Modified polyhalogenated styrene-1, 3-butadiene emulsion binder, preparation and application thereof
JP4552235B2 (en) Lithium ion secondary battery electrode and secondary battery
CN110492101B (en) Lithium ion battery cathode binder and preparation method and application thereof
CN117050237A (en) Solution type binder and preparation method and application thereof
CN116217794A (en) Solution type binder and preparation method and application thereof
CN115911391A (en) Adhesive for lithium ion battery, 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