CN108598486A - Water adhesive of lithium ion battery and preparation method thereof - Google Patents
Water adhesive of lithium ion battery and preparation method thereof Download PDFInfo
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- CN108598486A CN108598486A CN201810443255.3A CN201810443255A CN108598486A CN 108598486 A CN108598486 A CN 108598486A CN 201810443255 A CN201810443255 A CN 201810443255A CN 108598486 A CN108598486 A CN 108598486A
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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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- Adhesives Or Adhesive Processes (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention discloses a kind of water adhesive of lithium ion battery, it is made of lotion and the latex particle being dispersed in lotion, the latex particle is three-decker, kernel is made of the polymer of lower glass transition temperatures, intermediate layer is made of the polymer of medium glass transition temperature, outer shell is made of the polymer of high glass transition temperature, is gradually changed software strategy into software-hardware strategy from inside to outside；The solid content of lotion be 5~30%, interior nuclear polymer, middle transition one polymer, shell one polymer mass ratio be：（5~30）：（20~60）：（30~60）.The water adhesive of lithium ion battery that the present invention obtains, adhesive solve the environmental issue of lithium battery adhesive using water as decentralized medium；Using the synthetic method for being respectively synthesized kernel, transition zone, shell, the good mechanical stability for the adhesive agent emulsion prepared is not in the demulsifying phenomenons such as reunion in dispersion process；Surface tension is relatively low, greatly improves dispersion efficiency and film forming.
Description
Technical field
The present invention relates to a kind of field of lithium ion battery material, have related generally to a kind of water adhesive for lithium ion battery
And preparation method thereof.
Background technology
With the development of science and technology and the raising of the people's material and cultural life level, people are to moveable secondary electricity
The requirement in pond is also higher and higher.Lithium rechargeable battery disclosure satisfy that requirement of the people to mobile power at many aspects,
Lithium ion battery is widely used in mobile phone digital product, ship model toy, the fields such as electric vehicle and automobile at present.Simultaneously as lithium
Ion battery meets national energy conservation and emission reduction and the principles and policies of sustainable development, therefore, in new energy planning, advocates in future
10-15 in, greatly develop lithium ion battery.At the same time, with the sustainable growth of China's economic development, people are to life
Environmental concern degree greatly improve, therefore, while developing any project, it is necessary to protect we survive environment, in environment
In development plan, clearly propose：" innovation is coordinated, is green, open, shared " five great development theory, and in key area, emphasis
Industry promotes volatile organic matter overall control, and national total emission volumn declines 10% or more, and accelerates industry restructuring, in accordance with the law
Eliminate the production capacities not up to standard such as energy consumption, environmental protection.It can be seen that the new energy project even advocated energetically, it is also necessary to not with sacrificial
Domestic animal environmental protection is that cost is developed.
And during the lithium ion battery in current traditional year generates technical process, especially in the preparation process of anode pole piece,
Also use traditional solvent type adhesive, i.e., during use, need a large amount of solvent as solvent to dissolve adhesive,
Then the mode that solvent heats is evaporated into removing again in preparation process, thus not only causes great energy waste, also
Among solvent discharge to air（Even if using the best retracting device of present situation, it is also difficult to reach 100% recycling）, to environment
It pollutes.Therefore, adhesive progress oil is changed into water, at a unavoidable class in lithium ion battery manufacturing process
Topic.
Currently, researcher has done this large amount of research work both at home and abroad, CN01108511.8, CN01108524.X are public
A kind of adhesive has been opened, but has changed adhesive in actual use, there is also following disadvantages：Low-temperature bake is needed, is caused
Formation efficiency is low, and the pole piece of preparation is crisp, and flexibility is poor, causes to easily snap off in cell manufacturing process, and in manufacturing process
In be also easy to produce warpage, cause battery to be easy to be formed waste product, increase battery production cost；CN201410731027.8,
For CN200910300150.3 using low polar polymer as core, highly polar polymer, which does shell and synthesizes flexibility, improved lithium
Ion aqueous binder, still, since using having polymer as reaction core, selectivity and designability are poor, should
Product also not can be good at the problem of improving lithium ion battery manufacturing process.
Invention content
In view of the above shortcomings of the prior art, the present invention provides a kind of with stable structure, the lower lithium of surface tension
Ion battery aqueous binder, second purpose are to provide the preparation method of water adhesive of lithium ion battery.
In order to solve the above-mentioned technical problem, present invention employs the following technical solutions：
A kind of water adhesive of lithium ion battery, it is characterised in that：By lotion and the glue being dispersed in lotion
Milk particle forms, and the latex particle is three-decker, and kernel is made of the polymer of lower glass transition temperatures, intermediate
Transition zone is made of the polymer of medium glass transition temperature, and outer shell is made of the polymer of high glass transition temperature, from
It is interior gradually to change software strategy into software-hardware strategy to outer；The solid content of lotion is 5~30%, interior nuclear polymer, middle transition one polymer, shell strata
Close object mass ratio be：（5~30）：（20~60）：（30~60）.
Further feature is that the emulsifier of the lotion is acrylamido isopropyl sulfonate, 2- allyl ethers 3-
In hydroxy propane -1- sulfonate, vinylsulfonate, allylsulfonate, methacrylic sulfonic acids salt, styrene sulfonate
It is any or any two are mixed with the ratio for being each greater than 0 percent, or wantonly three kinds to be each greater than 0 percent ratio
It mixes, or wantonly four kinds are mixed with the ratio for being each greater than 0 percent, or wantonly five kinds mixed to be each greater than 0 percent ratio
It closes or six kinds is obtained by mixing with the ratio for being each greater than 0 percent；Wherein, the cation of salt be lithium ion, sodium ion or
Potassium ion, entire emulsifier weight are the 1~10% of gross mass.
The polymer of the lower glass transition temperatures of the kernel is to be less than 0 DEG C by glass transition temperature
Acrylic ester monomer or mixture polymer form, be ethyl acrylate, propyl acrylate, acrylic acid just/isobutyl ester,
N-octyl, the different monooctyl esters of acrylic acid 2-, acrylic acid just/isodecyl ester, dodecylacrylate, acrylic acid myristyl
Ester, aliphatic acrylate, lauryl acrylate, octadecyl acrylate, behenyl base ester, isobomyl acrylate
Ester, methacrylic acid just/isobutyl ester, the different monooctyl esters of methacrylic acid 2-, vinyl neodecanoate, dibutyl maleate, metering system
Sour 18 fat, glycidyl methacrylate, polyalkylene glycol acrylate monomethyl ether, Methylacrylic acid polyethylene glycol single armor ether,
Allyl polyglycol, any one of allyl polypropylene glycol etc. or any two are mixed with the ratio for being each greater than 0 percent
It closes, or wantonly three kinds are mixed with the ratio for being each greater than 0 percent, or wantonly four kinds are mixed with the ratio for being each greater than 0 percent,
Until aforementioned whole components are formed with the ratio mixed polymerization for being each greater than 0 percent.
The polymer of the outer shell high glass-transition temperature is the monomer or mixture for being higher than 0 DEG C by glass transition temperature
It is polymerized, is acrylic acid, methacrylic acid, acrylates, methacrylate, methyl methacrylate, methacrylic acid
Ethyl ester, acrylamide, Methacrylamide, methylene-bisacrylamide, itaconic acid, maleic acid, itaconate, maleate,
Hydroxy-ethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxy propyl methacrylate, acrylonitrile, butene nitrile, 5-
Hexene nitrile,-cyclohexene -1- nitriles, 2- nonenyl nitriles, vinylacetate, N hydroxymethyl acrylamide, hydroxylethyl uride, double third
Ketone acrylamide, diallyl phthalate, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, three
Methylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, the double metering systems of bisphenol-A glycerine
Acid esters, glycerine 1, bis- glycerine alkyd diacrylates of 3-, 1,6- hexylene glycol double methacrylate, two contracting propylene glycol double methacrylates,
Any one of tripropylene glycol double methacrylate or any two mixed with the ratio for being each greater than 0 percent, or wantonly three kinds
To be each greater than 0 percent ratio mixing, or wantonly four kinds are mixed with the ratio for being each greater than 0 percent, until aforementioned complete
Portion's component is formed with the ratio mixed polymerization for being each greater than 0 percent, wherein salt is potassium, sodium, lithium salts.
The transition one polymer by the lower glass transition temperatures simultaneously containing kernel at least one monomer and shell
The mixture of at least one monomer of the high glass-transition temperature of layer is polymerized, and is wrapped in core surface, forms transition
Layer structure.
The initiator of described adhesive is potassium peroxydisulfate, ammonium persulfate, sodium peroxydisulfate, sodium sulfite,
Sodium hydrogensulfite, azobisisoheptonitrile, azo-bis-isobutyrate hydrochloride（AIBA）, two isobutyl imidazoline hydrochloride of azo
（AIBI）And any one of azodiisobutyronitrile etc. or any two be each greater than 0 percent ratio mix, or appoint
Three kinds are mixed with the ratio for being each greater than 0 percent, or wantonly four kinds are mixed with the ratio for being each greater than 0 percent, until before
It states whole components and is mixed with the ratio for being each greater than 0 percent.
Mass percent of the nuclear polymer in entire molecule is 5~30 in described adhesive, and glass transition temperature is -60
~-10 DEG C, preferably -40~-20 DEG C；The mass percent of transition one polymer is 10~80, and glass transition temperature is -20~20
DEG C, preferably -10~10 DEG C；Outer shell shell polymeric mass percent be 30~80, glass transition temperature be 10~80 DEG C, preferably 20
~50 DEG C.
The glass transition temperature of nuclear polymer is -40~-20 DEG C in described adhesive；The glass transition temperature of transition one polymer
It is -10~10 DEG C；Outer shell shell polymeric glass transition temperature is 20~50 DEG C.
The preparation method of water adhesive of lithium ion battery, it is characterised in that include the following steps,
1）According to the component and proportioning of technological requirement, prepare emulsifier, interior nuclear monomer or mixture, intermediate layer monomer or mixed
Close object, outer shell monomer or mixture, initiator and deionized water；
2）Interior nuclear monomer or mixture and deionized water are added in reaction unit, stirring is to be uniformly mixed；Be warming up to 50 DEG C-
80 DEG C, initiator is added and causes polymerization, a period of time of constant temperature technological requirement, such as isothermal reaction 0.6-1.5 hours；
3）The speed of intermediate layer monomer or mixture is added dropwise in control, is added dropwise to complete in 1-5 hours, and temperature is controlled 60
DEG C -90 DEG C, and stir；Then at 60 DEG C -90 DEG C, a period of time of constant temperature technological requirement, such as isothermal reaction 2-5 hours；
4）The speed of outer shell monomer or mixture is added dropwise in control, is added dropwise to complete in 1-5 hour, and temperature is controlled 60 when addition
DEG C -90 DEG C, and stir；After being added dropwise to complete, 60 DEG C -90 DEG C are maintained the temperature at, a period of time of constant temperature technological requirement.
Compared with prior art, water adhesive of lithium ion battery that the present invention obtains and preparation method thereof has following excellent
Point：
1, invention adhesives solve the environmental issue of lithium battery adhesive using water as decentralized medium, are environment-friendly type bondings
Agent.
2, the present invention uses and is respectively synthesized kernel, transition zone, the synthetic method of shell, the machine for the adhesive agent emulsion prepared
Tool stability is good, is not in the demulsifying phenomenons such as reunion in dispersion process；Surface tension is relatively low, be more favorable for conductive agent and
The dispersion of negative material greatly improves dispersion efficiency and film forming.
3, adhesive agent emulsion of the invention has the characteristics that large arch dam, low viscosity, and production efficiency is high, easy to use；Simultaneously
Adhesives made of this method are had excellent performance, and flexibility is good, and the cathode pole piece prepared is smooth, and cyclicity is good.
4, the present invention is played in capacity and capacity keeps being better than existing adhesive, and is conducive to large-scale promotion.
Specific implementation mode
With reference to specific embodiment, the present invention is further described.
Water adhesive of lithium ion battery of the present invention is made of lotion and the latex particle being dispersed in lotion, the glue
Milk particle is three-decker, and kernel is made of the polymer of lower glass transition temperatures, and intermediate layer is by medium glass
The polymer of transition temperature forms, and outer shell is made of the polymer of high glass transition temperature, gradually by soft from kernel to outer shell
It is hardened, hardness gradually increases；Wherein, the solid content quality of lotion is 5~30%, i.e., the latex particle of solid constituent in lotion
Quality is very 5~30%；Interior nuclear polymer, middle transition one polymer, shell one polymer mass ratio be：（5~
30）：（20~60）：（30~60）.
The emulsifier of the lotion is acrylamido isopropyl sulfonate, 2- allyl ether 3- hydroxy propane -1- sulfonic acid
Any one of salt, vinylsulfonate, allylsulfonate, methacrylic sulfonic acids salt, styrene sulfonate or any two
Be each greater than 0 percent ratio mixing, or wantonly three kinds be each greater than 0 percent ratio mixing, or wantonly four kinds with
Each greater than 0 percent ratio mixing, wantonly five kinds be each greater than 0 percent ratio mix or six kinds with respective
Ratio more than 0 percent is obtained by mixing；Wherein, the cation of salt is lithium ion, sodium ion or potassium ion, entire emulsification
Agent mass ratio is 1~10%；
The polymer of the lower glass transition temperatures of the kernel is the esters of acrylic acid list for being less than 0 DEG C by glass transition temperature
Body mixture polymer forms, as, ethyl acrylate, propyl acrylate, acrylic acid just/isobutyl ester, n-octyl, third
The different monooctyl esters of olefin(e) acid 2-, acrylic acid just/isodecyl ester, dodecylacrylate, acrylic acid tetradecane base ester, acrylic acid cetyl
Ester, lauryl acrylate, octadecyl acrylate, behenyl base ester, isobornyl acrylate, methacrylic acid just/
Isobutyl ester, the different monooctyl esters of methacrylic acid 2-, vinyl neodecanoate, dibutyl maleate, 18 fat of methacrylic acid, metering system
Acid glycidyl ester, polyalkylene glycol acrylate monomethyl ether, Methylacrylic acid polyethylene glycol single armor ether, allyl polyglycol, alkene
Any one of propyl polypropylene glycol etc. or any two mixed with the ratio for being each greater than 0 percent, or wantonly three kinds with respective
Ratio more than 0 percent mixes, or wantonly four kinds are mixed with the ratio for being each greater than 0 percent, until aforementioned whole components
It is formed with the ratio mixed polymerization for being each greater than 0 percent；
The polymer of the outer shell high glass-transition temperature be by glass transition temperature higher than 0 DEG C monomer mixture polymerization and
At, as acrylic acid, methacrylic acid, acrylates, methacrylate, methyl methacrylate, ethyl methacrylate,
Acrylamide, Methacrylamide, methylene-bisacrylamide, itaconic acid, maleic acid, itaconate, maleate, acrylic acid
Hydroxyl ethyl ester, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxy propyl methacrylate, acrylonitrile, butene nitrile, 5- hexenes
Nitrile,-cyclohexene -1- nitriles, 2- nonenyl nitriles, vinylacetate, N hydroxymethyl acrylamide, hydroxylethyl uride, diacetone third
Acrylamide, diallyl phthalate, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, three hydroxyl first
Base propane trimethyl acrylic ester, ethoxylated trimethylolpropane triacrylate, bisphenol-A glycerine methacrylate
Ester, glycerine 1, bis- glycerine alkyd diacrylates of 3-, 1,6- hexylene glycol double methacrylate, two contracting propylene glycol double methacrylates, three
Any one of contracting propylene glycol double methacrylate or any two be each greater than 0 percent ratio mix, or wantonly three kinds with
Each greater than 0 percent ratio mixes, or wantonly four kinds are mixed with the ratio for being each greater than 0 percent, until aforementioned whole
Component is formed with the ratio mixed polymerization for being each greater than 0 percent, wherein salt is potassium, sodium, lithium salts；
The transition one polymer is by the polymer of the lower glass transition temperatures simultaneously containing kernel and the high glass of outer shell
At least one monomer or various of monomer mixture for changing the polymer of transition temperature are polymerized, and are wrapped in core surface, until
One layer of transition layer structure is formed less；
The initiator of described adhesive is potassium peroxydisulfate, ammonium persulfate, sodium peroxydisulfate, sodium sulfite, sodium hydrogensulfite, azo
Two different heptonitriles, azo-bis-isobutyrate hydrochloride（AIBA）, two isobutyl imidazoline hydrochloride of azo（AIBI）And two isobutyl of azo
Any one of nitrile etc. or any two mixed with the ratio for being each greater than 0 percent, or wantonly three kinds to be each greater than percent
Zero ratio mixes, or wantonly four kinds are mixed with the ratio for being each greater than 0 percent, until aforementioned whole components are with each greater than
0 percent ratio mixing.
Mass percent of the described adhesive inner core in entire molecule be 5~30, glass transition temperature be -60~-
10 DEG C, preferably -40~-20 DEG C；The mass percent of transition zone be 20~60, glass transition temperature be -20~20 DEG C, preferably -10
~10 DEG C；Shell structure mass percent is 30~60, and glass transition temperature is 10~80 DEG C, preferably 20~50 DEG C；
Containing admittedly for described adhesive is 8-30%, and viscosity is in 5000-100000mpas.
The preparation method of water adhesive of lithium ion battery, it is characterised in that include the following steps,
1）According to the component and proportioning of technological requirement, prepare emulsifier, interior nuclear monomer or mixture, intermediate layer monomer or mixed
Close object, outer shell monomer or mixture, initiator and deionized water；
2）Interior nuclear monomer or mixture and deionized water are added in reaction unit, stirring is to be uniformly mixed；Be warming up to 50 DEG C-
80 DEG C, initiator is added and causes polymerization, a period of time of constant temperature technological requirement, such as isothermal reaction 0.6-1.5 hours；
3）The speed of intermediate layer monomer or mixture is added dropwise in control, is added dropwise to complete in 1-5 hours, and temperature is controlled 60
DEG C -90 DEG C, and stir；Then at 60 DEG C -90 DEG C, a period of time of constant temperature technological requirement, such as isothermal reaction 2-5 hours；
4）The speed of outer shell monomer or mixture is added dropwise in control, is added dropwise to complete in 1-5 hour, and temperature is controlled 60 when addition
DEG C -90 DEG C, and stir；After being added dropwise to complete, 60 DEG C -90 DEG C are maintained the temperature at, a period of time of constant temperature technological requirement, such as constant temperature
Reaction 2-5 hours.
Embodiment 1：
The present embodiment uses sodium vinyl sulfonate for reactive emulsifier monomer, and interior nuclear monomer uses ethyl acrylate, transition zone
Monomer uses ethyl acrylate, methyl acrylate and acrylic acid, capsomere to use acrylic acid, acrylamide and methacrylic acid
Methyl esters, by monomer, initiator is individually identified as A, B, C according to core, transition zone, shell, and concrete composition is as follows：
A：Sodium vinyl sulfonate 5g, ethyl acrylate 20g, 141.6 grams of deionized water；
B：5 grams of acrylic acid, 25 grams of ethyl acrylate, 10 grams of methyl acrylate, 0.3 gram of sodium peroxydisulfate, 226.6 grams of deionized water；
C：15 grams of methyl methacrylate, 10 grams of acrylamide, 10 grams of acrylic acid, 0.3 gram of sodium peroxydisulfate, deionized water 198.3
Gram.
The preparation method of above-mentioned lithium ion battery adhesive agent emulsion is：A monomer mixtures are sequentially added, are stirred, rotating speed
200rpm, nitrogen protection are warming up to 75 DEG C, and 0.2 gram of sodium peroxydisulfate is added, and cause and polymerize, 1 hour reaction time, then slowly
B component monomer is added dropwise（It needs to be kept stirring when dropwise addition）, when dropwise addition temperature control at 78 DEG C, be added dropwise within 3 hours it is complete, then 78 DEG C
Component C monomer is finally added dropwise in constant temperature 30min（It needs to stir when dropwise addition）, 78 DEG C of dropping temperature is controlled, is added dropwise completely, so within 3 hours
After be warming up to 82 DEG C, the core-shell type aqueous adhesive of mentioned component is prepared, and viscosity is in 5000-6500 in and constant temperature 3 hours
Centipoise.
Embodiment 2：
The implementation case uses the process of above-mentioned case, with 1 the difference is that initiator uses ammonium persulfate, remaining
Equally, emulsion viscosity made from this method is bigger, and viscosity is in 6000-8000 centipoises.
Adhesive agent emulsion 200g, the deionized water 500g of the present embodiment synthesis are mixed slowly 10 minutes, are then added conductive
Agent 30g, high speed dispersion 60 minutes, then divide 2 addition LiMn2O4s, 1440g, high speed dispersion 120 minutes, worth LiMn2O4 slurry
Admittedly containing 69%, viscosity 6500 is coated on without obvious sediment after placing for 24 hours on aluminium foil, and apparent uniform, adhesive force is good.
Adhesive agent emulsion 200g, the deionized water 500g of the present embodiment synthesis are mixed slowly 10 minutes, are then added conductive
Agent 30g, high speed dispersion 60 minutes, then divide 2 times and tertiary cathode material (NCM523), 1440g, high speed dispersion 120 minutes, value is added
The LiMn2O4 slurry obtained contains 69% admittedly, and viscosity 4000 is coated on without obvious sediment after placing for 24 hours on aluminium foil, apparent uniform,
Adhesive force is good.
The adhesive agent emulsion of the present embodiment synthesis, negative material select artificial graphite.The proportioning of entire negative electrode slurry material
It is 3.0% for adhesive agent emulsion, BTR518 95.5%, conductive agent 1%, slurry is large arch dam 55%.Manufactured cathode pole piece is flat
Sliding, surface density is high.
Embodiment 3：
The preparation method of the present embodiment adhesive and 1 essentially identical, the difference is that initiator uses Ammonium Persulfate 98.5, and it is single
Body A, B, component C are different：Use 2- allyl ether 3- hydroxy propane -1- sodium sulfonates for reactive emulsifier monomer, interior nuclear monomer
Using ethyl acrylate, butyl acrylate and Isooctyl acrylate monomer mixture, transition zone monomer is using butyl acrylate, acrylic acid
Lithium, acrylamide and acrylic acid, capsomere use acrylic acid, lithium methacrylate, acrylamide and methyl methacrylate,
By monomer, initiator is individually identified as A, B, C according to core, transition zone, shell, and concrete composition is as follows：
A：2- allyl ether 3- hydroxy propane -1- sodium sulfonate 4g, ethyl acrylate 8g, 3 grams of butyl acrylate, Isooctyl acrylate monomer
2 grams, 96.3 grams of deionized water；
B：5 grams of Lithium acrylate, 15 grams of butyl acrylate, 5 grams of acrylic acid, 10 grams of acrylamide, 0.3 gram of Ammonium Persulfate 98.5, deionization
198.3 grams of water；
C：12 grams of acrylic acid, 5 grams of lithium methacrylate, 20 grams of acrylamide, 11 grams of methyl methacrylate, ammonium persulfate 0.3
Gram, 272 grams of deionized water.
The preparation method of above-mentioned lithium ion battery adhesive agent emulsion is：A monomer mixtures are sequentially added, are stirred, rotating speed
200rpm, nitrogen protection are warming up to 72 DEG C, and 0.2 gram of sodium peroxydisulfate is added, and cause and polymerize, 1 hour reaction time, then slow B
Constituent monomers（It needs to be kept stirring when dropwise addition）, when dropwise addition temperature control complete, then 76 DEG C of constant temperature 1 is added dropwise within 3 hours at 76 DEG C
Hour, component C monomer is finally added dropwise（It needs to stir when dropwise addition）, 76 DEG C of dropping temperature is controlled, is added dropwise completely within 3 hours, then rises
Temperature is to 80 DEG C, and constant temperature 6 hours, that is, the core-shell type aqueous adhesive of mentioned component is prepared, Gu containing being 15%.
The embodiment introduces the better butyl acrylate of flexibility in core and transition zone, thus adhesive obtained at
Film is more soft, and elasticity is excellent.
Embodiment 4：
The present embodiment and the method and process of embodiment 3 are essentially identical, and Main change is two different hydrochloric acid of azo in the initiator used
Salt, reaction temperature are controlled at 50-60 DEG C, and the adhesive agent emulsion viscosity of W-response time lengthening 6h, preparation are larger, mobility
It is good, there is water resistance, the excellent heat stability of the adhesive, decomposition temperature height.
Embodiment 5：
The preparation method of the present embodiment adhesive and 1 essentially identical, the difference is that initiator uses Ammonium Persulfate 98.5, and it is single
Body A, B, component C are different：Use 2- allyl ether 3- hydroxy propane -1- sodium sulfonates for reactive emulsifier monomer, interior nuclear monomer
Using lauryl acid esters, butyl acrylate and Isooctyl acrylate monomer mixture, transition zone monomer is using butyl acrylate, third
The different monooctyl ester of olefin(e) acid, Lithium acrylate and acrylic acid, capsomere use acrylic acid, lithium methacrylate, acrylamide and propylene
Nitrile, by monomer, initiator is individually identified as A, B, C according to core, transition zone, shell, and concrete composition is as follows：
A：2- allyl ether 3- hydroxy propane -1- sodium sulfonate 5g, lauryl acid esters 2g, 5 grams of butyl acrylate, acrylic acid is different
4 grams of monooctyl ester, 90.3 grams of deionized water；
B：8 grams of Lithium acrylate, 10 grams of butyl acrylate, 2 grams of Isooctyl acrylate monomer, 7 grams of acrylic acid, 0.3 gram of Ammonium Persulfate 98.5, go from
153 grams of sub- water；
C：10 grams of acrylic acid, 9 grams of lithium methacrylate, 20 grams of acrylamide, 11 grams of acrylonitrile, 0.3 gram of ammonium persulfate, deionization
283 grams of water.
The preparation method of above-mentioned lithium ion battery adhesive agent emulsion is：A monomer mixtures are sequentially added, are stirred, rotating speed
200rpm, nitrogen protection are warming up to 72 DEG C, and 0.2 gram of sodium peroxydisulfate is added, and cause and polymerize, 1 hour reaction time, then slow B
Constituent monomers（It needs to be kept stirring when dropwise addition）, when dropwise addition temperature control complete, then 76 DEG C of constant temperature 1 is added dropwise within 3 hours at 76 DEG C
Hour, component C monomer is finally added dropwise（It needs to stir when dropwise addition）, 76 DEG C of dropping temperature is controlled, is added dropwise completely within 3 hours, then rises
Temperature is to 80 DEG C, and constant temperature 6 hours, that is, the core-shell type aqueous adhesive of mentioned component is prepared, Gu containing being 15%.
The embodiment introduces the better Isooctyl acrylate monomer of flexibility and lauryl acid esters in core and transition zone,
Therefore adhesive film forming obtained is more soft, and elasticity is excellent.
Embodiment 6
The present embodiment and the method and process of embodiment 3 are essentially identical, and Main change is sodium peroxydisulfate in the initiator used, is prepared
Adhesive agent emulsion viscosity it is larger, good fluidity has water resistance, the excellent heat stability of the adhesive, and decomposition temperature is high.
Embodiment 7：
The present embodiment and the method and process of embodiment 3 are essentially identical, and Main change is two isobutyl miaow of azo in the initiator used
Oxazoline hydrochloride (abbreviation AIBA), at 50-60 DEG C, W-response time lengthening 6h, the adhesive of preparation is newborn for reaction temperature control
Fluid viscosity is larger, and good fluidity has water resistance, the excellent heat stability of the adhesive, and decomposition temperature is high.
Finally, it should be noted that technical side the above examples are only used to illustrate the technical scheme of the present invention and are not limiting
Case, although applicant describes the invention in detail with reference to preferred embodiment, those skilled in the art should manage
Solution, those are modified or replaced equivalently technical scheme of the present invention, without departing from the objective and range of the technical program,
It is intended to be within the scope of the claims of the invention.
Claims (9)
1. a kind of water adhesive of lithium ion battery, it is characterised in that：It is made of lotion and the latex particle being dispersed in lotion,
The latex particle is three-decker, and kernel is made of the polymer of lower glass transition temperatures, and intermediate layer is by medium
The polymer of glass transition temperature forms, and outer shell is made of the polymer of high glass transition temperature, from inside to outside gradually by soft
It is hardened；The solid content quality of lotion be 5~30%, interior nuclear polymer, middle transition one polymer, shell one polymer quality
Than for：（5~30）：（20~60）：（30~60）.
2. water adhesive of lithium ion battery according to claim 1, which is characterized in that the emulsifier of the lotion is third
Acrylamide base isopropyl sulfonate, 2- allyl ether 3- hydroxy propane -1- sulfonate, vinylsulfonate, allylsulfonate,
Any one of methacrylic sulfonic acids salt, styrene sulfonate or any two be each greater than 0 percent ratio mix,
Or wantonly three kinds be each greater than 0 percent ratio mix, or wantonly four kinds be each greater than 0 percent ratio mixing, or
Wantonly five kinds are obtained by mixing with the ratio mixing or six kinds that are each greater than 0 percent with the ratio for being each greater than 0 percent；Its
In, the cation of salt is lithium ion, sodium ion or potassium ion, and entire emulsifier is the 1~10% of gross mass.
3. water adhesive of lithium ion battery according to claim 1 or 2, which is characterized in that the low glass of the kernel
The polymer for changing transition temperature be acrylic ester monomer by glass transition temperature less than 0 DEG C or mixture polymer and
At, as ethyl acrylate, propyl acrylate, acrylic acid just/isobutyl ester, n-octyl, the different monooctyl esters of acrylic acid 2-, propylene
Acid just/isodecyl ester, dodecylacrylate, acrylic acid tetradecane base ester, aliphatic acrylate, lauryl acrylate,
Octadecyl acrylate, behenyl base ester, isobornyl acrylate, methacrylic acid just/isobutyl ester, methacrylic acid
The different monooctyl esters of 2-, vinyl neodecanoate, dibutyl maleate, 18 fat of methacrylic acid, glycidyl methacrylate, propylene
Acid polyethylene glycol monomethyl ether, Methylacrylic acid polyethylene glycol single armor ether, allyl polyglycol, appointing in allyl polypropylene glycol
One kind or any two be each greater than 0 percent ratio mix, or wantonly three kinds be each greater than 0 percent ratio mix
It closes, or wantonly four kinds are mixed with the ratio for being each greater than 0 percent, until aforementioned whole components are to be each greater than 0 percent
Ratio mixed polymerization forms.
4. water adhesive of lithium ion battery according to claim 1 or 2, which is characterized in that the shell floor height glass
Change transition temperature polymer be by glass transition temperature higher than 0 DEG C monomer or mixture be polymerized, be acrylic acid, methyl-prop
Olefin(e) acid, acrylates, methacrylate, methyl methacrylate, ethyl methacrylate, acrylamide, methacryl
Amine, methylene-bisacrylamide, itaconic acid, maleic acid, itaconate, maleate, hydroxy-ethyl acrylate, hydroxyethyl methacrylate
Ethyl ester, hydroxypropyl acrylate, hydroxy propyl methacrylate, acrylonitrile, butene nitrile, 5- hexene nitriles,-cyclohexene -1- nitriles, 2- nonenes
Nitrile, vinylacetate, N hydroxymethyl acrylamide, hydroxylethyl uride, Diacetone Acrylamide, diallyl phthalate third
Ester, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylol-propane trimethacrylate, second
Oxygroup trimethylolpropane trimethacrylate, bisphenol-A glycerine double methyl methacrylate, glycerine 1, bis- glycerine alkyd dipropyls of 3-
Olefin(e) acid ester, 1,6- hexylene glycol double methacrylate, two contracting propylene glycol double methacrylates, any in tripropylene glycol double methacrylate
It plants or any two is mixed with the ratio for being each greater than 0 percent, or wantonly three kinds are mixed with the ratio for being each greater than 0 percent,
Or wantonly four kinds mixed with the ratio for being each greater than 0 percent, until aforementioned whole components are to be each greater than 0 percent ratio
Mixed polymerization forms, wherein salt is potassium, sodium, lithium salts.
5. requiring water adhesive of lithium ion battery described in 1 or 2 according to power, which is characterized in that the transition one polymer by
The mixture of at least one monomer of at least one monomer containing kernel and outer shell is polymerized simultaneously, and is wrapped in kernel
Surface forms transition layer structure.
6. requiring water adhesive of lithium ion battery described in 1 according to power, which is characterized in that the initiator of described adhesive is
Potassium peroxydisulfate, ammonium persulfate, sodium peroxydisulfate, sodium sulfite, sodium hydrogensulfite, azobisisoheptonitrile, two NSC 18620 hydrochloric acid of azo
Salt（AIBA）, two isobutyl imidazoline hydrochloride of azo（AIBI）And any one of azodiisobutyronitrile etc. or any two with
Each greater than 0 percent ratio mixing, or wantonly three kinds to be each greater than 0 percent ratio mixing, or wantonly four kinds with each
From the ratio mixing more than 0 percent, until aforementioned whole components are mixed with the ratio for being each greater than 0 percent.
7. requiring 1,2,6 any water adhesive of lithium ion battery according to power, which is characterized in that described adhesive kernel
Mass percent of the polymer in entire molecule is 5~30, and glass transition temperature is -60~-10 DEG C；The matter of transition one polymer
It is 10~80 to measure percentage, and glass transition temperature is -20~20 DEG C,；Outer shell shell polymeric mass percent is 30~80, glass
It is 10~80 DEG C to change temperature.
8. requiring the water adhesive of lithium ion battery described in 7 according to power, which is characterized in that nuclear polymer in described adhesive
Glass transition temperature is -40~-20 DEG C；The glass transition temperature of transition one polymer is -10~10 DEG C；Outer shell shell polymeric glass
It is 20~50 DEG C to change temperature.
9. the preparation method of water adhesive of lithium ion battery, it is characterised in that include the following steps,
1）According to the component and proportioning of technological requirement, prepare emulsifier, interior nuclear monomer or mixture, intermediate layer monomer or mixed
Close object, outer shell monomer or mixture, initiator and deionized water；
2）Interior nuclear monomer or mixture and deionized water are added in reaction unit, stirring is to be uniformly mixed；Be warming up to 50 DEG C-
80 DEG C, initiator is added and causes polymerization, a period of time of constant temperature technological requirement；
3）The speed of intermediate layer monomer or mixture is added dropwise in control, is added dropwise to complete in 1-5 hours, and temperature is controlled 60
DEG C -90 DEG C, and stir；Then at 60 DEG C -90 DEG C, a period of time of constant temperature technological requirement；
4）The speed of outer shell monomer or mixture is added dropwise in control, is added dropwise to complete in 1-5 hour, and temperature is controlled 60 when addition
DEG C -90 DEG C, and stir；After being added dropwise to complete, 60 DEG C -90 DEG C are maintained the temperature at, a period of time of constant temperature technological requirement.
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|---|---|---|---|---|
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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 |
Cited By (21)
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| EP3736886A1 (en) | 2019-05-09 | 2020-11-11 | Fujian Blue Ocean & Black Stone Technology Co., Ltd. | Aqueous binder and preparation method thereof |
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