CN107384261A - A kind of lithium ion battery separator refractory layer aqueous binder, preparation method and applications - Google Patents
A kind of lithium ion battery separator refractory layer aqueous binder, preparation method and applications Download PDFInfo
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- CN107384261A CN107384261A CN201710602800.4A CN201710602800A CN107384261A CN 107384261 A CN107384261 A CN 107384261A CN 201710602800 A CN201710602800 A CN 201710602800A CN 107384261 A CN107384261 A CN 107384261A
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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
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
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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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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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
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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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
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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- 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
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/262—Alkali metal carbonates
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- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/52—Aqueous emulsion or latex, e.g. containing polymers of a glass transition temperature (Tg) below 20°C
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The present invention relates to a kind of lithium ion battery separator refractory layer aqueous binder, the raw material that the aqueous binder has following weight content is formulated：Relative to the acrylic ester monomer of 100 parts by weight, the parts by weight of function monomer 3~35, with the parts by weight of alkene unsaturated group reactive emulsifier 0.3~15, the parts by weight of water soluble starter 0.1~15, the parts by weight of electrolyte 0.01~3, the parts by weight of deionized water 100~700, the mass fraction of the aqueous binder is 20%~55%.The aqueous binder of invention is free of the sequestered emulsifying agent for migrating or being enriched with to film layer, during the lithium ion battery separator refractory coating of formation, the bubble point formed without micro-bubble, with good wetability, and excellent peeling force, heat resistance and electrolyte resistance, and higher toughness, intensity and preferable water resistance are kept, and preparation technology is simple, it is environmentally friendly, it is mainly used in lithium ion battery separator refractory layer field.
Description
Technical field
The present invention relates to technical field of lithium ion, particularly a kind of electrolyte resistance, peel strength and thermodynamics
The excellent aqueous binder of energy, and with the preparation side of good apparent lithium ion battery separator refractory layer aqueous binder
Method.
Background technology
In recent years, required in the industrial overall background of green, low-carbon, environmental protection under, carrying out electric automobile (EV), mixing
The exploitation of electric automobile (HEV) and fuel-cell vehicle (FCV).As these engine driving power supplys, discharge and recharge can be repeated
Secondary cell be optimal selection, particularly possess high power capacity, high-power lithium rechargeable battery gets most of the attention.In this need
Want high output, high power capacity, high-energy-density lithium rechargeable battery component in, porous septum, which plays, prevents positive pole and negative
The adjoint short circuit of the contact of pole, and by making electrolyte immerse in the hole of the barrier film to form two interelectrode ionic conductions
The effect of path.At present, as barrier film, the porous film being made up of polyethylene (PE) or polypropylene (PP) etc. is mostly used,
Thermal contraction can be caused when the temperature increases, cutting function is played using this point.But if the degree of thermal contraction is excessive, send out
The raw partial short-circuit as caused by rupture of membranes etc., and thus short circuit may be located further to expand, cause to catch fire or even explode.Cause
This, in order to suppress the thermal contraction of barrier film, further improves security, it is proposed that forms the skill of porous heat-resistant layer on the surface of barrier film
Art.Porous heat-resistant layer mainly contains the non-conductive particles such as heat resistance mineral particulates, adhesive and auxiliary agent.Lithium ion battery every
Uniformity and stability, higher cohesive force, wider electrochemical window, conjunction when film is coated with to binding agent principal security slurrying
Suitable electrolyte swelling and addition are as few as possible, and improve energy density, reduce internal resistance etc. and require.At present, PVDF is as one
The ripe binding agent of kind is widely used, although PVDF still has strong inoxidizability under of a relatively high potential
Can, but it easily softens in electrolyte solution, and crackle, delamination are also easy to produce due to lacking pliability in electric process is reset.Pass
System PVDF schemes are difficult to take into account conductance and adhesive property, pollution are easily produced, so being proposed to barrier film refractory layer with adhesive
High requirement, such as under conditions of multiple discharge and recharge, mechanical property loss is small, caking property is good, electrolyte resistance is swelled, heat resistance is excellent
It is good, and need environmental protection.At present, patent 201480012725.0 prepares aqueous systems class adhesive, and the adhesive includes water solubility
Polymer and particle shaped polymer, successively prepare two kinds of polymer, are then combined, and are used for lithium ion battery as adhesive
The preparation of barrier film refractory layer slurry, it is possible to achieve excellent lithium ion battery in terms of high-temperature cycle and security two, still
The patent in exothermal reaction process, is made by particle shape polymer particle diameter wider distribution made from traditional emulsion polymerization
Obtain polymerisation to be not easily controlled so that gel content increase；In addition, the emulsifying agent that the patent uses is conventional type emulsifying agent,
There is film forming cure stage in such emulsifying agent, it may occur that migrate and be enriched in the interface with air or base material, influence the bonding of film
Performance and electrolyte resistance, the emulsifying agent of residual can also be formed while the water resistance of film is reduced in heat-resisting layer composition
Micro-bubble, it is difficult to eliminate, coating appearance can be caused to have bubble point generation.The adhesive that patent 201610160971.1 is related to is
The emulsion polymerization carried out by oxidation-reduction initiator system, emulsifying agent is using conventional type and contains the emulsification of nonyl phenol group
Agent, while having above-mentioned insufficient, also there is certain influence on environment, in addition, oxidation-reduction initiator system has been used, wherein
Containing frerrous chloride, the meeting of iron ion is present in adhesive, further present in barrier film refractory layer, the presence meeting of iron ion
Reduce the electric cycle characteristics of lithium ion battery.
The content of the invention
The present invention makes for existing lithium ion battery separator refractory layer deficiency existing for aqueous binder technology of preparing
Improve, its problem to be solved has：
(1) solve the problems, such as that aqueous binder particle size analysis is wider；
(2) solve to have emulsifying agent migration in aqueous binder, be enriched in the interface with air or base material and influence to peel off
Power, water-fast sex chromosome mosaicism；
(3) solve the problems, such as that the apparent bubble point of lithium ion battery separator, percent thermal shrinkage are high, yield rate is low.
To solve the above problems, the technical solution adopted by the present invention is：
A kind of lithium ion battery separator refractory layer aqueous binder, the aqueous binder by following weight content original
Material is configured to：Using the acrylic ester monomer of 100 parts by weight as radix, the parts by weight of function monomer 3~35, have alkene unsaturated
The parts by weight of radical reaction type emulsifying agent 0.3~15, the parts by weight of water soluble starter 0.1~15, the parts by weight of electrolyte 0.01~3,
The parts by weight of deionized water 100~700, the mass fraction of the aqueous binder is 20%~55%.
Above-mentioned lithium ion battery separator refractory layer aqueous binder, the acrylic ester monomer are (methyl) acrylic acid
Propyl ester, (methyl) butyl acrylate, (methyl) tert-butyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) acrylic acid-2-ethyl
One or more in own ester, (methyl) acrylic acid nonyl ester.
Above-mentioned lithium ion battery separator refractory layer aqueous binder, the function monomer be allyl glycidyl ether,
Cyclobutenyl glycidol ether, (methyl) glycidyl acrylate, (methyl) acrylic acid -2- hydroxyl ethyl esters, (methyl) acrylic acid -2-
Hydroxypropyl acrylate, 4- hydroxyvinyls benzene, N hydroxymethyl acrylamide, N, N- bis- (methylol) acrylamide, diacetone (methyl) third
Acrylamide, acrylonitrile, methacrylonitrile, α-ethyl acrylonitrile, acrylic acid, methacrylic acid, itaconic acid, (methyl) maleic acid,
One or more in vinyl sulfonic acid, (methyl) allyl sulphonic acid, phosphoric acid -2- (methyl) acryloyloxyethyl ester.
Above-mentioned lithium ion battery separator refractory layer aqueous binder, described has alkene unsaturated group response type breast
Agent is allyl ether series sulfonate, acrylamido sulfonate, maleic acid derivatives, sodium allyl sulfosuccinic alkyl ester
And the one or more in corresponding carboxylate or phosphate.
Above-mentioned lithium ion battery separator refractory layer aqueous binder, described water soluble starter are potassium peroxydisulfate or mistake
Ammonium sulfate.
Above-mentioned lithium ion battery separator refractory layer aqueous binder, described electrolyte are sodium carbonate, potassium carbonate, carbonic acid
Hydrogen sodium, sodium acetate or sodium hydroxide.
A kind of method of lithium ion battery separator refractory layer aqueous binder, specific preparation process are：
(1) parts by weight of emulsifying agent 0.2~10 and the parts by weight of deionized water 40~400 are added in reactor, stir 5min
After~30min, the parts by weight of acrylic ester monomer 100 and the parts by weight of function monomer 3~35 are added, 10min~50min is stirred,
Obtain the monomer emulsion that mass fraction is 25%~70%；
(2) in another reactor, under the protection of inert gas, the parts by weight of emulsifying agent 0.1~5, the weight of electrolyte 0.01~3
Part and the parts by weight of deionized water 60~300 are measured, temperature adds the parts by weight of monomer emulsion 1~30, quality at 55 DEG C~85 DEG C
Fraction is 1%~10% parts by weight of initiator solution 1~30, continues after stirring 5min~40min, starts that remaining list is added dropwise
Body emulsion, it is synchronous that the initiator solution that remaining mass fraction is 1%~10% is added dropwise, 1h~7h is added dropwise；
(3) after being added dropwise, be incubated 1h~10h, be cooled to 35 DEG C~55 DEG C, with alkali compounds adjust pH to 6.0~
8.0, then the mesh filter screen filtering and discharging of 180 mesh~400, it is heat-resisting to obtain the lithium ion battery separator that mass fraction is 20%~55%
Layer aqueous binder.
Above-mentioned lithium ion battery separator refractory layer aqueous binder, the aqueous binder particle diameter D (50) be 50nm~
550nm, viscosity are 5mPas~200mPas.
A kind of lithium ion battery separator, by above-mentioned aqueous binder and alundum (Al2O3), carboxymethyl cellulose and stream
The formula of flat agent composition, it is coated in obtained by lithium ion battery separator.
Beneficial effect：
(1) lithium ion battery separator refractory layer of the invention is gentle with aqueous binder polymeric reaction condition, gained particle diameter
Narrowly distributing；
(2) emulsifying agent of the undirected surface migration enrichment of lithium ion battery separator refractory layer aqueous binder of the invention,
So that to improve caking property, water resistance.
(3) lithium ion battery separator refractory layer of the invention is low with aqueous binder viscosity, and coating is suitable, gained barrier film
Refractory layer good-looking is without bubble point, peeling force is high, electrolyte resistance is swelled, excellent heat resistance.
(4) lithium ion battery separator good-looking of the invention is without bubble point, and percent thermal shrinkage is laterally less than 2.0%, and longitudinal direction is small
Peeling force between 1.5%, refractory layer and barrier film is more than 1.0N/13mm.
Brief description of the drawings
Fig. 1 is the TG collection of illustrative plates of lithium ion battery separator refractory layer adhesive prepared by the embodiment of the present invention 1；
Fig. 2 is the particle diameter distribution collection of illustrative plates of lithium ion battery separator refractory layer adhesive prepared by the embodiment of the present invention 1.
Embodiment
The present invention relates to lithium ion battery separator refractory layer with aqueous binder be one kind in the form of polymer particles
The emulsion state being stable in the presence of in water, the polymer particles are through free radical principle seed by the function monomer of unsaturated olefin
Obtained by emulsion polymerization technique.
The present invention uses seeded emulsion polymerization technique, because seeded emulsion polymerization technological reaction thermal capacitance easily spreads, reaction temperature
With.It can be realized to latex particle size size, distribution and its emulsion particle structure control by the design of feed way, it is poly- so as to assign
The special function of compound emulsion and excellent performance.
, can be fine using reactive emulsifier present invention uses the reactive emulsifier containing ethylenic unsaturation hydrocarbyl group
Ground solves the problems of conventional emulsifier, and reactive emulsifier molecule is bonded in polymer billet by way of covalent bond
Surface, this strong bonding make emulsifier molecules emulsion storage, use when will not desorb.Mainly have following excellent
Point：(1) gained emulsion has stability in the presence of the various conditions such as high shear force, high/low temperature, electrolyte；(2) aqueous phase is almost
Not residual emulsifying agents, it can avoid producing foam so that after coating film forming, no bubble point produces, and improves yield rate, and do not pollute ring
Border, it can also accelerate film forming speed；(3) in film forming, the migration of emulsifying agent is avoided, makes the mechanical property of film, cementability, water-fast
Property etc., it is improved.
The raw material that the aqueous binder of the present invention has following weight content is configured to：Relative to the acrylic acid of 100 parts by weight
Esters monomer, the parts by weight of function monomer 3~35, there are the parts by weight of alkene unsaturated group reactive emulsifier 0.3~15, it is water-soluble
The property parts by weight of initiator 0.1~15, the parts by weight of electrolyte 0.01~3, the parts by weight of deionized water 40~400, the aqueous binder
The mass fraction of agent is 20%~55%.
The present invention relates to acrylate monomer, can there are (methyl) methyl acrylate, (methyl) ethyl acrylate, (first
Base) propyl acrylate, (methyl) butyl acrylate, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, (methyl) propylene
The own ester of acid, (methyl) acrylic acid-2-ethyl caproite, (methyl) acrylic acid nonyl ester, (methyl) lauryl acrylate, these monomers can
To be used alone a kind, two or more can also be applied in combination with arbitrary ratio, wherein, preferably acrylic acid-2-ethyl caproite, third
Olefin(e) acid butyl ester, it by making acrylate monomer, can reduce the Tg of polymer, flexibility improves, while can make peel strength
Improved with electrochemical stability.
The present invention relates to function monomer can for example there are allyl glycidyl ether, cyclobutenyl glycidol ether, (methyl) third
Olefin(e) acid ethylene oxidic ester, (methyl) acrylic acid -2- hydroxyl ethyl esters, (methyl) 2-hydroxypropyl acrylate, 4- hydroxyvinyls benzene, N-
NMA, N, N- bis- (methylol) acrylamide, diacetone (methyl) acrylamide, acrylonitrile, methacrylonitrile,
α-ethyl acrylonitrile, acrylic acid, methacrylic acid, itaconic acid, (methyl) maleic acid, vinyl sulfonic acid, (methyl) pi-allyl sulphur
Acid, phosphoric acid -2- (methyl) acryloyloxyethyl ester etc..These monomers can be used alone, can also be with arbitrary proportion group
Close, wherein it is preferred that allyl glycidyl ether, acrylic acid -2- hydroxyl ethyl esters, N, N- bis- (methylol) acrylamide, metering system
Acid.Wherein containing epoxy, hydroxyl, amide group cross-linkable monomer, can make adhesive and heat resistance inorganic particulate etc. formation
Composition and the lithium ion battery that manufactures has High temperature storage characteristic, high-temperature cycle.Because crosslink density is higher, particle
The swellbility of shaped polymer in the electrolytic solution is lower, therefore can control adhesive in the electrolytic solution by adjusting crosslink density
The flexibility of swellability and barrier film refractory layer.The nitrile monomer being directed to can adjust the flexibility and interlayer of barrier film refractory layer
Peeling force.Wherein the monomer containing acidic-group can improve adhesive polymerization technique stability and storage stability, can be with
While interlayer peeling force is kept, improve the lithium ion formed using lithium battery diaphragm refractory coating prepared by the adhesive
The cycle characteristics of battery.
The present invention relates to emulsifying agent be the reactive emulsifier with ethylenic unsaturation hydrocarbyl group, pi-allyl can be for example there are
Ethers sulfonate, acrylamido sulfonate, maleic acid derivatives, sodium allyl sulfosuccinic alkyl ester and corresponding carboxylic
Hydrochlorate or phosphate etc., can further for example there are allyloxy hydroxide sodium dimercaptosulphanatein AHPS, (Zhangjagang City's benevolence reaches the limited public affairs of chemical industry
Department), methacrylic acid hydroxide sodium dimercaptosulphanatein HMPS (Chinese section chemical industry), sodium vinyl sulfonate (happiness profit chemical industry), vinyl alkyl
Ester sodium sulfonate (SANYO GS), pi-allyl hydroxypropyl azochlorosulfonate acid sodium (French sieve sub-), acrylic -2- hydroxyl alkyl sulphonic acid sodium COPS-1
(Shanghai loyalty fine chemistry industry), allyloxy fatty alcohol oxygen ethene ether ammonium sulfate (Japanese Ai Dike), Ai Dike series SR-
1025th, SE-10, SR-10, SR-20, ER-10, ER-20, ER-30 etc., these can be used alone, can also be arbitrarily to compare
It is applied in combination.
The present invention relates to water soluble starter be potassium peroxydisulfate or ammonium persulfate.
Above-mentioned aqueous binder, described electrolyte are sodium carbonate, potassium carbonate, sodium acid carbonate, sodium acetate or sodium hydroxide.
The present invention preparation method be：
A kind of method of lithium ion battery separator refractory layer aqueous binder, specific preparation process are：
(1) parts by weight of emulsifying agent 0.2~10 and the parts by weight of deionized water 40~400 are added in reactor, stir 5min
After~30min, the parts by weight and the parts by weight of function monomer 3~35 of addition acrylic ester monomer 100, stirring 10min~
50min, obtain the monomer emulsion that mass fraction is 25%~70%；
(2) in another reactor, under the protection of inert gas, the parts by weight of emulsifying agent 0.1~5, the weight of electrolyte 0.01~3
Part and the parts by weight of deionized water 60~300 are measured, temperature adds the parts by weight of monomer emulsion 1~30, quality at 55 DEG C~85 DEG C
Fraction is 1%~10% parts by weight of initiator solution 1~30, continues after stirring 5min~40min, starts that remaining list is added dropwise
Body emulsion, it is synchronous that the initiator solution that remaining mass fraction is 1%~10% is added dropwise, 1h~7h is added dropwise；
(3) after being added dropwise, be incubated 1h~10h, be cooled to 35 DEG C~55 DEG C, with alkali compounds adjust pH to 6.0~
8.0, then the mesh filter screen filtering and discharging of 180 mesh~400, it is heat-resisting to obtain the lithium ion battery separator that mass fraction is 20%~55%
Layer aqueous binder.
The aqueous binder of the present invention, particle diameter D (50) is 50nm~550nm, and viscosity is 5mPas~200mPas.
A kind of lithium ion battery separator refractory layer, by aqueous binder and alundum (Al2O3), the carboxymethyl cellulose of the present invention
The formula of element and levelling agent composition, coated in obtained by lithium ion battery separator, good-looking is horizontal without bubble point, percent thermal shrinkage
Less than 2.0%, longitudinal direction is less than 1.5%, and the peeling force between refractory layer and barrier film is more than 1.0N/13mm.
Aqueous binder of the present invention is applied in lithium ion battery separator refractory layer preparation section, involved lithium
Ion battery barrier film is made up of polyethylene (PE) or polypropylene (PP), is more preferably prepared by polyethylene (PE) material of wet production
Film.
Characterizing method
Solid content：According to GB/T 72793-1995.
Size distribution：According to GB/T 29022-2012, Bettersize-2000 laser fineness gage measure.
Viscosity：According to GB/T 22237-2008, rotary viscosity design determining.
Emulsion film water resistance：By emulsion in transparency glass plate upper scraping plate, film is made, is put into 50 DEG C of baking ovens and toasts
30min, take out, be put in clear water, soak 96h, whether observation film whitens, bubbles.According to whiting result setting opinion rating 0
~4,0 grade preferably, and 4 grades worst.
Thickness：GB/T 6672-2001, calibrator.
It is apparent：Visual observations.
Gas permeability：；GB/T 458-2008, air permeability tester.
Percent thermal shrinkage：GB/T 12027-2004.
Peeling force：GB/T21302-2007.
The present invention will be further described with reference to embodiments, but embodiments of the present invention are not implemented by these
Example is limited.
Embodiment 1
(1) emulsifying agent allyloxy fatty alcohol oxygen ethene ether ammonium sulfate 2.5g, deionized water are added in reactor
245.0g, after stirring 15min, mix monomer GMA 20.0g, acrylic acid -2- hydroxyl ethyl ester 1.0g are added,
Acrylamide 3.0g, methacrylic acid 15.0g, acrylonitrile 5.0g, butyl acrylate 380.0g, 30min is stirred, obtain monomer breast
Change liquid；
(2) in another reactor, under the protection of inert gas, emulsifying agent propoxylated fatty alcohol oxygen ethene ether ammonium sulfate
0.5g, electrolyte sodium carbonate 0.1g and deionized water 350.0g, temperature add monomer emulsion 80.0g, quality point at 75 DEG C
Number is the 15% of 5% ammonium persulfate aqueous solution, is continued after stirring 25min, starts that remaining monomer emulsion is added dropwise, synchronous to be added dropwise
Remaining ammonium persulfate aqueous solution, 4h is added dropwise；
(3) after being added dropwise, 2h is incubated, is cooled to 50 DEG C, adjust pH to 7.0 with alkali compounds, then 400 mesh filter screen
Filtering and discharging, obtain the lithium ion battery separator refractory layer aqueous binder that mass fraction is 40.1%.
The aqueous binder of the present invention, particle diameter D (50) is 253nm, viscosity 10.8mPas.Emulsion film water resistance 0
Level.
Embodiment 2- embodiments 8, are shown in Table 1.
The embodiment of table 1. feeds intake table and performance test
Comparative example 1
(1) emulsifying agent allyloxy fatty alcohol oxygen ethene ether ammonium sulfate 2.5g, deionized water are added in reactor
245.0g, after stirring 15min, mix monomer GMA 20.0g, acrylic acid -2- hydroxyl ethyl ester 1.0g are added,
Acrylamide 3.0g, methacrylic acid 15.0g, acrylonitrile 5.0g, butyl acrylate 380.0g, 30min is stirred, obtain monomer breast
Change liquid；
(2) in another reactor, under the protection of inert gas, emulsifying agent propoxylated fatty alcohol oxygen ethene ether ammonium sulfate
0.5g, electrolyte sodium carbonate 0.1g and deionized water 350.0g, temperature at 75 DEG C start that monomer emulsion, synchronous drop is added dropwise
Add the ammonium persulfate aqueous solution 40.0g that mass fraction is 5%, 4h is added dropwise；
(3) after being added dropwise, 2h is incubated, is cooled to 50 DEG C, adjust pH to 7.0 with alkali compounds, then 400 mesh filter screen
Filtering and discharging, obtain the lithium ion battery separator refractory layer aqueous binder that mass fraction is 42.0%.
The aqueous binder of the present invention, particle diameter D (50) is 493nm, viscosity 51.0mPas.Emulsion film water resistance 1
Level.
Comparative example 2
(1) emulsifier sodium lauryl sulfate 2.5g, deionized water 245.0g are added in reactor, after stirring 15min,
Add mix monomer GMA 20.0g, acrylic acid -2- hydroxyl ethyl ester 1.0g, acrylamide 3.0g, methyl-prop
Olefin(e) acid 15.0g, acrylonitrile 5.0g, butyl acrylate 380.0g, 30min is stirred, obtains monomer emulsion；
(2) in another reactor, under the protection of inert gas, emulsifier sodium lauryl sulfate 1.0g, electrolyte carbon
Sour sodium 0.1g and deionized water 350.0g, temperature start that monomer emulsion is added dropwise, the synchronous mass fraction that is added dropwise is at 75 DEG C
5% ammonium persulfate aqueous solution 40.0g, 4h is added dropwise；
(3) after being added dropwise, 2h is incubated, is cooled to 50 DEG C, adjust pH to 7.0 with alkali compounds, then 400 mesh filter screen
Filtering and discharging, obtain the lithium ion battery separator refractory layer aqueous binder that mass fraction is 42.0%.
The aqueous binder of the present invention, particle diameter D (50) is 396nm, viscosity 105mPas.Emulsion film water resistance 4
Level.
The raw material of comparative example 1 are consistent with embodiment 1, and difference is not add partial monosomy emulsification liquid emulsion in advance to gather
It is legal.
The raw material of comparative example 2 are consistent with embodiment 1, and difference is that reactive emulsifier is replaced by into conventional type emulsification
Agent.
The comparative example part of table 2. feeds intake table and performance test
From comparative example as can be seen that changing into particle diameter distribution index increase after conventional emulsion polymerizations, after changing emulsifying agent, glue
Degree increase and water resistance variation.
Application example：
The adhesive that the present embodiment is prepared from embodiment 1, embodiment 5 and comparative example 1, comparative example 2.Alundum (Al2O3) selects
(particle diameter 350nm), 100 parts by weight, the parts by weight of adhesive 8, the parts by weight of levelling agent 0.2, eliminate bubble after being dispersed with stirring uniformly and obtain
To lithium battery diaphragm refractory layer slurry, the coating of PE materials lithium battery diaphragm (Lekai production) top layer is carried out.Test result is shown in Table 3.
The application performance test of table 3.
Analyzed from table 3, the adhesive of comparative example used, peeling force, which declines, and barrier film composite bed is apparent has because foam is difficult to
Eliminate and caused bubble point.
The present invention, by seeded emulsion polymerization, is prepared for lithium ion battery using the reactive emulsifier without nonyl phenol
Barrier film refractory layer aqueous binder, reaction condition is gentle, gained emulsion particle diameter narrowly distributing；Undirected surface is moved in film-forming process
The emulsifying agent of enrichment is moved, improves cementability, rate of film build, water resistance, foam is few and easy elimination, and coating is suitable, gained
Barrier film refractory layer good-looking, peel strength are high, electrolyte resistance is swelled, excellent heat resistance.
Claims (9)
1. a kind of lithium ion battery separator refractory layer aqueous binder, it is characterised in that the aqueous binder has following heavy
The raw material of amount content is configured to：Using the acrylic ester monomer of 100 parts by weight as radix, the parts by weight of function monomer 3~35, have
The parts by weight of alkene unsaturated group reactive emulsifier 0.3~15, the parts by weight of water soluble starter 0.1~15, electrolyte 0.01
~3 parts by weight, the parts by weight of deionized water 100~700, the mass fraction of the aqueous binder is 20%~55%.
2. lithium ion battery separator refractory layer aqueous binder according to claim 1, it is characterised in that the propylene
Esters of gallic acid monomer is (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) tert-butyl acrylate, (methyl) acrylic acid
One or more in own ester, (methyl) acrylic acid-2-ethyl caproite, (methyl) acrylic acid nonyl ester.
3. lithium ion battery separator refractory layer aqueous binder according to claim 2, it is characterised in that the function
Monomer be allyl glycidyl ether, cyclobutenyl glycidol ether, (methyl) glycidyl acrylate, (methyl) acrylic acid-
2- hydroxyl ethyl esters, (methyl) 2-hydroxypropyl acrylate, 4- hydroxyvinyls benzene, N hydroxymethyl acrylamide, N, N- bis- (methylol)
Acrylamide, diacetone (methyl) acrylamide, acrylonitrile, methacrylonitrile, α-ethyl acrylonitrile, acrylic acid, metering system
Acid, itaconic acid, (methyl) maleic acid, vinyl sulfonic acid, (methyl) allyl sulphonic acid, phosphoric acid -2- (methyl) acryloxy second
One or more in ester.
4. lithium ion battery separator refractory layer aqueous binder according to claim 3, it is characterised in that described tool
Have alkene unsaturated group reactive emulsifier for allyl ether series sulfonate, acrylamido sulfonate, maleic acid derivatives,
One or more in sodium allyl sulfosuccinic alkyl ester and corresponding carboxylate or phosphate.
5. aqueous binder according to claim 4, it is characterised in that described water soluble starter be potassium peroxydisulfate or
Ammonium persulfate.
6. aqueous binder according to claim 5, it is characterised in that described electrolyte is sodium carbonate, potassium carbonate, carbon
Sour hydrogen sodium, sodium acetate or sodium hydroxide.
7. according to the aqueous binder described in claims 6, it is characterised in that the aqueous binder particle diameter D (50) is
50nm~550nm, viscosity are 5mPas~200mPas.
8. a kind of method for preparing the lithium ion battery separator refractory layer aqueous binder as described in claim any one of 1-7,
Characterized in that, prepared according to the following steps：
(1) the addition parts by weight of emulsifying agent 0.2~10 and the parts by weight of deionized water 40~400 in reactor, stirring 5min~
After 30min, the parts by weight of acrylic ester monomer 100 and the parts by weight of function monomer 3~35 are added, 10min~50min is stirred, is obtained
To the monomer emulsion that mass fraction is 25%~70%；
(2) in another reactor, under the protection of inert gas, the parts by weight of emulsifying agent 0.1~5, the parts by weight of electrolyte 0.01~3
With the parts by weight of deionized water 60~300, temperature adds the parts by weight of monomer emulsion 1~30, mass fraction at 55 DEG C~85 DEG C
For 1%~10% parts by weight of initiator solution 1~30, continue after stirring 5min~40min, start that remaining monomer breast is added dropwise
Change liquid, it is synchronous that the initiator solution that remaining mass fraction is 1%~10% is added dropwise, 1h~7h is added dropwise；
(3) after being added dropwise, 1h~10h is incubated, is cooled to 35 DEG C~55 DEG C, pH to 6.0~8.0 is adjusted with alkali compounds,
Then the mesh filter screen filtering and discharging of 180 mesh~400, obtain the lithium ion battery separator refractory layer that mass fraction is 20%~55% and use
Aqueous binder.
9. a kind of lithium ion battery separator, it is characterised in that using the aqueous binder as described in any one of claim 1~7
Agent and the formula of alundum (Al2O3), carboxymethyl cellulose and levelling agent composition, it is coated in obtained by lithium ion battery separator.
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