CN105778834A - Adhesive for lithium ion battery ceramic diaphragm and preparation method of adhesive - Google Patents
Adhesive for lithium ion battery ceramic diaphragm and preparation method of adhesive Download PDFInfo
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- CN105778834A CN105778834A CN201610160971.1A CN201610160971A CN105778834A CN 105778834 A CN105778834 A CN 105778834A CN 201610160971 A CN201610160971 A CN 201610160971A CN 105778834 A CN105778834 A CN 105778834A
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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
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Abstract
The invention relates to an adhesive for a lithium ion battery ceramic diaphragm and a preparation method of the adhesive. The preparation method includes: adopting a method of emulsion polymerization; mixing acrylic acid type soft monomer and hard monomer in a specific proportion through dispersing effect of a compound emulsifier to form stable latex bundle; under action of an initiator, enabling polymerization monomer to be polymerized in the latex bundle to form a stable polymer emulsion. Through formed copolymer, the adhesive has high wettability and initial adhesion, and certain hardness and tensile strength are maintained, so that the adhesive has excellent binding strength, low coating viscosity and high mechanical strength. In addition, the adhesive emulsion has excellent performance in dispersing ceramic particles, the preparation method is simple and environment-friendly, and requirements on heat resistance of a base material are lowered greatly.
Description
Technical field
The present invention relates to field of lithium ion battery, particularly to a kind of lithium ion battery ceramic diaphragm binding agent and preparation method thereof.
Background technology
Lithium ion battery owing to having voltage height, specific energy is big, working range width, specific power big, electric discharge steadily, the advantage such as storage time length, it is widely used in the various fields such as mobile phone, computer, energy storage device and electric automobile at present, continuous increase along with battery capacity and voltage, its security risk also incrementally increases, its septation can affect the interfacial structure of battery, internal resistance and battery capacity, cycle-index and security performance, and the safety of battery is played vital effect by its heat-resisting and stability.
Due to traditional polyethylene (Polyethylene, PE) barrier film and polypropylene (Polypropylene, PP) fusing point of barrier film is relatively low, respectively 125 DEG C and 158 DEG C, thus under battery generation overheat condition both barrier films to be susceptible to deformation even melted, both positive and negative polarity is short-circuited, thus causing serious security incident.In order to improve this situation, people develop PP/PE composite diaphragm.Owing to the fusing point of PE is lower than PP, first occur melted in battery temperature-rise period, thus inaccessible micropore, breaking current, make battery temperature no longer increase, PP gives barrier film stability in the large simultaneously, it is to avoid short circuit between both positive and negative polarity.But the difference of the stress-strain characteristics due to PP, PE, internal stress is easily produced being coaxially drawn in membrane process, thus barrier film can be made to a certain extent to produce the undesirable conditions such as fold deformation at the applicable middle of battery, composite diaphragm also can increase the thickness of barrier film simultaneously, can increase macrocnemic internal resistance to a certain extent.
In order to improve heat stability and the oxidation resistance of barrier film further, it has been developed that ceramic diaphragm, by improving heat stability and the oxidation resistance of barrier film at traditional polymer membrane surface coated ceramic layers such as PE or PP.At present, ceramic diaphragm application inorganic particle be generally high-temperature stable nanometer or submicro inorganic oxide powder, its preparation mainly through by inorganic particle, binding agent dispersion form slurry in a solvent, be coated with to surface of polymer substrates formed ceramic layer.The performances such as the heat stability of ceramic diaphragm, pore size, mechanical strength, air penetrability and closed pore temperature are subject to the impact of inorganic particle, binding agent and preparation technology.
Owing on market, binding agent kind is many, physicochemical property difference is big, and the thermal contraction of binding agent itself also results in the contraction of ceramic diaphragm；The more important thing is, being in electric field in barrier film use procedure, binding agent is except requiring to possess basic adhesive property, it is necessary to have stable chemical property.Prior art CN104064712A also discloses that each variant due to the fusing point of binding agent, dissolubility, molecular weight etc., the selection of binding agent certainly can affect the performance of ceramic diaphragm, to ceramic diaphragm continuous heating, it is by observing whether ceramic diaphragm forms perforation, thus screening the binding agent used by ceramic diaphragm.Therefore, the performance of binding agent becomes the key factor determining that ceramic diaphragm performance is good and bad.
nullAt present，In prior art, binding agent is typically chosen high molecular polymer，Such as fluorocarbon resin is such as poly-inclined 1,1-difluoroethylene (Polyvinylidenefluoride，PVDF)、Politef (Polytetrafluoroethylene，And tetrafluoraoethylene-hexafluoropropylene copolymer (Hexafluoropropene-tetrafluoroethylenecopolymer PTFE)，FEP) etc.，And polyacrylic acid derivative、HPAM Degraded Bacteria、Polyethylene、Poly-propionic acid amide. (Polyscrylamide，PAM)、Butadiene-styrene rubber (Styrene,1,3-butadienepolymer，Etc. SBR) there is the binding agent of thermostability and electrolyte-resistant.But, the binding agent such as PVDF, PTFE, FEP is a kind of binding agent based on organic solvent, to bad environmental；And aqueous binder such as polyacrylic acid derivative, HPAM Degraded Bacteria and SBR etc., although environmentally friendly, but adhesion strength is less, and it is used for the binding agent of negative electrode material powder, and the application in ceramic diaphragm is restricted.
Prior art CN203571420A discloses the bonding force into improving ceramic diaphragm binding agent and solvent resistance, utilize the modified water soluble acrylic acid ester adhesive prepared by four or more monomer copolymerization of epoxy resin graft, this binding agent is by the cross-linking reaction of the groups such as the epoxide group in epoxy resin and the carboxyl in acrylate, amino, imino group, thus increasing molecule inner injection energy, and then the enhancing of polymer-bonded power, heat stability is made to improve.But, this adhesive viscosities is more than 2000 centipoises, and application viscosity is high, it is possible to affects binding agent flow leveling, and then is likely to affect the planarization of ceramic diaphragm and spatial stability；Additionally, the environmentally friendly property of epoxy resin adopted in the method is poor, and Long Term Contact is unfavorable for healthy.
Be currently, there are and develop a kind of Heat stability is good, adhesion strength is high, application viscosity is low, the demand of the high simple ceramic diaphragm binding agent of environmentally friendly, preparation technology simultaneously of mechanical strength.
Summary of the invention
It is an object of the invention to provide a kind of Heat stability is good, adhesion strength is high, application viscosity is low, the high simple ceramic diaphragm binding agent of environmentally friendly, preparation technology simultaneously of mechanical strength and preparation method thereof.
In order to realize the purpose of the present invention, one aspect of the present invention provides a kind of lithium ion battery ceramic diaphragm binding agent, described binding agent includes the copolymer being made up of acrylic compounds hard monomer and acrylic compounds soft monomer copolymerization, wherein, described acrylic compounds hard monomer and acrylic compounds soft monomer are 1～9:1 by weight.
In the embodiment of the invention, the glass transition temperature of described copolymer is-15 DEG C～10 DEG C.
The present invention passes through acrylic compounds soft monomer and the hard monomer copolymerization of special ratios, the copolymer formed is while having good wellability and initial bonding strength, also keep certain hardness and hot strength, so that binding agent possesses the adhesion strength of excellence, low application viscosity and high mechanical strength.
In the present invention, described acrylic compounds hard monomer refers to the polymer glass temperature acrylic monomer more than 0 DEG C, and described acrylic compounds soft monomer refers to the polymer glass temperature acrylic monomer less than or equal to 0 DEG C.
In the embodiment of the invention, described acrylic compounds hard monomer and acrylic compounds soft monomer are 1.5～4:1 by weight, it is preferred to 2～4:1.
In the embodiment of the invention, described acrylic compounds hard monomer is selected from one or more in methyl methacrylate, acrylamide, acrylic acid, methacrylic acid, acrylonitrile monemer, and described acrylic compounds soft monomer is selected from one or more in ethyl acrylate, n-butyl acrylate, Isobutyl 2-propenoate, Isooctyl acrylate monomer (acrylic acid-2-ethyl caproite), acrylic acid-2-hydroxyl ethyl ester, lauryl acid esters, octadecyl acrylate monomer.
In the embodiment of the invention, described acrylic compounds hard monomer is methyl methacrylate and acrylonitrile, it is preferred that described methyl methacrylate and acrylonitrile are by weight for 5:1～3.
In the embodiment of the invention, described acrylic compounds soft monomer is selected from one or more in n-butyl acrylate, Isobutyl 2-propenoate, Isooctyl acrylate monomer, it is preferable that from Isooctyl acrylate monomer.
In the embodiment of the invention, the particle diameter of described copolymer is 30nm～400nm, it is preferred that the particle diameter of described copolymer is 40nm～300nm, it is furthermore preferred that the particle diameter of described copolymer is 60nm～300nm.
In the embodiment of the invention, described binding agent is emulsion form, and viscosity is 10～200 centipoises (at 25 DEG C), it is preferred that the viscosity of described binding agent is 10～100 centipoises (at 25 DEG C).
The preparation method that further aspect of the present invention provides a kind of lithium ion battery ceramic diaphragm binding agent, comprises the steps:
Acrylic compounds hard monomer, acrylic compounds soft monomer, Compositional type emulsifying agent and water being added in pre-emulsification reactor, dispersion forms stable pre-emulsion；
Water and part pre-emulsion are added in polymerization reaction kettle, heat to polymeric reaction temperature, dropping redox initiator, reaction 5min～20min, drip remaining pre-emulsion, 2h～3h drips off, insulation reaction 30min～60min, obtains copolymer and be lithium ion battery ceramic diaphragm binding agent after cooling；
Wherein, described acrylic compounds hard monomer and acrylic compounds soft monomer are 1～9:1 by weight.
In the embodiment of the invention, described acrylic compounds hard monomer and acrylic compounds soft monomer are 1.5～4:1 by weight, it is preferred to 2～4:1.
In the embodiment of the invention, described acrylic compounds hard monomer is selected from one or more in the monomers such as methyl methacrylate, acrylamide, acrylic acid, methacrylic acid, acrylonitrile, and described acrylic compounds soft monomer is selected from one or more in the monomers such as ethyl acrylate, n-butyl acrylate, Isobutyl 2-propenoate, Isooctyl acrylate monomer (acrylic acid-2-ethyl caproite), acrylic acid-2-hydroxyl ethyl ester, lauryl acid esters, octadecyl acrylate.
In the embodiment of the invention, described acrylic compounds hard monomer is methyl methacrylate and acrylonitrile, it is preferred that described methyl methacrylate and acrylonitrile are by weight for 5:1～3.
In the embodiment of the invention, described acrylic compounds soft monomer is selected from one or more in n-butyl acrylate, Isobutyl 2-propenoate, Isooctyl acrylate monomer, it is preferable that from Isooctyl acrylate monomer.
In the embodiment of the invention, described Compositional type emulsifying agent adopts one or more in anion emulsifier, cationic emulsifier, nonionic emulsifier, ionic/nonionic emulsifying agent.Preferably, described Compositional type emulsifying agent adopt anion emulsifier and nonionic emulsifier with the use of.
Anion emulsifier of the present invention can be one or more in carboxylic acid type emulsifying agent, sulfonate type emulsifying agent, sulfuric ester salt form emulsifying agent etc..Wherein, carboxylic acid type emulsifying agent formula is RCOOM, R is C7-C20Alkyl, aryl or aryl alkyl, M is metal；Sulfonate type emulsifying agent includes Fatty sulphonates, di-fatty acid ester sulfonates, fatty acid amide sulfonate, alkylbenzenesulfonate, formaldehyde condensation naphthalene sulfonate etc., such as: dodecyl sodium sulfate (SDS), dodecylbenzene sodium sulfonate, enuatrol, potassium oleate, alkyl acrylic-2-ethanesulfonic acid sodium salt, 2-acrylamide-2,2-dimethyl ethyl sulfonic acid sodium, sodium p styrene sulfonate, acrylamide stearic acid sodium salt, sodium allyl sulfosuccinic alkyl ester etc..
nullNonionic emulsifier of the present invention is polyoxyethylene polyoxyethylene carboxylic ester、Polyol carboxylate、Polyoxyethylene polyols carboxylate、Polyoxyethylene alkyl ether、Polyoxyethylene alkyl aryl ether、Polyoxyethylate amide、One or more in alkylolamides etc.，Such as: polyoxyethylene carboxylate、Sorbitan fatty acid ester (Span series) is such as sorbitan mono-laurate (Span20)、Sorbitan monopalmitate (Span40)、Sorbitan monostearate (Span60)、Sorbitan monooleate (Span80)、Sorbitan trioleate (Span85)、Polyoxyethylene sorbitan fatty acid ester (Tween series) is such as polyoxyethylene 20 sorbitan monolaurate (Tween20)、Polyoxyethylene sorbitan list Petiolus Trachycarpi ester (Tween40)、Polyoxyethylene 20 sorbitan monostearate (Tween60)、Polyoxyethylene 20 sorbitan monooleate (Tween80)、Polyoxyethylene 20 sorbitan trioleate (Tween85) etc..
Cationic emulsifier of the present invention is one or more in alkylammonium salt and quaternary ammonium salt, for instance: lauryl 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, such as, fatty alcohol polyoxy alkene ether sodium sulfate (AES) or NPE-2-sulfonic group amber acid monoester disodium salt (MS-1) etc..
Preferably, the consumption of described Compositional type emulsifying agent is by weight for the 0.8%～8% of raw material gross weight, and HLB is 8～35, it is preferred that HLB is 11-17.
In the embodiment of the invention, described redox initiator is selected from Ammonium persulfate ./sodium formaldehyde sulfoxylate, Ammonium persulfate ./sodium sulfite, potassium peroxydisulfate/sodium sulfite, potassium peroxydisulfate/silver nitrate, persulfate/sulfur alcohol, Ammonium persulfate ./ferrous sulfate, potassium peroxydisulfate/ferrous chloride, hydrogen peroxide/tartaric acid, hydrogen peroxide/sodium formaldehyde sulfoxylate, hydrogen peroxide/sulfuric acid is ferrous, hydrogen peroxide/ferrous chloride, tert-butyl hydroperoxide/sodium formaldehyde sulfoxylate, tert-butyl hydroperoxide/sodium pyrosulfite, benzoyl peroxide/N, accelerine, benzoyl peroxide //N, N-diethylaniline, benzoyl peroxide/ferrous pyrophosphate, isopropyl benzene hydroperoxide/ferrous chloride, one in isopropyl benzene hydroperoxide/tetra-aziridine.
Preferably, the consumption of described redox initiator is by weight for the 0.05%～0.8% of acrylic compounds hard monomer and acrylic compounds soft monomer gross weight.
In the embodiment of the invention, the consumption of described water is by weight for the 70%～86% of raw material gross weight.
In the embodiment of the invention, described polymeric reaction temperature is 30 DEG C～80 DEG C, it is preferred to 40 DEG C～70 DEG C.
The method have the benefit that
Invention adhesives particle diameter is less, ceramic particle dispersive property is excellent, by the acrylic compounds soft monomer of special ratios and hard monomer copolymerization, the copolymer formed is while having good wellability and initial bonding strength, also keep certain hardness and hot strength, so that binding agent possesses the adhesion strength of excellence, low application viscosity and high mechanical strength.In addition, invention adhesives is using water as solvent, production process avoids the volatilization of solvent, reduce the discharge of VOC, simultaneously with water for solvent, can effectively drop low operating temperature, reduce energy consumption, requiring to be substantially reduced to the heat resistance of base material itself, its preparation process is environmentally friendly, preparation technology is simple.
Accompanying drawing explanation
Fig. 1 show the TG-DSC spectrogram of the ceramic diaphragm binding agent of the embodiment of the present invention 1 preparation.
Detailed description of the invention
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 clearly and completely described, it is clear that described embodiment is only a part of embodiment of the present invention, rather than whole embodiments.Based on the embodiment in the present invention, the every other embodiment that those of ordinary skill in the art obtain under not making creative work premise, broadly fall into the scope of protection of the invention.
Embodiment 1:
In the present embodiment, ceramic diaphragm binding agent adopts SDS and sorbitan fatty acid ester composite as emulsifying agent, using Ammonium persulfate. and sodium formaldehyde sulfoxylate as initiator, polymerization adopts methyl methacrylate and acrylonitrile with acrylic compounds hard monomer, polymerization acrylic compounds soft monomer adopts Isooctyl acrylate monomer, and wherein the ratio by mass of methyl methacrylate, acrylonitrile and Isooctyl acrylate monomer three ratio is for 5:3:2.
The preparation method of above-mentioned ceramic diaphragm binding agent is particularly as follows: add 10 parts of SDS, 50 parts of sorbitan fatty acid esters and 300 parts of water and be sufficiently mixed in being placed in pre-emulsification bottle, it is sequentially added into 375 parts of methyl methacrylates, 225 parts of acrylonitrile and 150 parts of Isooctyl acrylate monomer high-speed stirred afterwards, rotating speed 600rpm, dispersion forms stable pre-emulsion；
Take out 100g pre-emulsion after 30min and add in reaction bulb, it is simultaneously introduced 400g water to begin to warm up, when temperature be increased to 65 DEG C start drip add Ammonium persulfate. and sodium formaldehyde sulfoxylate initiator respectively, start to drip pre-emulsion after dropping 5min, keeping pre-emulsion to dropwise at 180min, pre-emulsion dropwises, and is incubated 40min, reduce temperature to 40 DEG C, namely prepare above-mentioned ceramic diaphragm adhesive agent emulsion.
The binding agent solid content prepared is 48%, is creamy white, and the Diameter of Binder Particles scope prepared is at 80nm-200nm, and viscosity is lower than 20 centipoises.The TG-DSC spectrogram of this binding agent is as it is shown in figure 1, by the excellent heat stability of spectrogram this binding agent known, decomposition temperature is higher than 300 DEG C, Heat stability is good.
Embodiment 2:
In the present embodiment, ceramic diaphragm binding agent adopts dodecylbenzene sodium sulfonate and sorbitan fatty acid ester composite as emulsifying agent, the ratio by mass ratio of polymerization methyl methacrylate, acrylonitrile and Isooctyl acrylate monomer three is 5:1:4, and all the other steps are with embodiment 1.
The binding agent solid content prepared is 40%, is creamy white, and the particle size range of emulsion is at 100nm-300nm, and viscosity is less than 10 centipoises.
Embodiment 3:
In the present embodiment, ceramic diaphragm binding agent adopts SDS and polyoxyethylene sorbitan fatty acid ester composite as emulsifying agent, polymerization adopts methyl methacrylate and acrylonitrile with acrylic compounds hard monomer, polymerization acrylic compounds soft monomer adopts Isobutyl 2-propenoate, and wherein the ratio by mass of methyl methacrylate, acrylonitrile and Isobutyl 2-propenoate three ratio is for 5:2:3.
The binding agent solid content prepared is 45%, is creamy white, and the particle size range of emulsion is at 100nm-300nm, and viscosity is 40 centipoises.
Application Example 1:
The present embodiment selects the adhesive agent emulsion of embodiment 1-3 synthesis, the aluminium oxide (ceramic particle is the aqueous solution of 48%) that ceramic particle selects particle diameter to be 200nm.Wherein consumption respectively 100g and 80g of ceramic particle solution and adhesive agent emulsion, disperses 30min under 800rpm rotating speed, final vacuum eliminate the bubble in solution, obtain slurry, be coated on uniformly on base material PP barrier film.
The ceramic diaphragm prepared, ceramic particle dispersion is homogeneous, places 4h and all generates without flocculate, ceramic particle slurry is good to the wettability of PP simultaneously, can be good at sprawling on PP film, and the barrier film after coated ceramic particle can under 180 DEG C of conditions homogeneous film formation, it does not have deformation.
Prepared slurry carrying out 16+4 μ coating on PP barrier film, tests after film forming, result is referring to table 1 below, and by testing result it can be seen that be coated with the barrier film after slurry, less than 1.5%, relatively basement membrane is significantly improved its percent thermal shrinkage (150 DEG C/1)；Being undertaken the ceramic coating after film forming peeling off test, the peel strength between ceramic coating and basement membrane, more than 90N/m, shows the adhesion strength of excellence.
Table 1
Claims (10)
1. a lithium ion battery ceramic diaphragm binding agent, described binding agent includes the copolymer being made up of acrylic compounds hard monomer and acrylic compounds soft monomer copolymerization, and wherein, described acrylic compounds hard monomer and acrylic compounds soft monomer are 1～9:1 by weight.
2. binding agent as claimed in claim 1, it is characterised in that: described acrylic compounds hard monomer and acrylic compounds soft monomer are 1.5～4:1 by weight, it is preferred to 2～4:1.
3. binding agent as claimed in claim 2, it is characterized in that: described acrylic compounds hard monomer is selected from one or more in methyl methacrylate, acrylamide, acrylic acid, methacrylic acid, acrylonitrile monemer, described acrylic compounds soft monomer is selected from one or more in ethyl acrylate, n-butyl acrylate, Isobutyl 2-propenoate, Isooctyl acrylate monomer, acrylic acid-2-hydroxyl ethyl ester, lauryl acid esters, octadecyl acrylate monomer.
4. binding agent as claimed in claim 3, it is characterised in that: described acrylic compounds hard monomer is methyl methacrylate and acrylonitrile, it is preferred that described methyl methacrylate and acrylonitrile are by weight for 5:1～3；And/or,
Described acrylic compounds soft monomer is selected from one or more in n-butyl acrylate, Isobutyl 2-propenoate, Isooctyl acrylate monomer, it is preferable that from Isooctyl acrylate monomer.
5. the binding agent as described in any one of claim 1-4, it is characterised in that: the particle diameter of described copolymer is 30nm～400nm, it is preferred that the particle diameter of described copolymer is 40nm～300nm, it is furthermore preferred that the particle diameter of described copolymer is 60nm～300nm.
6. the binding agent as described in any one of claim 1-4, it is characterised in that: described binding agent is emulsion form, and viscosity is 10～200 centipoises, it is preferred that the viscosity of described binding agent is 10～100 centipoises.
7. a preparation method for lithium ion battery ceramic diaphragm binding agent, comprises the steps:
Acrylic compounds hard monomer, acrylic compounds soft monomer, Compositional type emulsifying agent and water being added in pre-emulsification reactor, dispersion forms stable pre-emulsion；
Water and part pre-emulsion are added in polymerization reaction kettle, heat to polymeric reaction temperature, dropping redox initiator, reaction 5min～20min, drip remaining pre-emulsion, 2h～3h drips off, insulation reaction 30min～60min, obtains copolymer and be lithium ion battery ceramic diaphragm binding agent after cooling；
Wherein, described acrylic compounds hard monomer and acrylic compounds soft monomer are 1～9:1 by weight.
8. preparation method as claimed in claim 7, it is characterised in that: described acrylic compounds hard monomer and acrylic compounds soft monomer are 1.5～4:1 by weight；
Described acrylic compounds hard monomer is methyl methacrylate and acrylonitrile, and described methyl methacrylate and acrylonitrile are by weight for 5:1～3；
Described acrylic compounds soft monomer is selected from one or more in n-butyl acrylate, Isobutyl 2-propenoate, Isooctyl acrylate monomer.
9. preparation method as claimed in claim 7, it is characterized in that: described Compositional type emulsifying agent adopts one or more in anion emulsifier, cationic emulsifier, nonionic emulsifier, ionic/nonionic emulsifying agent, the consumption of described Compositional type emulsifying agent is by weight for the 0.8%～8% of raw material gross weight, and HLB is 8～35；And/or,
nullDescribed redox initiator is selected from Ammonium persulfate ./sodium formaldehyde sulfoxylate、Ammonium persulfate ./sodium sulfite、Potassium peroxydisulfate/sodium sulfite、Potassium peroxydisulfate/silver nitrate、Persulfate/mercaptan、Ammonium persulfate ./ferrous sulfate、Potassium peroxydisulfate/ferrous chloride、Hydrogen peroxide/tartaric acid、Hydrogen peroxide/sodium formaldehyde sulfoxylate、Hydrogen peroxide/sulfuric acid is ferrous、Hydrogen peroxide/ferrous chloride、Tert-butyl hydroperoxide/sodium formaldehyde sulfoxylate、Tert-butyl hydroperoxide/sodium pyrosulfite、Benzoyl peroxide/N，Accelerine、Benzoyl peroxide //N，N-diethylaniline、Benzoyl peroxide/ferrous pyrophosphate、Isopropyl benzene hydroperoxide/ferrous chloride、One in isopropyl benzene hydroperoxide/tetra-aziridine，The consumption of described redox initiator is by weight for the 0.05%～0.8% of acrylic compounds hard monomer and acrylic compounds soft monomer gross weight；And/or,
The consumption of described water is by weight for the 70%～86% of raw material gross weight.
10. preparation method as claimed in claim 7, it is characterised in that: described polymeric reaction temperature is 30 DEG C～80 DEG C, it is preferred to 40 DEG C～70 DEG C.
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| CN106905475A (en) * | 2017-03-10 | 2017-06-30 | 湖南高瑞电源材料有限公司 | The ceramic diaphragm that a kind of lithium battery ceramic diaphragm is prepared with the preparation method of fluorine-containing adhesive and using the adhesive |
| 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 |
| CN108467503A (en) * | 2018-03-02 | 2018-08-31 | 上海三瑞高分子材料股份有限公司 | A kind of preparation method of heat resistant type lithium battery diaphragm |
| CN108949074A (en) * | 2018-06-05 | 2018-12-07 | 深圳市辰玉科技有限公司 | A kind of lithium ion battery separator coating binder and preparation method |
| CN109802081A (en) * | 2019-02-18 | 2019-05-24 | 深圳市德立新材料科技有限公司 | A kind of application of acrylic-based adhesives on lithium battery diaphragm |
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| CN111909631A (en) * | 2020-08-24 | 2020-11-10 | 临沂天勤塑业有限公司 | Bactericidal emulsion pressure-sensitive adhesive, dust-sticking pad and preparation method thereof |
| CN112341961A (en) * | 2020-10-28 | 2021-02-09 | 欣旺达电动汽车电池有限公司 | Adhesive, diaphragm and preparation method thereof |
| WO2023178690A1 (en) * | 2022-03-25 | 2023-09-28 | 宁德时代新能源科技股份有限公司 | Binder and related separator, electrode sheet, battery, battery module, battery pack and electric device |
| CN117050692A (en) * | 2023-10-11 | 2023-11-14 | 江苏道赢科技有限公司 | Water-based binder, preparation method, ceramic diaphragm and lithium battery |
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| CN117050692A (en) * | 2023-10-11 | 2023-11-14 | 江苏道赢科技有限公司 | Water-based binder, preparation method, ceramic diaphragm and lithium battery |
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