CN105778834B - Lithium ion battery ceramic diaphragm adhesive and preparation method thereof - Google Patents
Lithium ion battery ceramic diaphragm adhesive and preparation method thereof Download PDFInfo
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- CN105778834B CN105778834B CN201610160971.1A CN201610160971A CN105778834B CN 105778834 B CN105778834 B CN 105778834B CN 201610160971 A CN201610160971 A CN 201610160971A CN 105778834 B CN105778834 B CN 105778834B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/10—Homopolymers or copolymers of methacrylic acid esters
- C09J133/12—Homopolymers or copolymers of methyl methacrylate
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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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
Abstract
The present invention relates to a kind of lithium ion battery ceramic diaphragm adhesive and preparation method thereof, the method that described adhesive uses emulsion polymerization, the acrylic compounds soft monomer and hard monomer of special ratios are mixed to form to stable latex beam by the peptizaiton of Compositional type emulsifying agent, in the presence of initiator, polymerized monomer polymerize in micella, forms stable polymer emulsion.Described adhesive, with good wellability and while initial bonding strength, also keeps certain hardness and tensile strength, so that adhesive possesses excellent adhesion strength, low application viscosity and high mechanical strength by the copolymer of formation；In addition, invention adhesives emulsion is excellent to ceramic particle dispersive property, preparation technology is simple, environmentally friendly, and the heat resistance requirement to base material is substantially reduced.
Description
Technical field
The present invention relates to field of lithium ion battery, more particularly to a kind of lithium ion battery ceramic diaphragm adhesive and its system
Preparation Method.
Background technology
Lithium ion battery due to voltage is high, specific energy is big, working range is wide, specific power is big, electric discharge is steady, store when
Between it is long the advantages of, be widely used in the various fields such as mobile phone, computer, energy storage device and electric automobile at present, with battery
The continuous increase of capacity and voltage, its security risk is also incrementally increased, and its septation can influence the interfacial structure of battery, internal resistance
And battery capacity, cycle-index and security performance, its heat-resisting and stability plays vital effect to the safety of battery.
Due to traditional polyethylene (Polyethylene, PE) barrier film and polypropylene (Polypropylene, PP) barrier film
Fusing point is relatively low, respectively 125 DEG C and 158 DEG C, thus both barrier films are easily deformed upon very in the case where overheat condition occurs for battery
To melting so that short circuit occurs for both positive and negative polarity, so as to trigger serious security incident.In order to improve this case, people develop
Carry out PP/PE composite diaphragms.Because PE fusing point is less than PP, melted first in battery temperature-rise period, so that inaccessible micropore,
Breaking current, makes battery temperature no longer rise, while PP assigns barrier film resistance to overturning, it is to avoid short circuit between both positive and negative polarity.But
It is due to the difference of PP, PE stress-strain characteristics, internal stress is easily produced in coaxially stretching film forming procedure, so that can be one
Determine to make barrier film be applicable the undesirable conditions such as middle generation fold deformation in battery in degree, while composite diaphragm can also increase barrier film
Thickness, can increase the internal resistance of barrier film to a certain extent.
In order to further improve the heat endurance and oxidation resistance of barrier film, it has been developed that ceramic diaphragm, by
The traditional polymer membrane surface such as PE or PP coated ceramic layer improves the heat endurance and oxidation resistance of barrier film.At present, make pottery
The inorganic particle of porcelain diaphragm application is usually the nanometer or submicro inorganic oxide powder of high-temperature stable, and its preparation mainly passes through
Inorganic particle, binding agent are disperseed to form slurry in a solvent, are coated with to surface of polymer substrates formation ceramic layer.Ceramics every
The performances such as heat endurance, pore size, mechanical strength, air penetrability and the closed pore temperature of film by inorganic particle, binding agent and
The influence of preparation technology.
Because in the market binding agent species is more, physicochemical property difference is big, and the thermal contraction of binding agent in itself also results in ceramics
The contraction of barrier film；Importantly, being in during barrier film use in electric field, adhesive is except requiring to possess basic caking property
Can be outer, it is necessary to have stable chemical property.Prior art CN104064712A also discloses that fusing point due to binding agent, molten
Xie Du, molecular weight etc. are each variant, and the selection of binding agent certainly can influence the performance of ceramic diaphragm, and it to ceramic diaphragm by holding
Whether continuous heating observation ceramic diaphragm forms perforation, so as to screen the adhesive used in ceramic diaphragm.Therefore, the performance of binding agent
The key factor good and bad as ceramic diaphragm performance is determined.
At present, adhesive is typically chosen high molecular polymer in the prior art, and such as fluorocarbon resin is as gathered inclined 1,1- difluoros
Ethene (Polyvinylidene fluoride, PVDF), polytetrafluoroethylene (PTFE) (Polytetrafluoroethylene, PTFE) and
Tetrafluoraoethylene-hexafluoropropylene copolymer (Hexafluoropropene-tetrafluoroethylene copolymer, FEP)
Deng, and polyacrylic acid derivative, HPAM Degraded Bacteria, polyethylene, poly- propionamide (Polyscrylamide, PAM), butylbenzene
Rubber (Styrene, 1,3-butadiene polymer, SBR) etc. has the adhesive of heat resistance and electrolyte-resistant.However,
The adhesives such as PVDF, PTFE, FEP are a kind of adhesives based on organic solvent, harmful to environment；And aqueous binder for example poly- third
Gadoleic acid derivative, HPAM Degraded Bacteria and SBR etc., although environmentally friendly, but adhesion strength is smaller, and it is used for negative pole
The adhesive of material powder, the application in ceramic diaphragm is restricted.
Prior art CN203571420A is disclosed to improve the bonding force and solvent resistance of ceramic diaphragm binding agent, is utilized
Epoxy resin graft modification water soluble acrylic acid ester adhesive as made from four or more monomer copolymerization, the adhesive passes through
The cross-linking reaction of the groups such as the carboxyl in epoxide group and acrylate, amino, imino group in epoxy resin, so as to increase point
Sub- cohesive energy, and then improve polymer-bonded power enhancing, heat endurance.However, the adhesive viscosities are more than 2000 centipoises, apply
Cloth viscosity is high, may influence adhesive flow leveling, and then may influence the planarization and spatial stability of ceramic diaphragm；This
Outside, the environmentally friendly property of epoxy resin used in this method is poor, and Long Term Contact be unfavorable for it is healthy.
Be currently, there are and develop that a kind of heat endurance is good, adhesion strength is high, application viscosity is low, high mechanical strength simultaneously
The demand of the simple ceramic diaphragm adhesive of environmentally friendly, preparation technology.
The content of the invention
It is an object of the invention to provide a kind of heat endurance is good, adhesion strength is high, application viscosity is low, high mechanical strength simultaneously
Simple ceramic diaphragm adhesive of environmentally friendly, preparation technology and preparation method thereof.
In order to realize the purpose of the present invention, one aspect of the present invention is bonded there is provided a kind of lithium ion battery ceramic diaphragm
Agent, described adhesive includes the copolymer being made up of acrylic compounds hard monomer and acrylic compounds soft monomer copolymerization, wherein, described third
Olefin(e) acid class hard monomer and acrylic compounds soft monomer are 1~9 by weight:1.
In the embodiment of the invention, the glass transition temperature of the copolymer is -15 DEG C~10 DEG C.
Acrylic compounds soft monomer and hard monomer copolymerization of the present invention by special ratios, the copolymer of formation is with good
While wellability and initial bonding strength, certain hardness and tensile strength are also kept, so as to possess excellent bonding strong for adhesive
Degree, low application viscosity and high mechanical strength.
In the present invention, the acrylic compounds hard monomer refers to that polymer glass temperature is more than 0 DEG C of acrylic monomer,
The acrylic compounds soft monomer refers to that polymer glass temperature is less than or equal to 0 DEG C of acrylic monomer.
In the embodiment of the invention, the acrylic compounds hard monomer and acrylic compounds soft monomer are by weight
1.5~4:1, preferably 2~4:1.
In the embodiment of the invention, the acrylic compounds hard monomer is selected from methyl methacrylate, acryloyl
One or more in amine, acrylic acid, methacrylic acid, acrylonitrile monemer, the acrylic compounds soft monomer is selected from acrylic acid second
Ester, n-butyl acrylate, isobutyl acrylate, Isooctyl acrylate monomer (acrylic acid-2-ethyl caproite), acrylic acid -2- hydroxyl ethyl esters,
One or more in lauryl acid esters, octadecyl acrylate monomer.
In the embodiment of the invention, the acrylic compounds hard monomer be methyl methacrylate and acrylonitrile,
It is preferred that, the methyl methacrylate and acrylonitrile are 5 by weight:1~3.
In the embodiment of the invention, it is different that the acrylic compounds soft monomer is selected from n-butyl acrylate, acrylic acid
One or more in butyl ester, Isooctyl acrylate monomer, preferably are selected from Isooctyl acrylate monomer.
In the embodiment of the invention, the particle diameter of the copolymer is 30nm~400nm, it is preferred that described common
The particle diameter of polymers is 40nm~300nm, it is furthermore preferred that the particle diameter of the copolymer is 60nm~300nm.
In the embodiment of the invention, described adhesive is emulsion form, and viscosity is (25 DEG C of 10~200 centipoises
Under), it is preferred that the viscosity of described adhesive is 10~100 centipoises (at 25 DEG C).
Further aspect of the present invention provides a kind of preparation method of lithium ion battery ceramic diaphragm adhesive, including as follows
Step：
Acrylic compounds hard monomer, acrylic compounds soft monomer, Compositional type emulsifying agent and water are added in pre-emulsification reactor,
It is scattered to form stable pre-emulsion；
Water and part pre-emulsion are added in polymerization reaction kettle, polymeric reaction temperature is heated to, Redox Initiator is added dropwise
Agent, reacts 5min~20min, and remaining pre-emulsion is added dropwise, and 2h~3h is dripped off, insulation reaction 30min~60min, after cooling
It is lithium ion battery ceramic diaphragm adhesive to copolymer；
Wherein, the acrylic compounds hard monomer and acrylic compounds soft monomer are 1~9 by weight:1.
In the embodiment of the invention, the acrylic compounds hard monomer and acrylic compounds soft monomer are by weight
1.5~4:1, preferably 2~4:1.
In the embodiment of the invention, the acrylic compounds hard monomer is selected from methyl methacrylate, acryloyl
One or more in the monomers such as amine, acrylic acid, methacrylic acid, acrylonitrile, the acrylic compounds soft monomer is selected from acrylic acid
Ethyl ester, n-butyl acrylate, isobutyl acrylate, Isooctyl acrylate monomer (acrylic acid-2-ethyl caproite), acrylic acid -2- hydroxyl second
One or more in the monomers such as ester, lauryl acid esters, octadecyl acrylate.
In the embodiment of the invention, the acrylic compounds hard monomer be methyl methacrylate and acrylonitrile,
It is preferred that, the methyl methacrylate and acrylonitrile are 5 by weight:1~3.
In the embodiment of the invention, it is different that the acrylic compounds soft monomer is selected from n-butyl acrylate, acrylic acid
One or more in butyl ester, Isooctyl acrylate monomer, preferably are selected from Isooctyl acrylate monomer.
In the embodiment of the invention, the Compositional type emulsifying agent is using anion emulsifier, cation emulsified
One or more in agent, nonionic emulsifier, ionic/nonionic emulsifying agent.It is preferred that, the Compositional type emulsifying agent is using cloudy
Ionic emulsifying agent and nonionic emulsifier are used cooperatively.
Anion emulsifier of the present invention can be carboxylic acid type emulsifying agent, sulfonate type emulsifying agent, sulfuric ester salt form breast
One or more in agent etc..Wherein, carboxylic acid type emulsifying agent formula is RCOOM, and R is C7-C20Alkyl, aryl or aryl
Alkyl, M is metal；Sulfonate type emulsifying agent include Fatty sulphonates, di-fatty acid ester sulfonates, fatty acid amide sulfonate,
Alkylbenzenesulfonate, formaldehyde condensation naphthalene sulfonate etc., for example：Dodecyl sodium sulfate (SDS), neopelex, oil
Sour sodium, potassium oleate, alkyl acrylic -2-ethanesulfonic acid sodium salt, 2- acrylamide -2,2- dimethyl ethyl sulfonic acids sodium, to styrene sulphur
Sour sodium, acrylamide stearic acid sodium salt, sodium allyl sulfosuccinic alkyl ester etc..
Nonionic emulsifier of the present invention is polyoxyethylene polyoxyethylene carboxylic ester, polyol carboxylate, polyoxyethylene polyols carboxylic
One or more in acid esters, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylate amide, alkylolamides etc.,
For example：Polyoxyethylene carboxylate, sorbitan fatty acid ester (Span series) are such as sorbitan mono-laurate
(Span20), sorbitan monopalmitate (Span 40), sorbitan monostearate (Span60), Sorbitan
Alcohol monoleate (Span 80), sorbitan trioleate (Span 85), polyoxyethylene sorbitan fatty acid ester
(Tween series) is such as polyoxyethylene 20 sorbitan monolaurate (Tween 20), polyoxyethylene sorbitan list palm
Ester (Tween 40), polyoxyethylene 20 sorbitan monostearate (Tween 60), polyoxyethylene sorbitan list oleic acid
Ester (Tween 80), polyoxyethylene 20 sorbitan trioleate (Tween 85) etc..
Cationic emulsifier of the present invention is the one or more in alkylammonium salt and quaternary ammonium salt, for example：Dodecyl
Ammonium chloride, hexadecyltrimethylammonium chloride, dodecylpyridinium bromide, cetyl pyridinium bromide or octadecyldimethyl
Vinyl phenyl ammonium chloride etc..
Ionic/nonionic emulsifying agent of the present invention is the emulsifying agent simultaneous with ionic group and non-ionic group, example
Such as, fatty alcohol polyoxy alkene ether sodium sulfate (AES) or NPE -2- sulfonic group amber acid monoester disodium salts (MS-1)
Deng.
It is preferred that, the consumption of the Compositional type emulsifying agent is by weight being 8 for 0.8%~8%, HLB of raw material gross weight
~35, it is preferred that HLB is 11-17.
In the embodiment of the invention, the redox initiator is selected from ammonium persulfate/sodium formaldehyde sulfoxylate, persulfuric acid
Ammonium/sodium hydrogensulfite, potassium peroxydisulfate/sodium hydrogensulfite, potassium peroxydisulfate/silver nitrate, persulfate/mercaptan, ammonium persulfate/sulfuric acid
Ferrous iron, potassium peroxydisulfate/frerrous chloride, hydrogen peroxide/tartaric acid, hydrogen peroxide/sodium formaldehyde sulfoxylate, hydrogen peroxide/sulfuric acid ferrous iron, peroxide
Change hydrogen/frerrous chloride, TBHP/sodium formaldehyde sulfoxylate, TBHP/sodium pyrosulfite, benzoyl peroxide/N,
Accelerine, benzoyl peroxide //N, N- diethylanilines, benzoyl peroxide/ferrous pyrophosphate, isopropylbenzene peroxide
Change one kind in hydrogen/frerrous chloride, the aziridine of isopropyl benzene hydroperoxide/tetra-.
It is preferred that, the consumption of the redox initiator is acrylic compounds hard monomer and the soft list of acrylic compounds by weight
The 0.05%~0.8% of body gross weight.
In the embodiment of the invention, the consumption of the water by weight 70% for raw material gross weight~
86%.
In the embodiment of the invention, the polymeric reaction temperature is 30 DEG C~80 DEG C, preferably 40 DEG C~70
℃。
Beneficial effect of the present invention：
Invention adhesives particle diameter is smaller, excellent to ceramic particle dispersive property, and the acrylic compounds by special ratios are soft
Monomer and hard monomer copolymerization, the copolymer of formation also keep certain hardness with good wellability and while initial bonding strength
And tensile strength, so that adhesive possesses excellent adhesion strength, low application viscosity and high mechanical strength.In addition, this
Invention adhesive avoids the volatilization of solvent using water as solvent in production process, VOC discharge is reduced, while using water to be molten
Agent, can effectively reduce operation temperature, reduce energy consumption, the heat resistance requirement of base material in itself be substantially reduced, its preparation process pair
Environment-friendly, preparation technology is simple.
Brief description of the drawings
Fig. 1 show the TG-DSC spectrograms of the ceramic diaphragm adhesive of the preparation of the embodiment of the present invention 1.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Site preparation is described, it is clear that described embodiment is only a part of embodiment of the invention, rather than whole embodiments.Based on this
Embodiment in invention, the every other reality that those of ordinary skill in the art are obtained under the premise of creative work is not made
Example is applied, the scope of protection of the invention is belonged to.
Embodiment 1:
In the present embodiment, ceramic diaphragm is compounded as emulsifying agent with adhesive using SDS and sorbitan fatty acid ester,
Using ammonium persulfate and sodium formaldehyde sulfoxylate as initiator, polymerization uses methyl methacrylate and acrylonitrile with acrylic compounds hard monomer,
Polymerization uses Isooctyl acrylate monomer, wherein methyl methacrylate, acrylonitrile and Isooctyl acrylate monomer with acrylic compounds soft monomer
The ratio by mass ratio of three is 5:3:2.
Above-mentioned ceramic diaphragm is specially with the preparation method of adhesive：Add 10 parts of SDS, 50 parts of sorbitan fatty acid
Ester and 300 parts of water are sufficiently mixed in being placed in pre-emulsification bottle, and 375 parts of methyl methacrylates, 225 parts of propylene are sequentially added afterwards
Nitrile and 150 parts of Isooctyl acrylate monomer high-speed stirreds, rotating speed 600rpm disperse to form stable pre-emulsion；
100g pre-emulsions are taken out after 30min to add in reaction bulb, are begun to warm up while adding 400g water, when temperature is increased to
65 DEG C start drop and add ammonium persulfate and sodium formaldehyde sulfoxylate initiator respectively, start that pre-emulsion is added dropwise after 5min is added dropwise, keep pre-emulsion
In 180min completion of dropping, pre-emulsion completion of dropping is incubated 40min, and reduction temperature is made above-mentioned ceramic diaphragm to 40 DEG C, that is, and used
Adhesive agent emulsion.
Obtained adhesive solid content is 48%, is creamy white, and obtained Diameter of Binder Particles scope is glued in 80nm-200nm
Degree is less than 20 centipoises.The TG-DSC spectrograms of the adhesive as shown in figure 1, understand the excellent heat stability of the adhesive by spectrogram,
Decomposition temperature is higher than 300 DEG C, and heat endurance is good.
Embodiment 2：
In the present embodiment, ceramic diaphragm is multiple using neopelex and sorbitan fatty acid ester with adhesive
It is 5 with the ratio by mass ratio as emulsifying agent, polymerization methyl methacrylate, acrylonitrile and Isooctyl acrylate monomer three:
1:4, remaining step be the same as Example 1.
Obtained adhesive solid content is 40%, is creamy white, the particle size range of emulsion is in 100nm-300nm, and viscosity is small
In 10 centipoises.
Embodiment 3：
In the present embodiment, ceramic diaphragm is made with adhesive using SDS and polyoxyethylene sorbitan fatty acid ester compounding
For emulsifying agent, polymerization uses methyl methacrylate and acrylonitrile with acrylic compounds hard monomer, and acrylic compounds soft monomer is used in polymerization
Using isobutyl acrylate, the ratio by mass ratio of wherein methyl methacrylate, acrylonitrile and isobutyl acrylate three is
5:2:3。
Obtained adhesive solid content is 45%, is creamy white, the particle size range of emulsion is in 100nm-300nm, and viscosity is
40 centipoises.
Application Example 1：
The present embodiment selects the adhesive agent emulsion that embodiment 1-3 is synthesized, and ceramic particle is from the aluminum oxide that particle diameter is 200nm
(ceramic particle is 48% aqueous solution).The consumption of wherein ceramic particle solution and adhesive agent emulsion is respectively 100g and 80g,
Under 800rpm rotating speeds disperse 30min, afterwards vacuum eliminate solution in bubble, obtain slurry, be uniformly coated on base material PP every
On film.
The ceramic diaphragm prepared, ceramic particle disperses homogeneous, places 4h and is generated without flocculate, while ceramic particle
Slurry is good to PP wetability, can be good at being sprawled on PP films, and the barrier film after coated ceramic particle can be
Homogeneous film formation under the conditions of 180 DEG C, without deformation.
Tested after obtained slurry is carried out into 16+4 μ coatings, film forming on PP barrier films, as a result referring to table 1 below, by examining
Survey result to understand, the barrier film after coating slurry, its percent thermal shrinkage (150 DEG C/1) is less than 1.5%, is significantly improved compared with basement membrane；
Ceramic coating after film forming is subjected to peel test, the peel strength between ceramic coating and basement membrane is more than 90N/m, shows excellent
Adhesion strength.
Table 1
Claims (15)
1. a kind of lithium ion battery ceramic diaphragm adhesive, described adhesive is included by acrylic compounds hard monomer and acrylic compounds
The copolymer of soft monomer copolymerization composition, wherein, the acrylic compounds hard monomer and acrylic compounds soft monomer are 1~9 by weight:
1；The acrylic compounds hard monomer is methyl methacrylate and acrylonitrile.
2. adhesive as claimed in claim 1, it is characterised in that：The acrylic compounds hard monomer and acrylic compounds soft monomer are pressed
Weight ratio is 1.5~4:1.
3. adhesive as claimed in claim 2, it is characterised in that：The acrylic compounds hard monomer and acrylic compounds soft monomer are pressed
Weight ratio is 2~4:1.
4. adhesive as claimed in claim 1, it is characterised in that：The methyl methacrylate and acrylonitrile are by weight
5:1~3；And/or,
The one kind or many of the acrylic compounds soft monomer in n-butyl acrylate, isobutyl acrylate, Isooctyl acrylate monomer
Kind.
5. adhesive as claimed in claim 4, it is characterised in that：The acrylic compounds soft monomer is selected from Isooctyl acrylate monomer.
6. the adhesive as described in claim any one of 1-5, it is characterised in that：The particle diameter of the copolymer be 30nm~
400nm。
7. adhesive as claimed in claim 6, it is characterised in that：The particle diameter of the copolymer is 40nm~300nm.
8. adhesive as claimed in claim 6, it is characterised in that：The particle diameter of the copolymer is 60nm~300nm.
9. the adhesive as described in claim any one of 1-5, it is characterised in that：Described adhesive is emulsion form, and viscosity is
10~200 centipoises.
10. adhesive as claimed in claim 9, it is characterised in that：The viscosity of described adhesive is 10~100 centipoises.
11. a kind of preparation method of lithium ion battery ceramic diaphragm adhesive, comprises the following steps:
Acrylic compounds hard monomer, acrylic compounds soft monomer, Compositional type emulsifying agent and water are added in pre-emulsification reactor, disperseed
Form stable pre-emulsion；
Water and part pre-emulsion are added in polymerization reaction kettle, polymeric reaction temperature is heated to, redox initiator is added dropwise, instead
5min~20min is answered, remaining pre-emulsion is added dropwise, 2h~3h is dripped off, and insulation reaction 30min~60min obtains copolymerization after cooling
Thing is lithium ion battery ceramic diaphragm adhesive；
Wherein, the acrylic compounds hard monomer and acrylic compounds soft monomer are 1~9 by weight:1；The acrylic compounds are firmly single
Body is methyl methacrylate and acrylonitrile.
12. preparation method as claimed in claim 11, it is characterised in that：The soft list of the acrylic compounds hard monomer and acrylic compounds
Body is 1.5~4 by weight:1；
The acrylic compounds hard monomer is methyl methacrylate and acrylonitrile, and the methyl methacrylate and acrylonitrile are by weight
Amount is than being 5:1~3；
The one kind or many of the acrylic compounds soft monomer in n-butyl acrylate, isobutyl acrylate, Isooctyl acrylate monomer
Kind.
13. preparation method as claimed in claim 11, it is characterised in that：The Compositional type emulsifying agent is using anionic emulsifying
One or more in agent, cationic emulsifier, nonionic emulsifier, ionic/nonionic emulsifying agent, the Compositional type emulsifying agent
Consumption by weight being that 0.8%~8%, HLB of raw material gross weight is 8~35；And/or,
The redox initiator is selected from ammonium persulfate/sodium formaldehyde sulfoxylate, ammonium persulfate/sodium hydrogensulfite, potassium peroxydisulfate/sulfurous acid
Hydrogen sodium, potassium peroxydisulfate/silver nitrate, persulfate/mercaptan, ammonium persulfate/ferrous sulfate, potassium peroxydisulfate/frerrous chloride, peroxidating
Hydrogen/tartaric acid, hydrogen peroxide/sodium formaldehyde sulfoxylate, hydrogen peroxide/sulfuric acid ferrous iron, hydrogen peroxide/frerrous chloride, TBHP/
Sodium formaldehyde sulfoxylate, TBHP/sodium pyrosulfite, benzoyl peroxide/DMA, benzoyl peroxide //N,
N- diethylanilines, benzoyl peroxide/ferrous pyrophosphate, isopropyl benzene hydroperoxide/frerrous chloride, isopropyl benzene hydroperoxide/
One kind in four aziridines, the consumption of the redox initiator is acrylic compounds hard monomer and acrylic compounds by weight
The 0.05%~0.8% of soft monomer gross weight；And/or,
The consumption of the water is by weight 70%~86% for raw material gross weight.
14. preparation method as claimed in claim 11, it is characterised in that：The polymeric reaction temperature is 30 DEG C~80 DEG C.
15. preparation method as claimed in claim 14, it is characterised in that：The polymeric reaction temperature is 40 DEG C~70 DEG C.
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| CN201610160971.1A CN105778834B (en) | 2016-03-21 | 2016-03-21 | Lithium ion battery ceramic diaphragm adhesive and preparation method thereof |
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| CN201610160971.1A CN105778834B (en) | 2016-03-21 | 2016-03-21 | Lithium ion battery ceramic diaphragm adhesive and preparation method thereof |
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| CN107189724A (en) * | 2017-06-14 | 2017-09-22 | 深圳市星源材质科技股份有限公司 | A kind of lithium battery ceramic diaphragm Aqueous Adhesives and preparation method thereof |
| CN108467503B (en) * | 2018-03-02 | 2021-08-10 | 瑞固新能(上海)材料科技有限公司 | Preparation method of heat-resistant lithium battery diaphragm |
| CN108949074B (en) * | 2018-06-05 | 2020-10-02 | 深圳市辰玉科技有限公司 | Binder for lithium ion battery diaphragm coating and preparation method thereof |
| CN109802081B (en) * | 2019-02-18 | 2022-03-22 | 深圳市德立新材料科技有限公司 | Application of acrylic adhesive to lithium battery diaphragm |
| CN111087518B (en) * | 2019-11-29 | 2022-03-11 | 合肥国轩高科动力能源有限公司 | Water-based binder, preparation method thereof and lithium ion battery |
| CN111909631B (en) * | 2020-08-24 | 2022-05-13 | 临沂天勤塑业有限公司 | Bactericidal emulsion pressure-sensitive adhesive, dust-sticking pad and preparation method thereof |
| CN112341961B (en) * | 2020-10-28 | 2023-01-13 | 欣旺达电动汽车电池有限公司 | Adhesive, diaphragm and preparation method thereof |
| KR20240021275A (en) * | 2022-03-25 | 2024-02-16 | 컨템포러리 엠퍼렉스 테크놀로지 씨오., 리미티드 | Binder and related separators, electrode plates, cells, battery modules, battery packs and electrical devices |
| CN117050692B (en) * | 2023-10-11 | 2023-12-26 | 江苏道赢科技有限公司 | Water-based binder, preparation method, ceramic diaphragm and lithium battery |
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| US7604895B2 (en) * | 2004-03-29 | 2009-10-20 | Lg Chem, Ltd. | Electrochemical cell with two types of separators |
| CN103947020B (en) * | 2011-11-22 | 2016-04-06 | Jsr株式会社 | Electric energy storage device adhesive composition, electric energy storage device electrode slurry, electric energy storage device electrode, diaphragm formation slurry, diaphragm and electric energy storage device |
| CN103509500B (en) * | 2012-06-26 | 2016-06-08 | 湖州欧美化学有限公司 | For the aqueous binder of lithium-ion secondary cell |
| CN103342777B (en) * | 2013-06-19 | 2015-09-16 | 广东精进能源有限公司 | The preparation method of the lithium ion battery gel polymer electrolyte of doped nanoparticle |
| CN104725550B (en) * | 2013-12-19 | 2017-02-15 | 上海华谊丙烯酸有限公司 | Water resistant whiting emulsion pressure sensitive adhesive synthesis method |
| CN103915591A (en) * | 2014-04-09 | 2014-07-09 | 深圳市星源材质科技股份有限公司 | Water-based ceramic coating lithium ion battery diaphragm and processing method thereof |
| CN104269509A (en) * | 2014-10-14 | 2015-01-07 | 上海电气集团股份有限公司 | Ceramic coating diaphragm for lithium battery and preparation method of ceramic coating diaphragm |
| CN105131875B (en) * | 2015-08-26 | 2017-07-07 | 深圳市贝特瑞新能源材料股份有限公司 | A kind of water adhesive for lithium ion battery, preparation method and its usage |
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