CN108598486B - Lithium ion battery aqueous adhesive and preparation method thereof - Google Patents
Lithium ion battery aqueous adhesive and preparation method thereof Download PDFInfo
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- CN108598486B CN108598486B CN201810443255.3A CN201810443255A CN108598486B CN 108598486 B CN108598486 B CN 108598486B CN 201810443255 A CN201810443255 A CN 201810443255A CN 108598486 B CN108598486 B CN 108598486B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
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- 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
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
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- 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
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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- 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
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- Graft Or Block Polymers (AREA)
Abstract
The invention discloses a lithium ion battery aqueous adhesive, which consists of emulsion and latex particles dispersed in the emulsion, wherein the latex particles have a three-layer structure, an inner core consists of a polymer with low glass transition temperature, a middle transition layer consists of a polymer with medium glass transition temperature, and an outer shell layer consists of a polymer with high glass transition temperature and is gradually hardened from inside to outside; the solid content of the emulsion is 5-30%, and the mass ratio of the inner core polymer to the intermediate transition layer polymer to the outer shell polymer is as follows: (5-30): (20-60): (30-60). The lithium ion battery aqueous adhesive obtained by the invention takes water as a dispersion medium, so that the environmental protection problem of the lithium ion battery adhesive is solved; by adopting a synthesis method of respectively synthesizing the inner core, the transition layer and the shell, the prepared adhesive emulsion has good mechanical stability, and emulsion breaking phenomena such as agglomeration and the like can not occur in the dispersion process; the surface tension is low, and the dispersion efficiency and the film forming property are greatly improved.
Description
Technical Field
The invention relates to the field of lithium ion battery materials, and mainly relates to a water-based adhesive for a lithium ion battery and a preparation method thereof.
Background
With the development of science and technology and the improvement of the living standard of people's material culture, people have higher and higher requirements on mobile secondary batteries. The lithium ion secondary battery can meet the use requirements of people on the mobile power supply in many aspects, and the lithium ion battery is widely applied to the fields of mobile phone digital products, model airplane toys, electric vehicles, automobiles and the like at present. Meanwhile, the lithium ion battery conforms to the national policy of energy conservation, emission reduction and sustainable development, so that the lithium ion battery is advocated to be vigorously developed in the future 10-15 years in new energy planning. Meanwhile, with the continuous growth of economic development in China, the environmental concern of people on life is greatly improved, so that the living environment must be protected while any project is developed, and the method specifically provides the following steps in environmental development planning: five development concepts of innovation, coordination, green, openness and sharing are adopted, the total amount control of volatile organic compounds is promoted in key areas and key industries, the total amount discharged in the whole country is reduced by more than 10%, the adjustment of industrial structures is accelerated, and unqualified capacity such as energy consumption and environmental protection is eliminated legally. It follows that even the energetically advocated new energy projects must be developed without sacrificing environmental protection.
In the conventional process for producing the lithium ion battery, especially in the process for preparing the positive electrode plate, the conventional solvent-based adhesive is used, that is, a large amount of solvent is needed to be used as a solvent to dissolve the adhesive in the using process, and then the solvent is evaporated and removed in a heating manner in the preparation process, so that the energy waste is great, the solvent is discharged into the atmosphere (the solvent is difficult to be recovered by 100 percent even if the best recovery device is adopted), and the environment is polluted. Therefore, changing the binder into oil or water has become an unavoidable problem in the process of manufacturing lithium ion batteries.
At present, researchers at home and abroad do a lot of research work on the adhesive, and CN01108511.8, cn01108524.x discloses an adhesive, but the adhesive has the following defects in the actual use process: low-temperature baking is needed, so that the generation efficiency is low, the prepared pole piece is brittle and has poor flexibility, the pole piece is easy to break in the preparation process of the battery, the battery is easy to warp in the preparation process, waste products are easy to form, and the production cost of the battery is increased; CN201410731027.8 and CN200910300150.3 adopt a low-polarity polymer as a core and a high-polarity polymer as a shell to synthesize a lithium ion water-based adhesive with improved flexibility, but because the existing polymer is adopted as a reaction core, the selectivity and the designability are poor, and the product does not have the problem of being capable of well improving the manufacturing process of the lithium ion battery.
Disclosure of Invention
In view of the above-mentioned disadvantages of the prior art, the present invention provides a lithium ion battery aqueous adhesive having a stable structure and a low surface tension, and a second object is to provide a method for preparing the lithium ion battery aqueous adhesive.
In order to solve the technical problems, the invention adopts the following technical scheme:
a lithium ion battery aqueous adhesive is characterized in that: comprises emulsion and glue dispersed in the emulsion
The latex particles are of a three-layer structure, the inner core is made of a polymer with a low glass transition temperature, the middle transition layer is made of a polymer with a medium glass transition temperature, and the outer shell is made of a polymer with a high glass transition temperature and gradually becomes soft and hard from inside to outside; the solid content of the emulsion is 5-30%, and the mass ratio of the inner core polymer to the intermediate transition layer polymer to the outer shell polymer is as follows: (5-30): (20-60): (30-60).
The emulsion is further characterized in that the emulsifier of the emulsion is any one of acrylamide isopropyl sulfonate, 2-allyl ether 3-hydroxy propane-1-sulfonate, vinyl sulfonate, allyl sulfonate, methacrylic acid sulfonate and styrene sulfonate, or any two of the emulsifiers are mixed in a proportion of more than zero, or any three of the emulsifiers are mixed in a proportion of more than zero, or any four of the emulsifiers are mixed in a proportion of more than zero, or any five of the emulsifiers are mixed in a proportion of more than zero, or six of the emulsifiers are mixed in a proportion of more than zero; wherein the cation of the salt is lithium ion, sodium ion or potassium ion, and the weight of the whole emulsifier is 1-10% of the total mass.
The polymer with low glass transition temperature of the inner core is formed by the polymer with the glass transition temperature lower than 0 DEG C
Acrylate monomers or a mixture polymer, which is any one or two of ethyl acrylate, propyl acrylate, n/isobutyl acrylate, n-octyl acrylate, 2-isooctyl acrylate, n/isodecyl acrylate, dodecyl acrylate, tetradecyl acrylate, hexadecyl acrylate, lauryl acrylate, octadecyl acrylate, docosyl acrylate, isobornyl acrylate, n/isobutyl methacrylate, 2-isooctyl methacrylate, vinyl neodecanoate, dibutyl maleate, octadecyl methacrylate, glycidyl methacrylate, polyethylene glycol monomethyl ether acrylate, polyethylene glycol monomethyl ether methacrylate, allyl polyethylene glycol, allyl polypropylene glycol and the like, or any three of the above are mixed in a proportion of more than zero percent, or any four of the components are mixed in a proportion of more than zero percent respectively until all the components are mixed and polymerized in a proportion of more than zero percent respectively.
The polymer with high glass transition temperature of the shell layer is polymerized by a monomer or a mixture with the glass transition temperature higher than 0 ℃ and is composed of acrylic acid, methacrylic acid, acrylate, methacrylate, methyl methacrylate, ethyl methacrylate, acrylamide, methacrylamide, methylene bisacrylamide, itaconic acid, maleic acid, itaconate, maleate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, acrylonitrile, butenenitrile, 5-hexenenitrile, cyclohexene-1-nitrile, 2-nonenenitrile, vinyl acetate, N-methylolacrylamide, hydroxyethyl acrylurea, diacetone acrylamide, diallyl phthalate, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, any one of ethoxylated trimethylolpropane triacrylate, bisphenol A glycerol dimethacrylate, glycerol 1, 3-diglycerol alkyd diacrylate, 1, 6-hexanediol diacrylate, dipropylene glycol diacrylate and tripropylene glycol diacrylate, or any two of the two are mixed in a proportion of more than zero, or any three of the three are mixed in a proportion of more than zero, or any four of the four are mixed in a proportion of more than zero until all the components are mixed and polymerized in a proportion of more than zero, wherein the salt is potassium, sodium and lithium salt.
The transition layer polymer is polymerized by a mixture of at least one monomer with low glass transition temperature and containing the inner core and at least one monomer with high glass transition temperature and containing the outer shell, and wraps the surface of the inner core to form a transition layer structure.
The initiator for the adhesive is potassium persulfate, ammonium persulfate, sodium sulfite,
Any one of sodium bisulfite, azobisisoheptonitrile, azobisisobutyramidine hydrochloride (AIBA), azobisisobutyrimidazoline hydrochloride (AIBI), and azobisisobutyronitrile, or any two thereof are mixed in a proportion of greater than zero percent, or any three thereof are mixed in a proportion of greater than zero percent, or any four thereof are mixed in a proportion of greater than zero percent, until all of the foregoing components are mixed in a proportion of greater than zero percent.
The mass percentage of the core polymer of the adhesive in the whole molecule is 5-30, the glass transition temperature is-60 to-10 ℃, and the optimum temperature is-40 to-20 ℃; the mass percentage of the transition layer polymer is 10-80, the glass transition temperature is-20 ℃, and the optimal selection is-10 ℃; the mass percentage of the polymer of the shell layer shell is 30-80, the glass transition temperature is 10-80 ℃, and the optimal selection is 20-50 ℃.
The glass transition temperature of the core polymer of the adhesive is-40 to-20 ℃; the glass transition temperature of the transition layer polymer is-10 to 10 ℃; the glass transition temperature of the shell layer and shell polymer is 20-50 ℃.
The preparation method of the lithium ion battery aqueous adhesive is characterized by comprising the following steps,
1) preparing an emulsifier, an inner core monomer or mixture, an intermediate transition layer monomer or mixture, an outer shell monomer or mixture, an initiator and deionized water according to the components and the proportion required by the process;
2) adding the core monomer or the mixture and deionized water into a reaction device, and stirring to mix uniformly; heating to 50-80 deg.c, adding initiator to initiate polymerization for 0.6-1.5 hr;
3) controlling the speed of dripping the intermediate transition layer monomer or mixture, finishing the dripping within 1-5 hours, controlling the temperature to be 60-90 ℃, and stirring; then reacting for a period of time required by constant temperature process at 60-90 ℃, such as constant temperature for 2-5 hours;
4) controlling the speed of dripping the monomers or the mixture of the outer shell layer, finishing the dripping within 1 to 5 hours, controlling the temperature to be between 60 and 90 ℃ during the adding, and stirring; after the dripping is finished, the temperature is kept between 60 ℃ and 90 ℃ for a period of time required by the constant temperature process.
Compared with the prior art, the lithium ion battery aqueous adhesive and the preparation method thereof have the following advantages:
1. the adhesive of the invention takes water as a dispersion medium, solves the environmental protection problem of the adhesive for the lithium battery, and is an environment-friendly adhesive.
2. The invention adopts a synthesis method of respectively synthesizing the inner core, the transition layer and the shell, so that the prepared adhesive emulsion has good mechanical stability, and emulsion breaking phenomena such as agglomeration and the like can not occur in the dispersion process; the surface tension is lower, which is more beneficial to the dispersion of the conductive agent and the negative electrode material, and the dispersion efficiency and the film forming property are greatly improved.
3. The adhesive emulsion has the characteristics of high solid content, low viscosity and the like, and is high in production efficiency and convenient to use; meanwhile, the adhesive prepared by the method has excellent bonding performance and good flexibility, and the prepared negative pole piece is smooth and flat and has good cyclicity.
4. The invention is superior to the existing adhesive in capacity exertion and capacity maintenance, and is beneficial to large-scale popularization.
Detailed Description
The present invention is further illustrated by the following specific examples.
The lithium ion battery aqueous adhesive consists of emulsion and latex particles dispersed in the emulsion, wherein the latex particles have a three-layer structure, an inner core consists of a polymer with low glass transition temperature, a middle transition layer consists of a polymer with medium glass transition temperature, and an outer shell layer consists of a polymer with high glass transition temperature, and the polymer gradually becomes hard from the inner core to the outer shell layer, and the hardness gradually increases; wherein the solid content of the emulsion is 5-30% by mass, namely the mass percentage of latex particles of solid components in the emulsion is 5-30%; the mass ratio of the core polymer to the intermediate transition layer polymer to the shell polymer is as follows: (5-30): (20-60): (30-60).
The emulsifier of the emulsion is any one of acrylamide isopropyl sulfonate, 2-allyl ether 3-hydroxy propane-1-sulfonate, vinyl sulfonate, allyl sulfonate, methacrylic acid sulfonate and styrene sulfonate, or any two of the emulsifiers are mixed in a proportion which is respectively larger than zero percent, or any three of the emulsifiers are mixed in a proportion which is respectively larger than zero percent, or any four of the emulsifiers are mixed in a proportion which is respectively larger than zero percent, or any five of the emulsifiers are mixed in a proportion which is respectively larger than zero percent, or six of the emulsifiers are mixed in a proportion which is respectively larger than zero percent; wherein the positive ions of the salt are lithium ions, sodium ions or potassium ions, and the mass ratio of the whole emulsifier is 1-10%;
the polymer with the low glass transition temperature of the inner core is formed by acrylate monomer mixture polymer with the glass transition temperature lower than 0 ℃, namely, any one of ethyl acrylate, propyl acrylate, n/isobutyl acrylate, n-octyl acrylate, 2-isooctyl acrylate, n/isodecyl acrylate, dodecyl acrylate, tetradecyl acrylate, hexadecyl acrylate, lauryl acrylate, octadecyl acrylate, docosyl acrylate, isobornyl acrylate, n/isobutyl methacrylate, 2-isooctyl methacrylate, vinyl neodecanoate, dibutyl maleate, octadecyl methacrylate, glycidyl methacrylate, polyethylene glycol monomethyl acrylate, polyethylene glycol monomethyl methacrylate, allyl polyethylene glycol, allyl polypropylene glycol and the like, or any two of the components are mixed in a proportion which is respectively more than zero percent, or any three of the components are mixed in a proportion which is respectively more than zero percent, or any four of the components are mixed in a proportion which is respectively more than zero percent, until all the components are mixed and polymerized in a proportion which is respectively more than zero percent;
the polymer with high glass transition temperature of the shell layer is polymerized by a monomer mixture with the glass transition temperature higher than 0 ℃, namely acrylic acid, methacrylic acid, acrylate, methacrylate, methyl methacrylate, ethyl methacrylate, acrylamide, methacrylamide, methylene bisacrylamide, itaconic acid, maleic acid, itaconate, maleate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, acrylonitrile, butenenitrile, 5-hexenenitrile, cyclohexene-1-nitrile, 2-nonenenitrile, vinyl acetate, N-methylolacrylamide, hydroxyethyl acrylurea, diacetone acrylamide, diallyl phthalate, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, any one of ethoxylated trimethylolpropane triacrylate, bisphenol A glycerol dimethacrylate, glycerol 1, 3-diglycerol alkyd diacrylate, 1, 6-hexanediol diacrylate, dipropylene glycol diacrylate and tripropylene glycol diacrylate, or any two of the two are mixed in a proportion which is respectively larger than zero percent, or any three of the three are mixed in a proportion which is respectively larger than zero percent, or any four of the four are mixed in a proportion which is respectively larger than zero percent until all the components are mixed and polymerized in a proportion which is respectively larger than zero percent, wherein the salt is potassium, sodium and lithium salt;
the transition layer polymer is formed by polymerizing at least one monomer or a mixture of a plurality of monomers of a polymer with low glass transition temperature and containing an inner core and a polymer with high glass transition temperature and containing an outer shell, and wraps the surface of the inner core to form at least one transition layer structure;
the initiator for the adhesive is any one of potassium persulfate, ammonium persulfate, sodium sulfite, sodium bisulfite, azobisisoheptonitrile, azobisisobutyramidine hydrochloride (AIBA), azobisisobutyrimidazoline hydrochloride (AIBI), azobisisobutyronitrile and the like, or any two of the above components are mixed in a proportion of more than zero percent, or any three of the above components are mixed in a proportion of more than zero percent, or any four of the above components are mixed in a proportion of more than zero percent until all the above components are mixed in a proportion of more than zero percent.
The mass percentage of the core structure of the adhesive in the whole molecule is 5-30, the glass transition temperature is-60 to-10 ℃, and the optimum temperature is-40 to-20 ℃; the mass percentage of the transition layer is 20-60, the glass transition temperature is-20 ℃, and the optimal selection is-10 ℃; the mass percentage of the shell structure is 30-60, the glass transition temperature is 10-80 ℃, and the optimal selection is 20-50 ℃;
the solid content of the adhesive is 8-30%, and the viscosity is 5000-100000 mpas.
The preparation method of the lithium ion battery aqueous adhesive is characterized by comprising the following steps,
1) preparing an emulsifier, an inner core monomer or mixture, an intermediate transition layer monomer or mixture, an outer shell monomer or mixture, an initiator and deionized water according to the components and the proportion required by the process;
2) adding the core monomer or the mixture and deionized water into a reaction device, and stirring to mix uniformly; heating to 50-80 deg.c, adding initiator to initiate polymerization for 0.6-1.5 hr;
3) controlling the speed of dripping the intermediate transition layer monomer or mixture, finishing the dripping within 1-5 hours, controlling the temperature to be 60-90 ℃, and stirring; then reacting for a period of time required by constant temperature process at 60-90 ℃, such as constant temperature for 2-5 hours;
4) controlling the speed of dripping the monomers or the mixture of the outer shell layer, finishing the dripping within 1 to 5 hours, controlling the temperature to be between 60 and 90 ℃ during the adding, and stirring; after the dripping is finished, keeping the temperature at 60-90 ℃, and reacting for a period of time required by constant temperature process, such as constant temperature for 2-5 hours.
Example 1:
in this embodiment, sodium vinylsulfonate is used as a reactive emulsifier monomer, an inner core monomer is ethyl acrylate, a transition layer monomer is ethyl acrylate, methyl acrylate and acrylic acid, a shell monomer is acrylic acid, acrylamide and methyl methacrylate, a monomer, an initiator are respectively marked as a, B and C according to the core, the transition layer and the shell, and the composition is as follows:
a: 5g of sodium vinyl sulfonate, 20g of ethyl acrylate and 141.6 g of deionized water;
b: 5g of acrylic acid, 25 g of ethyl acrylate, 10 g of methyl acrylate, 0.3 g of sodium persulfate and 226.6 g of deionized water;
c: 15 g of methyl methacrylate, 10 g of acrylamide, 10 g of acrylic acid, 0.3 g of sodium persulfate and 198.3 g of deionized water.
The preparation method of the adhesive emulsion for the lithium ion battery comprises the following steps: sequentially adding a monomer mixture A, stirring, rotating at the speed of 200rpm, heating to 75 ℃, adding 0.2 g of sodium persulfate, initiating polymerization, reacting for 1 hour, slowly dropwise adding a component B monomer (stirring is required during dropwise adding), controlling the temperature at 78 ℃, completely dropwise adding within 3 hours, keeping the temperature at 78 ℃ for 30 minutes, finally dropwise adding a component C monomer (stirring is required during dropwise adding), controlling the dropwise adding temperature at 78 ℃, completely dropwise adding within 3 hours, heating to 82 ℃, and keeping the temperature for 3 hours, thus obtaining the core-shell type water-based adhesive with the components, wherein the viscosity is 5000-6500 centipoises.
Example 2:
the difference between the method and the method 1 is that the initiator is ammonium persulfate, and the other differences are that the viscosity of the emulsion prepared by the method is slightly higher, and the viscosity is 6000-8000 centipoises.
200g of the adhesive emulsion synthesized in the embodiment and 500g of deionized water are slowly stirred for 10 minutes, then 30g of a conductive agent is added, high-speed dispersion is carried out for 60 minutes, 1440g of lithium manganate is added for 2 times, high-speed dispersion is carried out for 120 minutes, the solid content of the obtained lithium manganate slurry is 69%, the viscosity is 6500, no obvious precipitate is generated after the lithium manganate slurry is placed for 24 hours, and the lithium manganate slurry is coated on an aluminum foil, so that the appearance is uniform, and the adhesive force is good.
200g of the adhesive emulsion synthesized in the embodiment and 500g of deionized water are slowly stirred for 10 minutes, then 30g of a conductive agent is added, high-speed dispersion is carried out for 60 minutes, then 2 times of addition of a ternary cathode material (NCM523) and 1440g of the ternary cathode material are carried out, high-speed dispersion is carried out for 120 minutes, the solid content of the obtained lithium manganate slurry is 69%, the viscosity is 4000, no obvious precipitate exists after standing for 24 hours, and the obtained lithium manganate slurry is coated on an aluminum foil, and the adhesive has uniform appearance and good adhesive force.
In the binder emulsion synthesized in this example, artificial graphite was used as the negative electrode material. The proportion of the whole negative electrode slurry material is that the adhesive emulsion is 3.0%, the BTR518 is 95.5%, the conductive agent is 1%, and the slurry is 55% of high solid content. The prepared negative pole piece is smooth and has high surface density.
Example 3:
the adhesive of this example was prepared essentially as described in 1, except that amine persulfate was used as the initiator and the monomers A, B and C were different in composition: the preparation method comprises the following steps of adopting 2-allyl ether 3-hydroxy propane-1-sodium sulfonate as a reactive emulsifier monomer, adopting a mixture of ethyl acrylate, butyl acrylate and isooctyl acrylate as a core monomer, adopting butyl acrylate, lithium acrylate, acrylamide and acrylic acid as a transition layer monomer, adopting acrylic acid, lithium methacrylate, acrylamide and methyl methacrylate as a shell monomer, and respectively marking A, B and C according to the core, the transition layer and the shell by a monomer and an initiator, wherein the specific components are as follows:
a: 4g of 2-allyl ether 3-hydroxy propane-1-sodium sulfonate, 8g of ethyl acrylate, 3 g of butyl acrylate, 2g of isooctyl acrylate and 96.3 g of deionized water;
b: 5g of lithium acrylate, 15 g of butyl acrylate, 5g of acrylic acid, 10 g of acrylamide, 0.3 g of ammonium persulfate and 198.3 g of deionized water;
c: 12 g of acrylic acid, 5g of lithium methacrylate, 20g of acrylamide, 11 g of methyl methacrylate, 0.3 g of ammonium persulfate and 272 g of deionized water.
The preparation method of the adhesive emulsion for the lithium ion battery comprises the following steps: sequentially adding a monomer mixture A, stirring, rotating at the speed of 200rpm, heating to 72 ℃, adding 0.2 g of sodium persulfate to initiate polymerization, reacting for 1 hour, slowly adding a component B monomer (stirring is required to be kept during dropwise adding), controlling the temperature at 76 ℃ during dropwise adding, completely dropwise adding within 3 hours, keeping the temperature at 76 ℃ for 1 hour, finally dropwise adding a component C monomer (stirring is required during dropwise adding), controlling the dropwise adding temperature at 76 ℃ during 3 hours, completely dropwise adding, heating to 80 ℃, and keeping the temperature for 6 hours to prepare the core-shell type water-based adhesive with the components, wherein the solid content is 15%.
This example incorporates butyl acrylate in the core and transition layers, which is more flexible, and therefore the resulting adhesive films are softer and have excellent elasticity.
Example 4:
the method and the process of the embodiment are basically the same as those of the embodiment 3, the main change is that the used initiator is azodiisohydrochloride, the reaction temperature is controlled to be 50-60 ℃, the whole reaction time is prolonged by 6 hours, and the prepared adhesive emulsion has the advantages of high viscosity, good fluidity, water resistance, excellent thermal stability and high decomposition temperature.
Example 5:
the adhesive of this example was prepared essentially as described in 1, except that amine persulfate was used as the initiator and the monomers A, B and C were different in composition: the preparation method comprises the following steps of adopting 2-allyl ether 3-hydroxy propane-1-sodium sulfonate as a reactive emulsifier monomer, adopting lauryl acrylate, butyl acrylate and isooctyl acrylate as a core monomer, adopting butyl acrylate, isooctyl acrylate, lithium acrylate and acrylic acid as a transition layer monomer, adopting acrylic acid, lithium methacrylate, acrylamide and acrylonitrile as a shell monomer, and respectively marking A, B and C according to the core, the transition layer and the shell by a monomer, wherein the monomer specifically comprises the following components:
a: 5g of 2-allyl ether 3-hydroxy propane-1-sodium sulfonate, 2g of acrylic laurate, 5g of butyl acrylate, 4g of isooctyl acrylate and 90.3 g of deionized water;
b: 8g of lithium acrylate, 10 g of butyl acrylate, 2g of isooctyl acrylate, 7 g of acrylic acid, 0.3 g of ammonium persulfate and 153 g of deionized water;
c: 10 g of acrylic acid, 9 g of lithium methacrylate, 20g of acrylamide, 11 g of acrylonitrile, 0.3 g of ammonium persulfate and 283 g of deionized water.
The preparation method of the adhesive emulsion for the lithium ion battery comprises the following steps: sequentially adding a monomer mixture A, stirring, rotating at the speed of 200rpm, heating to 72 ℃, adding 0.2 g of sodium persulfate to initiate polymerization, reacting for 1 hour, slowly adding a component B monomer (stirring is required to be kept during dropwise adding), controlling the temperature at 76 ℃ during dropwise adding, completely dropwise adding within 3 hours, keeping the temperature at 76 ℃ for 1 hour, finally dropwise adding a component C monomer (stirring is required during dropwise adding), controlling the dropwise adding temperature at 76 ℃ during 3 hours, completely dropwise adding, heating to 80 ℃, and keeping the temperature for 6 hours to prepare the core-shell type water-based adhesive with the components, wherein the solid content is 15%.
This example incorporates isooctyl acrylate and lauryl acrylate in the core and transition layers, which are more flexible, and therefore the resulting adhesive films are softer and have excellent elasticity.
Example 6
This example is substantially the same as example 3, except that sodium persulfate was used as the initiator, and the adhesive emulsion prepared therefrom was high in viscosity, good in fluidity, water-resistant, excellent in thermal stability, and high in decomposition temperature.
Example 7:
the process of this example is substantially the same as that of example 3, the main change is that azodiisobutyl imidazoline hydrochloride (AIBA) is used as the initiator, the reaction temperature is controlled at 50-60 ℃, the overall reaction time is prolonged by 6 hours, the prepared adhesive emulsion has high viscosity, good fluidity and water resistance, and the adhesive has excellent thermal stability and high decomposition temperature.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the technical solutions, and although the present invention has been described in detail by referring to the preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions to the technical solutions of the present invention can be made without departing from the spirit and scope of the technical solutions, and all the modifications and equivalent substitutions should be covered by the claims of the present invention.
Claims (2)
1. A lithium ion battery aqueous adhesive is characterized in that: the latex particles are of a three-layer structure, the inner core is made of a polymer with a low glass transition temperature, the middle transition layer is made of a polymer with a medium glass transition temperature, and the outer shell is made of a polymer with a high glass transition temperature and gradually becomes soft and hard from inside to outside; the solid content of the emulsion is 5-30% by mass, and the mass ratio of the core polymer to the intermediate transition layer polymer to the shell polymer is as follows: (5-30): (20-60): (30-60);
the polymer with the low glass transition temperature of the inner core is formed by acrylate monomers or mixture polymers with the glass transition temperature lower than-20 ℃, namely any one of ethyl acrylate, propyl acrylate, n/isobutyl acrylate, n-octyl acrylate, 2-isooctyl acrylate, n/isodecyl acrylate, dodecyl acrylate, tetradecyl acrylate, hexadecyl acrylate, lauryl acrylate, octadecyl acrylate, docosyl acrylate, isobornyl acrylate, n/isobutyl methacrylate, 2-isooctyl methacrylate, vinyl neodecanoate, dibutyl maleate, octadecyl methacrylate, glycidyl methacrylate, polyethylene glycol monomethyl acrylate, polyethylene glycol monomethyl methacrylate, allyl polyethylene glycol and allyl polypropylene glycol, or any two of the components are mixed in a proportion which is respectively more than zero percent, or any three of the components are mixed in a proportion which is respectively more than zero percent, or any four of the components are mixed in a proportion which is respectively more than zero percent, until all the components are mixed and polymerized in a proportion which is respectively more than zero percent;
the polymer with high glass transition temperature of the shell layer is polymerized by a monomer or a mixture with the glass transition temperature higher than 20 ℃ and is composed of acrylic acid, methacrylic acid, acrylate, methacrylate, methyl methacrylate, ethyl methacrylate, acrylamide, methacrylamide, methylene bisacrylamide, itaconic acid, maleic acid, itaconate, maleate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, acrylonitrile, crotononitrile, 5-hexenenitrile, cyclohexene-1-nitrile, 2-nonenenitrile, vinyl acetate, N-methylolacrylamide, hydroxyethyl acrylurea, diacetone acrylamide, diallyl phthalate, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, any one of ethoxylated trimethylolpropane triacrylate, bisphenol A glycerol dimethacrylate, glycerol 1, 3-diglycerol alkyd diacrylate, 1, 6-hexanediol diacrylate, dipropylene glycol diacrylate and tripropylene glycol diacrylate, or any two of the two are mixed in a proportion which is respectively larger than zero percent, or any three of the three are mixed in a proportion which is respectively larger than zero percent, or any four of the four are mixed in a proportion which is respectively larger than zero percent until all the components are mixed and polymerized in a proportion which is respectively larger than zero percent, wherein the salt is potassium, sodium and lithium salt;
the transition layer polymer is polymerized by a mixture of at least one monomer containing the inner core and at least one monomer containing the outer shell, and wraps the surface of the inner core to form a transition layer structure;
the glass transition temperature of the polymer of the inner core of the adhesive is-40 to-20 ℃; transition layer polymer with the glass transition temperature of-10 to 10 ℃; the glass transition temperature of the shell polymer is 20-50 ℃;
the solid content of the adhesive is 8-30%, and the viscosity is 100000mpas of 5000-;
the emulsifier of the emulsion is any one of acrylamide isopropyl sulfonate, 2-allyl ether 3-hydroxy propane-1-sulfonate, vinyl sulfonate, allyl sulfonate, methacrylic acid sulfonate and styrene sulfonate, or any two of the emulsifiers are mixed in a proportion which is respectively larger than zero percent, or any three of the emulsifiers are mixed in a proportion which is respectively larger than zero percent, or any four of the emulsifiers are mixed in a proportion which is respectively larger than zero percent, or any five of the emulsifiers are mixed in a proportion which is respectively larger than zero percent, or six of the emulsifiers are mixed in a proportion which is respectively larger than zero percent; wherein the cation of the salt is lithium ion, sodium ion or potassium ion, and the using amount of the whole emulsifier is 1-10% of the total mass.
2. The aqueous binder for lithium ion batteries according to claim 1, characterized in that the initiator for the binder is any one of potassium persulfate, ammonium persulfate, sodium sulfite, sodium bisulfite, azobisisoheptonitrile, azobisisobutyramidine hydrochloride (AIBA), azobisisobutyrimidazoline hydrochloride (AIBI), and azobisisobutyronitrile, or any two thereof are mixed in a proportion of more than zero percent each, or any three thereof are mixed in a proportion of more than zero percent each, or any four thereof are mixed in a proportion of more than zero percent each, until all the aforementioned components are mixed in a proportion of more than zero percent each.
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| CN109378478A (en) * | 2018-12-03 | 2019-02-22 | 珠海光宇电池有限公司 | A kind of negative electrode of lithium ion battery binder |
| CN110183584B (en) * | 2019-05-05 | 2023-05-05 | 欣旺达惠州动力新能源有限公司 | Acrylonitrile polymer emulsion binder and preparation method thereof |
| CN110218285B (en) | 2019-05-09 | 2021-09-07 | 福建蓝海黑石新材料科技有限公司 | Water-based adhesive and preparation method thereof |
| CN110627945B (en) * | 2019-10-31 | 2021-11-30 | 湖南高瑞电源材料有限公司 | Acrylate adhesive modified by long-chain unsaturated carboxylic acid or derivative thereof, and preparation method and application thereof |
| CN112662348B (en) * | 2020-01-21 | 2023-08-29 | 四川茵地乐科技有限公司 | Adhesive for battery, lithium ion battery negative plate and lithium ion battery |
| CN112271324B (en) * | 2020-09-15 | 2021-07-30 | 赖见 | High-voltage solid-state lithium battery and preparation method thereof |
| CN113939927B (en) * | 2020-12-31 | 2022-12-06 | 东莞新能源科技有限公司 | Electrochemical device, electronic device and electrochemical device preparation method |
| JP7265581B2 (en) * | 2021-05-06 | 2023-04-26 | 花王株式会社 | Dispersant for storage device electrodes |
| CN113929827A (en) * | 2021-09-16 | 2022-01-14 | 深圳知行新能源材料科技有限公司 | Battery coating material and preparation method thereof, battery coating slurry and secondary battery |
| CN116284551A (en) * | 2023-03-22 | 2023-06-23 | 广东吉美帮新材料有限公司 | Quick-drying high-molecular emulsion with strong wet adhesion and preparation method thereof |
| CN116462792B (en) * | 2023-06-19 | 2023-09-01 | 广州纳诺新材料技术有限公司 | Lithium battery carbon-coated foil conductive slurry, modified acrylic composite resin emulsion and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1876731A (en) * | 2005-06-09 | 2006-12-13 | 北京化工大学 | Aqueous coating containing three layer nuclear shell structure rubber particle latex and its preparation method |
| CN101457131A (en) * | 2009-01-12 | 2009-06-17 | 成都茵地乐电源科技有限公司 | Water binding agent for lithium ionic cell electric pole material and preparation method thereof |
| CN105324868A (en) * | 2013-07-10 | 2016-02-10 | 日本瑞翁株式会社 | Adhesive for lithium ion secondary batteries, separator for lithium ion secondary batteries, and lithium ion secondary battery |
| CN106663813A (en) * | 2014-09-05 | 2017-05-10 | 日本瑞翁株式会社 | Binder composition for secondary-battery electrode, slurry composition for secondary-battery electrode, secondary-battery electrode, and secondary battery |
-
2018
- 2018-05-10 CN CN201810443255.3A patent/CN108598486B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1876731A (en) * | 2005-06-09 | 2006-12-13 | 北京化工大学 | Aqueous coating containing three layer nuclear shell structure rubber particle latex and its preparation method |
| CN101457131A (en) * | 2009-01-12 | 2009-06-17 | 成都茵地乐电源科技有限公司 | Water binding agent for lithium ionic cell electric pole material and preparation method thereof |
| CN105324868A (en) * | 2013-07-10 | 2016-02-10 | 日本瑞翁株式会社 | Adhesive for lithium ion secondary batteries, separator for lithium ion secondary batteries, and lithium ion secondary battery |
| CN106663813A (en) * | 2014-09-05 | 2017-05-10 | 日本瑞翁株式会社 | Binder composition for secondary-battery electrode, slurry composition for secondary-battery electrode, secondary-battery electrode, and secondary battery |
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