CN104332578A - Adhesive composite diaphragm and manufacturing method thereof - Google Patents
Adhesive composite diaphragm and manufacturing method thereof Download PDFInfo
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- CN104332578A CN104332578A CN201410670327.XA CN201410670327A CN104332578A CN 104332578 A CN104332578 A CN 104332578A CN 201410670327 A CN201410670327 A CN 201410670327A CN 104332578 A CN104332578 A CN 104332578A
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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
- H01M50/463—Separators, membranes or diaphragms characterised by their shape
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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
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses an adhesive composite diaphragm, comprising a polyolefin porous membrane and one or two hybrid coatings applied onto one or two sides of the polyolefin porous membrane, wherein each hybrid coating is 2-8 microns thick and comprises 10-50 parts by mass of polymer particles and 50-90 parts by mass of ceramic particles. The invention also discloses a manufacturing method of the composite diaphragm. The diaphragm disclosed by the invention has the advantages that the thermal stability of the diaphragm is effectively improved, and the diaphragm and a battery pole piece can bond with each other.
Description
Technical field
The present invention relates to lithium ion battery, especially relate to a kind of thermal stability that effectively can improve barrier film, the composite diaphragm that can bond that barrier film and battery pole piece can be bonded together again and manufacture method thereof.
Background technology
In lithium ion battery, the Main Function of barrier film is that the positive and negative electrode of battery is separated, and prevents the two poles of the earth from contacting and short circuit, is one of interior layer assembly of key.The performance of barrier film determines the interfacial structure, internal resistance etc. of battery, directly affects the characteristics such as the capacity of battery, circulation and security performance, and the barrier film of excellent performance has important effect to the combination property improving lithium ion battery.
At present, the barrier film that lithium ion battery uses is generally Polyolefin-based porous film, because this Polyolefin-based porous film fusing point is lower than 200 DEG C, when battery temperature raises because of inside or external factor, this barrier film can shrink or melting, cause the direct contact between positive pole and negative pole, cause battery short circuit, thus cause the generation of the contingencies such as cells burst blast.
Summary of the invention
For overcoming above-mentioned shortcoming, provide a kind of thermal stability that effectively can improve barrier film, the composite diaphragm that barrier film and battery pole piece can be bonded together again, another object of the present invention is to provide a kind of free of contamination manufacture method of the composite diaphragm that can bond.
The object of the invention is to be realized by following technical measures, a kind of can the composite diaphragm of bonding, comprise polyolefin porous membrane and be coated on the mixed coating of polyolefin porous membrane one or both sides, coating layer thickness is 2-8 μm; Described mixed coating comprises polymer beads 10-50 part and ceramic particle 50-90 part of calculating by mass parts.
As a kind of optimal way, described mixed coating coating slurry used is made up of composition and deionized water; Described composition comprises the polymer beads 10-50 part calculated according to mass parts, ceramic particle 50-90 part, Aqueous Adhesives 3-10 part, aqueous dispersion 1-5 part, water-based thickener 1-5 part, wetting agent 1-5 part.
As a kind of optimal way, described polymer beads is one or more in Kynoar-hexafluoropropylene copolymer, polyacrylonitrile, polyethylene glycol oxide, polymethyl methacrylate, and particle diameter is 0.1-2um.
As a kind of optimal way, described ceramic particle is one or more in silicon dioxide, alundum (Al2O3), titanium dioxide, boehmite, magnesium dioxide, barium sulfate.
As a kind of optimal way, described Aqueous Adhesives is one or more in polymethyl methacrylate, polybutyl methacrylate, butadiene-styrene latex, styrene-acrylic latex, polyethyl acrylate, ethylene-vinyl acetate copolymer, polyvinyl alcohol, polyvinyl acetate.
As a kind of optimal way, described aqueous dispersion is one or more in metal carboxylate fluorine dispersant, Sulfonates fluorine dispersant, Sodium Polyacrylate (PAA-Na), polyacrylic acid potassium (PAA-K).
As a kind of optimal way, described water soluble polymer thickener is one or more in hydroxyethylcellulose, methyl hydroxyethylcellulose, sodium carboxymethylcellulose (CMC-Na), polyacrylamide (PAM), sodium alginate; Described wetting agent is one or more in fluoro-alkyl methoxyl group ether alcohol, fluoro-alkyl ethyoxyl ether alcohol, APES, AEO, aliphatic acid polyethenoxy ether.
As a kind of optimal way, described polyolefin porous membrane is polyethylene film, polypropylene screen, polypropylene, polyethylene/polypropylene screen, and the thickness of described polyolefin porous membrane is 5-40 μm, and porosity is 30-60%.
The invention also discloses a kind of manufacture method of composite diaphragm, comprise the following steps:
(1), the water soluble polymer thickener of formula ratio, aqueous dispersion and deionized water are joined in pre-agitator tank, dissolve completely, obtain mixture I;
(2), in said mixture I add polymer beads, stirring on-line velocity after 30-60 minute is carry out high speed dispersion in the dispersion machine of 50m/s, obtains mixture II;
(3), in said mixture II add Aqueous Adhesives, wetting agent, after slowly stirring, filter to obtain waterborne polymeric slurry with 400 eye mesh screens;
(4), the water soluble polymer thickener of formula ratio, aqueous dispersion and deionized water are joined in pre-agitator tank, dissolve completely, obtain mixture III;
(5), in said mixture III add ceramic particle, stirring on-line velocity after 30-60 minute is carry out high speed dispersion in the dispersion machine of 30-60m/s, obtains mixture IV;
(6), in said mixture IV add Aqueous Adhesives, after slowly stirring, filter to obtain aqueous ceramic slurry with 300 eye mesh screens;
(7), in above-mentioned aqueous ceramic slurry, the waterborne polymeric slurry prepared early stage is added, obtained mixed coating coating slurry used after slowly stirring;
(8), by coating slurry the one or both sides of polyolefin film are coated, the obtained composite diaphragm that can bond after dry.
As a kind of optimal way, the coating process in described step (8) is nick version, slit extrusion coated, dip-coating or spraying.
Compared with prior art, its advantage and beneficial effect are in the present invention:
The composite diaphragm with attachment function adopting the present invention to prepare can not only utilize ceramic material wherein to reduce the thermal contraction of polyolefin film, improves the heat resistance of barrier film; And polymeric material wherein can be utilized pole piece and barrier film to be bonded together, thus strengthen the security performance of battery.A method energy of the present invention coated and molded, do not need repeatedly to be coated with, production efficiency significantly improves.The present invention adopts water to make solvent in the preparation, therefore has that cost is low, the feature of safety and environmental protection.
Accompanying drawing explanation
The electron microscopic picture of Fig. 1 embodiment of the present invention composite diaphragm.
Embodiment
Contrast accompanying drawing below in conjunction with embodiment the present invention is described in further detail.
The composite diaphragm that can bond, comprise polyolefin porous membrane and be coated on the mixed coating of polyolefin porous membrane one or both sides, coating layer thickness is 2-8 μm; Described mixed coating comprises polymer beads 10-50 part and ceramic particle 50-90 part of calculating by mass parts.Fig. 1 is the electron microscopic picture of the composite diaphragm that the present embodiment can bond.
The composite diaphragm that can bond of the present embodiment, the basis of previous technique scheme can also be specifically, and mixed coating coating slurry used is made up of composition and deionized water; Described composition comprises the polymer beads 10-50 part calculated according to mass parts, ceramic particle 50-90 part, Aqueous Adhesives 3-10 part, aqueous dispersion 1-5 part, water-based thickener 1-5 part, wetting agent 1-5 part.
The composite diaphragm that can bond of the present embodiment, the basis of previous technique scheme can also be specifically, polymer beads is one or more in Kynoar-hexafluoropropylene copolymer, polyacrylonitrile, polyethylene glycol oxide, polymethyl methacrylate, and particle diameter is 0.1-2um.
As a kind of optimal way, described ceramic particle is one or more in silicon dioxide, alundum (Al2O3), titanium dioxide, boehmite, magnesium dioxide, barium sulfate.
The composite diaphragm that can bond of the present embodiment, the basis of previous technique scheme can also be specifically Aqueous Adhesives is one or more in polymethyl methacrylate, polybutyl methacrylate, butadiene-styrene latex, styrene-acrylic latex, polyethyl acrylate, ethylene-vinyl acetate copolymer, polyvinyl alcohol, polyvinyl acetate.
The composite diaphragm that can bond of the present embodiment, the basis of previous technique scheme can also be specifically aqueous dispersion is one or more in metal carboxylate fluorine dispersant, Sulfonates fluorine dispersant, Sodium Polyacrylate (PAA-Na), polyacrylic acid potassium (PAA-K).
The composite diaphragm that can bond of the present embodiment, the basis of previous technique scheme can also be specifically water soluble polymer thickener is one or more in hydroxyethylcellulose, methyl hydroxyethylcellulose, sodium carboxymethylcellulose (CMC-Na), polyacrylamide (PAM), sodium alginate; Described wetting agent is one or more in fluoro-alkyl methoxyl group ether alcohol, fluoro-alkyl ethyoxyl ether alcohol, APES, AEO, aliphatic acid polyethenoxy ether.
The composite diaphragm that can bond of the present embodiment, the basis of previous technique scheme can also be specifically, polyolefin porous membrane is polyethylene film, polypropylene screen, polypropylene, polyethylene/polypropylene screen, and the thickness of described polyolefin porous membrane is 5-40 μm, and porosity is 30-60%.
The invention also discloses a kind of manufacture method of composite diaphragm, comprise the following steps:
(1), the water soluble polymer thickener of formula ratio, aqueous dispersion and deionized water are joined in pre-agitator tank, dissolve completely, obtain mixture I;
(2), in said mixture I add polymer beads, stirring on-line velocity after 30-60 minute is carry out high speed dispersion in the dispersion machine of 50m/s, obtains mixture II;
(3), in said mixture II add Aqueous Adhesives, wetting agent, after slowly stirring, filter to obtain waterborne polymeric slurry with 400 eye mesh screens;
(4), the water soluble polymer thickener of formula ratio, aqueous dispersion and deionized water are joined in pre-agitator tank, dissolve completely, obtain mixture III;
(5), in said mixture III add ceramic particle, stirring on-line velocity after 30-60 minute is carry out high speed dispersion in the dispersion machine of 30-60m/s, obtains mixture IV;
(6), in said mixture IV add Aqueous Adhesives, after slowly stirring, filter to obtain aqueous ceramic slurry with 300 eye mesh screens;
(7), in above-mentioned aqueous ceramic slurry, the waterborne polymeric slurry prepared early stage is added, obtained mixed coating coating slurry used after slowly stirring;
(8), by coating slurry the one or both sides of polyolefin film are coated, the obtained composite diaphragm that can bond after dry.
Wherein, the coating process in step (8) can be nick version, slit extrusion coated, dip-coating or spraying.
Below in conjunction with specific embodiment and comparative example, such scheme is described further.Should be understood that these embodiments are for illustration of the present invention, be not limited to limit the scope of the invention.The implementation condition adopted in embodiment can do further adjustment as the case may be, and not marked implementation condition is generally the condition in normal experiment.
Embodiment 1
A kind of composite diaphragm that can bond, comprise polypropylene porous film and the mixed coating being coated on polypropylene porous film side, wherein polypropylene porous film thickness is 16um, and porosity is 42%, coating layer thickness is 4um, and mixed coating coating slurry used is made up of composition and deionized water; Described composition comprises Kynoar-hexafluoropropylene copolymer particle 30 parts that the particle diameter calculated according to mass parts is 200nm, ceramic particle silicon dioxide 70 parts, Aqueous Adhesives polyvinyl alcohol 2 parts, Aqueous Adhesives polymethyl methacrylate 4 parts, metal carboxylate fluorine dispersant 1 part, aqueous dispersion Sodium Polyacrylate 1 part, water water soluble polymer thickener hydroxyethylcellulose 2 parts, wetting agent fluoro-alkyl methoxyl group ether alcohol 5 parts of formations.
The composite diaphragm with attachment function described in preparation; Comprise following preparation process:
(1), 1 part of water soluble polymer thickener hydroxyethylcellulose, 1 part of metal carboxylate fluorine dispersant and deionized water are joined in pre-agitator tank, dissolve completely, obtain mixture I;
(2), in said mixture I, add Kynoar-hexafluoropropylene copolymer 30 parts that particle diameter is 200nm, stirring on-line velocity after 30-60 minute is carry out high speed dispersion in the dispersion machine of 50m/s, obtains mixture II;
(3), in said mixture II, add Aqueous Adhesives polyvinyl alcohol 2 parts, wetting agent fluoro-alkyl methoxyl group ether alcohol 2 parts, after low rate mixing is even, filter to obtain Kynoar-hexafluoropropylene copolymer slurry with 400 eye mesh screens;
(4), 1 part of water soluble polymer thickener hydroxyethylcellulose, aqueous dispersion Sodium Polyacrylate 1 part and deionized water are joined in pre-agitator tank, dissolve completely, obtain mixture III;
(5), in said mixture III add ceramic particle silicon dioxide 70 parts, stirring on-line velocity after 30-60 minute is carry out high speed dispersion in the dispersion machine of 30-60m/s, obtains mixture IV;
(6), in said mixture IV add Aqueous Adhesives polymethyl methacrylate 4 parts, after low rate mixing is even, filter to obtain water-based SiO 2-ceramic slurry with 300 eye mesh screens;
(7), in above-mentioned water-based SiO 2-ceramic slurry, add the Kynoar-hexafluoropropylene copolymer slurry prepared early stage, low rate mixing evenly obtains mixed coating coating slurry used afterwards.
(8), coating slurry nick version is coated the side of polyolefin film, the obtained composite diaphragm with attachment function after dry.
Embodiment 2
A kind of composite diaphragm that can bond, comprise polyethylene porous membrane and the mixed coating being coated on polyethylene porous membrane both sides, wherein polyethylene porous film thickness is 5um, and porosity is 30%, both sides coating layer thickness is 2um, and mixed coating coating slurry used is made up of composition and deionized water; Described composition comprises the polyacrylonitrile particle 50 parts that the particle diameter calculated according to mass parts is 1um, ceramic particle alundum (Al2O3) 50 parts, Aqueous Adhesives butadiene-styrene latex 5 parts, Aqueous Adhesives polybutyl methacrylate 3 parts, aqueous dispersion Sulfonates fluorine dispersant 0.5 part, aqueous dispersion polyacrylic acid potassium 0.5 part, water soluble polymer thickener sodium carboxymethylcellulose 3 parts, wetting agent fluoro-alkyl ethyoxyl ether alcohol 1 part of formation.
The composite diaphragm with attachment function described in preparation; Comprise following preparation process:
(1), 2 parts of water soluble polymer thickener sodium carboxymethylcelluloses, 0.5 part of Sulfonates fluorine dispersant and deionized water are joined in pre-agitator tank, dissolve completely, obtain mixture I;
(2), in said mixture I, add the polyacrylonitrile 50 parts that particle diameter is 1um, stirring on-line velocity after 30-60 minute is carry out high speed dispersion in the dispersion machine of 50m/s, obtains mixture II;
(3), in said mixture II, add Aqueous Adhesives butadiene-styrene latex 5 parts, wetting agent fluoro-alkyl ethyoxyl ether alcohol 1 part, after low rate mixing is even, filter to obtain polyacrylonitrile pulp with 400 eye mesh screens;
(4), 1 part of water soluble polymer thickener sodium carboxymethylcellulose, aqueous dispersion polyacrylic acid potassium 0.5 part and deionized water are joined in pre-agitator tank, dissolve completely, obtain mixture III;
(5), in said mixture III add ceramic particle alundum (Al2O3) 50 parts, stirring on-line velocity after 30-60 minute is carry out high speed dispersion in the dispersion machine of 30-60m/s, obtains mixture IV;
(6), in said mixture IV add Aqueous Adhesives polybutyl methacrylate 3 parts, after low rate mixing is even, filter to obtain water-based aluminum oxide ceramic slurry with 300 eye mesh screens;
(7), in above-mentioned water-based aluminum oxide ceramic slurry, add the polyacrylonitrile pulp prepared early stage, low rate mixing evenly obtains mixed coating coating slurry used afterwards.
(8), coating slurry dip coating manner is coated the both sides of polyolefin film, the obtained composite diaphragm with attachment function after dry.
Embodiment 3
A kind of composite diaphragm that can bond, comprise polypropylene, polyethylene/polypropylene composite materials porous membrane and the mixed coating being coated on polypropylene, polyethylene/polypropylene composite materials porous membrane side, wherein polypropylene, polyethylene/polypropylene composite materials porous membrane thickness is 20um, porosity is 39%, coating layer thickness is 5um, and mixed coating coating slurry used is made up of composition and deionized water; Described composition comprises the polyethylene glycol oxide particle 20 parts that the particle diameter calculated according to mass parts is 2um, ceramic particle boehmite 80 parts, Aqueous Adhesives ethylene-vinyl acetate copolymer 5 parts, aqueous dispersion Sodium Polyacrylate 3 parts, water soluble polymer thickener polyacrylamide 5 parts, wetting agent APES 3 parts formation.
The composite diaphragm with attachment function described in preparation; Comprise following preparation process:
(1), 3 parts of water soluble polymer thickener polyacrylamides, 1 part of aqueous dispersion Sodium Polyacrylate and deionized water are joined in pre-agitator tank, dissolve completely, obtain mixture I;
(2), in said mixture I, add the polyethylene glycol oxide 20 parts that particle diameter is 2um, stirring on-line velocity after 30-60 minute is carry out high speed dispersion in the dispersion machine of 50m/s, obtains mixture II;
(3), in said mixture II, add Aqueous Adhesives ethylene-vinyl acetate copolymer 1 part, wetting agent APES 1 part, after low rate mixing is even, filter to obtain polyethylene glycol oxide slurry with 400 eye mesh screens;
(4), 2 parts of water soluble polymer thickener polyacrylamides, aqueous dispersion Sodium Polyacrylate 2 parts and deionized water are joined in pre-agitator tank, dissolve completely, obtain mixture III;
(5), in said mixture III add ceramic particle boehmite 80 parts, stirring on-line velocity after 30-60 minute is carry out high speed dispersion in the dispersion machine of 30-60m/s, obtains mixture IV;
(6), in said mixture IV add Aqueous Adhesives ethylene-vinyl acetate copolymer 4 parts, after low rate mixing is even, filter to obtain water-based boehmite slurry with 300 eye mesh screens;
(7), in above-mentioned water-based boehmite ceramic size, add the polyethylene glycol oxide slurry prepared early stage, low rate mixing evenly obtains mixed coating coating slurry used afterwards.
(8), coating slurry crack fashion of extrusion is coated the side of polyolefin film, the obtained composite diaphragm with attachment function after dry.
Embodiment 4
A kind of composite diaphragm that can bond, comprise polyethylene porous film and the mixed coating being coated on polyethylene porous film side, wherein polyethylene porous film thickness is 9um, and porosity is 45%, coating layer thickness is 3um, and mixed coating coating slurry used is made up of composition and deionized water; Described composition comprises the poly methyl methacrylate particle 10 parts that the particle diameter calculated according to mass parts is 0.1um, 90 parts, ceramic particle barium sulfate, Aqueous Adhesives polyethyl acrylate 3 parts, Aqueous Adhesives polyvinyl acetate 3 parts, aqueous dispersion polyacrylic acid potassium 5 parts, water soluble polymer thickener sodium alginate 4 parts, wetting agent AEO 5 parts formation.
The composite diaphragm with attachment function described in preparation; Comprise following preparation process:
(1), 2 parts of water soluble polymer thickener sodium alginates, 3 parts of aqueous dispersion polyacrylic acid potassiums and deionized water are joined in pre-agitator tank, dissolve completely, obtain mixture I;
(2), in said mixture I, add the poly methyl methacrylate particle 10 parts that particle diameter is 0.1um, stirring on-line velocity after 30-60 minute is carry out high speed dispersion in the dispersion machine of 50m/s, obtains mixture II;
(3), in said mixture II, add Aqueous Adhesives Aqueous Adhesives polyethyl acrylate 3 parts, wetting agent AEO 5 parts, after low rate mixing is even, filter to obtain polymethylmethacrylate syrup with 400 eye mesh screens;
(4), 2 parts of water soluble polymer thickener ALG sodium, aqueous dispersion polyacrylic acid potassium 2 parts and deionized waters are joined in pre-agitator tank, dissolve completely, obtain mixture III;
(5), in said mixture III add 90 parts, ceramic particle barium sulfate, stirring on-line velocity after 30-60 minute is carry out high speed dispersion in the dispersion machine of 30-60m/s, obtains mixture IV;
(6), in said mixture IV add Aqueous Adhesives polyvinyl acetate 3 parts, after low rate mixing is even, filter to obtain sulfuric acid barium slurry with 300 eye mesh screens;
(7), in above-mentioned sulfuric acid titanate ceramics slurry, add the polymethylmethacrylate syrup prepared early stage, low rate mixing evenly obtains mixed coating coating slurry used afterwards.
(8), coating slurry spraying method is coated the side of polyolefin film, the obtained composite diaphragm with attachment function after dry.
Comparative example 1
This comparative example provides a kind of alumina ceramic coating lithium ion battery separator, comprise polypropylene porous film and the aluminum oxide coating layer being coated on polypropylene porous film side, wherein polypropylene porous film thickness is 16um, and porosity is 42%, and aluminum oxide coating layer thickness is 4um.
Comparative example 2
This comparative example provides polymer coating lithium ion battery separator, comprise polypropylene porous film and the polymer coating playing cementation being coated on polypropylene porous film side, wherein polypropylene porous film thickness is 16um, and porosity is 42%, and polymer coating thickness is 1um.
Comparative example 3
This comparative example adopts thickness to be 16um, and porosity is 42% polypropylene porous membrane, shows and does not carry out any coating process.
Thermal contraction test is carried out: test barrier film toasts 1h at 130 DEG C, and toast the heat resistance of 30min at 150 DEG C, same barrier film tests 5 times, and test result is listed in table 1 to adopting the lithium ion battery separator of embodiment 1-4 and comparative example 1-3.
Adhesion strength between composite diaphragm and battery pole piece can be measured as follows: by the lithium ion battery separator of embodiment 1 to 4 and comparative example 1-3 and positive plate, negative plate is wound into battery core (barrier film coated side is facing to anode pole piece), load in aluminum plastic film, inject electrolyte, sealing, leave standstill, it is 60 DEG C in temperature, pressure is that 0.5MPa/cm2 places 5min, then battery is disassembled, the positive plate adhered to each other and barrier film are cut into 100mm (TD) × 15mm (MD), and be attached on steel plate with two-sided tape (3M), by the adhesion strength between puller system measuring diaphragm and positive plate, same barrier film tests 5 times, test result is listed in table 1.
Table 1
Wherein, MD refers to longitudinal direction, and TD refers to transverse direction.
As shown in Table 1, under the combined high temperature adopting the present invention to prepare, the thermal contraction performance of (130 DEG C and 150 DEG C) has clear improvement, the both positive and negative polarity short-circuit risks that battery causes because of diaphragm retracts in abnormal conditions such as high temperature can be reduced, there is cementation between barrier film and battery pole piece simultaneously, can reduce battery to misplace between pole piece and barrier film under external force the short-circuit risks caused, the security performance of battery is improved.Comparative example 1 and comparative example 2 all can only provide the effect on the one hand such as heat insulation or bonding, promote limited to the security performance of battery.
Foregoing description is only set forth section Example of the present invention; the present invention is understood for helping; but embodiments of the present invention are not restricted to the described embodiments; any do not deviate from the principle of the invention under do change, modification, substitute, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. the composite diaphragm that can bond, is characterized in that: comprise polyolefin porous membrane and be coated on the mixed coating of polyolefin porous membrane one or both sides, and coating layer thickness is 2-8 μm; Described mixed coating comprises polymer beads 10-50 part and ceramic particle 50-90 part of calculating by mass parts.
2. composite diaphragm according to claim 1, is characterized in that: described mixed coating coating slurry used is made up of composition and deionized water; Described composition comprises the polymer beads 10-50 part calculated according to mass parts, ceramic particle 50-90 part, Aqueous Adhesives 3-10 part, aqueous dispersion 1-5 part, water-based thickener 1-5 part, wetting agent 1-5 part.
3. composite diaphragm according to claim 1 and 2, is characterized in that: described polymer beads is one or more in Kynoar-hexafluoropropylene copolymer, polyacrylonitrile, polyethylene glycol oxide, polymethyl methacrylate, and particle diameter is 0.1-2um.
4. composite diaphragm according to claim 1 and 2, is characterized in that: described ceramic particle is one or more in silicon dioxide, alundum (Al2O3), titanium dioxide, boehmite, magnesium dioxide, barium sulfate.
5. composite diaphragm according to claim 2, is characterized in that: described Aqueous Adhesives is one or more in polymethyl methacrylate, polybutyl methacrylate, butadiene-styrene latex, styrene-acrylic latex, polyethyl acrylate, ethylene-vinyl acetate copolymer, polyvinyl alcohol, polyvinyl acetate.
6. composite diaphragm according to claim 2, is characterized in that: described aqueous dispersion is one or more in metal carboxylate fluorine dispersant, Sulfonates fluorine dispersant, Sodium Polyacrylate, polyacrylic acid potassium.
7. composite diaphragm according to claim 2, is characterized in that: described water soluble polymer thickener is one or more in hydroxyethylcellulose, methyl hydroxyethylcellulose, sodium carboxymethylcellulose, polyacrylamide, sodium alginate; Described wetting agent is one or more in fluoro-alkyl methoxyl group ether alcohol, fluoro-alkyl ethyoxyl ether alcohol, APES, AEO, aliphatic acid polyethenoxy ether.
8. composite diaphragm according to claim 1 and 2, is characterized in that: described polyolefin porous membrane is polyethylene film, polypropylene screen, polypropylene, polyethylene/polypropylene screen, and the thickness of described polyolefin porous membrane is 5-40 μm, and porosity is 30-60%.
9. a manufacture method for composite diaphragm, is characterized in that comprising the following steps:
(1), the water soluble polymer thickener of formula ratio, aqueous dispersion and deionized water are joined in pre-agitator tank, dissolve completely, obtain mixture I;
(2), in said mixture I add polymer beads, stirring on-line velocity after 30-60 minute is carry out high speed dispersion in the dispersion machine of 50m/s, obtains mixture II;
(3), in said mixture II add Aqueous Adhesives, wetting agent, after slowly stirring, filter to obtain waterborne polymeric slurry with 400 eye mesh screens;
(4), the water soluble polymer thickener of formula ratio, aqueous dispersion and deionized water are joined in pre-agitator tank, dissolve completely, obtain mixture III;
(5), in said mixture III add ceramic particle, stirring on-line velocity after 30-60 minute is carry out high speed dispersion in the dispersion machine of 30-60m/s, obtains mixture IV;
(6), in said mixture IV add Aqueous Adhesives, after slowly stirring, filter to obtain aqueous ceramic slurry with 300 eye mesh screens;
(7), in above-mentioned aqueous ceramic slurry, the waterborne polymeric slurry prepared early stage is added, obtained mixed coating coating slurry used after slowly stirring;
(8), by coating slurry the one or both sides of polyolefin film are coated, the obtained composite diaphragm that can bond after dry.
10. method according to claim 9, is characterized in that: the coating process in described step (8) is nick version, slit extrusion coated, dip-coating or spraying.
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