CN103515564B - A kind of composite diaphragm and preparation method thereof - Google Patents
A kind of composite diaphragm and preparation method thereof Download PDFInfo
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- CN103515564B CN103515564B CN201310482147.4A CN201310482147A CN103515564B CN 103515564 B CN103515564 B CN 103515564B CN 201310482147 A CN201310482147 A CN 201310482147A CN 103515564 B CN103515564 B CN 103515564B
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- 239000002131 composite material Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims description 22
- 239000002245 particle Substances 0.000 claims abstract description 39
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 32
- 229920000642 polymer Polymers 0.000 claims abstract description 23
- 239000000853 adhesive Substances 0.000 claims abstract description 22
- 230000001070 adhesive effect Effects 0.000 claims abstract description 22
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 19
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 19
- 239000010410 layer Substances 0.000 claims abstract description 17
- 239000004743 Polypropylene Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 229920001155 polypropylene Polymers 0.000 claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011148 porous material Substances 0.000 claims abstract description 6
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 4
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 4
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 4
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 4
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 4
- 239000011247 coating layer Substances 0.000 claims abstract description 3
- 229920001577 copolymer Polymers 0.000 claims abstract description 3
- 239000004094 surface-active agent Substances 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000002002 slurry Substances 0.000 claims description 22
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 19
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 19
- 230000004888 barrier function Effects 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical group FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 14
- 239000012528 membrane Substances 0.000 claims description 13
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 11
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 239000002270 dispersing agent Substances 0.000 claims description 9
- 239000004698 Polyethylene Substances 0.000 claims description 8
- 239000002562 thickening agent Substances 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 6
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 5
- 229930195725 Mannitol Natural products 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000000594 mannitol Substances 0.000 claims description 5
- 235000010355 mannitol Nutrition 0.000 claims description 5
- 229920001451 polypropylene glycol Polymers 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 238000007761 roller coating Methods 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 229920003169 water-soluble polymer Polymers 0.000 claims description 3
- NKSOSPOXQKNIKJ-CLFAGFIQSA-N Polyoxyethylene dioleate Polymers CCCCCCCC\C=C/CCCCCCCC(=O)OCCOC(=O)CCCCCCC\C=C/CCCCCCCC NKSOSPOXQKNIKJ-CLFAGFIQSA-N 0.000 claims description 2
- 239000002174 Styrene-butadiene Substances 0.000 claims description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 2
- 150000005215 alkyl ethers Chemical class 0.000 claims description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- 239000003292 glue Substances 0.000 claims description 2
- 239000004816 latex Substances 0.000 claims description 2
- 229920000126 latex Polymers 0.000 claims description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 2
- 239000011115 styrene butadiene Substances 0.000 claims description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
- RFVNOJDQRGSOEL-UHFFFAOYSA-N 2-hydroxyethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCO RFVNOJDQRGSOEL-UHFFFAOYSA-N 0.000 claims 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 229940084030 carboxymethylcellulose calcium Drugs 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 229920005862 polyol Polymers 0.000 claims 1
- 150000003077 polyols Chemical class 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 10
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 abstract description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 abstract description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 abstract description 4
- 239000004642 Polyimide Substances 0.000 abstract description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract description 2
- 229920006231 aramid fiber Polymers 0.000 abstract description 2
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000010954 inorganic particle Substances 0.000 abstract description 2
- 239000011146 organic particle Substances 0.000 abstract description 2
- 229920001721 polyimide Polymers 0.000 abstract description 2
- 239000011347 resin Substances 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 23
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 22
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 22
- 238000003756 stirring Methods 0.000 description 21
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 20
- 239000000843 powder Substances 0.000 description 12
- 210000004379 membrane Anatomy 0.000 description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 229920000098 polyolefin Polymers 0.000 description 6
- 229920006184 cellulose methylcellulose Polymers 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 235000009508 confectionery Nutrition 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000004040 pyrrolidinones Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 210000002469 basement membrane Anatomy 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229920000891 common polymer Polymers 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000011242 organic-inorganic particle Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 150000003235 pyrrolidines Chemical class 0.000 description 1
- 102220043159 rs587780996 Human genes 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Laminated Bodies (AREA)
Abstract
Supporting layer and organic/inorganic particle the invention discloses a kind of composite diaphragm, including stacking are blended coat；The coat includes being evenly mixed in polymer particle and inorganic particulate in adhesive, the coating layer surface and it is internal there is microcellular structure, porosity ranges are 20% 80%, and average pore size is 0.01 μm 10 μm；The polymer particle includes that polytetrafluoroethylene (PTFE), Kynoar, Kynoar hexafluoropropylene copolymer, polyimides, polypropylene be fine, one or more in aramid fiber resin, the particle size range of the polymer particle is 0.01 μm~10 μm, and the inorganic particulate includes SiO2、Al2O3、CaO、TiO2、MgO、ZnO、SnO2、ZrO2In any one or it is various, the particle size range of the inorganic particulate is 0.01 μm~10 μm, and the mass ratio of the polymer particle and inorganic particulate is 1: 10~10: 1.Method the invention also discloses this composite diaphragm is prepared.The present invention has thermal safety good and strong to the absorption holding capacity of electrolyte；The advantage of low cost and low stain can be realized simultaneously.
Description
Technical field
The present invention relates to lithium battery diaphragm, more particularly, to a kind of composite diaphragm high of security performance under high temperature and its preparation
Method.
Background technology
Barrier film as one of big material of lithium battery four, although and the electrochemical reaction that is not involved in battery, but lithium is electric
Significant components in pond, while membrane technique is also one of key technology of the lithium battery development of restriction China and application.The appearance of battery
The key performances such as amount, cycle performance and charging and discharging currents density all have direct relation with barrier film, and the improvement of membrane properties is right
The combination property for improving lithium battery plays an important role.
At present, the lithium battery diaphragm of commercialization is with polyolefin（PP、PE）Based on single thin film or plural layers.Polyolefin
Material has intensity and preferable chemical stability higher, and used as a kind of thermoplastic, porous polyolefin is being higher than
Self-closing function with shrinkage porosity under conditions of glass transition temperature, impedance is substantially risen, is limited by the electric current of battery
System, can to a certain extent prevent the phenomenons such as the blast that causes due to overheat, be a kind of relatively reliable lithium battery diaphragm material
Material.But, the fusing point of polyolefin-based separator is general below 180 DEG C, deforms under high temperature serious.When battery temperature outside or
Internal factor effect is lower to be raised, and barrier film can deform contraction, it is likely that cause battery short circuit, cause the generation of accident.Especially
The electrokinetic cell of high power discharge, internal temperature of battery is higher during use, and it is preferably thermally safe that this requires that barrier film has
Property.
The content of the invention
There is potential safety hazard at high temperature to overcome existing polyalkene diaphragm, it is an object of the invention to provide one
Safe composite diaphragm and preparation method thereof under kind high temperature.
The present invention is achieved through the following technical measures, a kind of composite diaphragm, including stacking supporting layer and organic/nothing
Machine particle is blended coat；The coat includes the polymer particle and inorganic particulate that are evenly mixed in adhesive, described
Coating layer surface and inside have microcellular structure, and porosity ranges are 20%-80%, and average pore size is 0.01 μm -10 μm；It is described poly-
Polymer particle includes polytetrafluoroethylene (PTFE), Kynoar, Kynoar-hexafluoropropylene copolymer, polyimides, polypropylene
One or more in fine, aramid fiber resin, the particle size range of the polymer particle is 0.01 μm~10 μm, the inorganic grain
Attached bag includes SiO2、Al2O3、CaO、TiO2、MgO、ZnO、SnO2、ZrO2In any one or it is various, the inorganic particulate
Particle size range is 0.01 μm~10 μm, and the mass ratio of the polymer particle and inorganic particulate is 1: 10~10: 1.
Used as a kind of preferred embodiment, the supporting layer is polyethylene porous film, polypropylene porous membrane or polypropylene/poly-
Ethylene/polypropylene composite porous film, at 8 μm~100 μm, porosity ranges are 30%~80% to the thickness range of supporting layer, are put down
Equal aperture is 0.01 μm~10 μm.
Used as a kind of preferred embodiment, the thickness range of the supporting layer is 8 μm~25 μm, porosity ranges are 30%~
50%, average pore size is 100nm~150nm.
Used as a kind of preferred embodiment, the polymer particle is that Kynoar or Kynoar-hexafluoropropene are common
Polymers, the particle size range of the polymer particle is 0.1 μm~2 μm.
Used as a kind of preferred embodiment, the inorganic particulate is SiO2Or Al2O3, the particle size range of the inorganic particulate is 0.1
μm~3 μm.
Used as a kind of preferred embodiment, the thickness of the coat is 1 μm~10 μm.
Used as a kind of preferred embodiment, the thickness of the coat is 1 μm~4 μm.
The invention also discloses a kind of preparation method of composite diaphragm, comprise the following steps：
1）, using deionized water as solvent, Aqueous Adhesives, surfactant, dispersant, thickener etc. is high in normal temperature
Speed stirring lower dissolving, wiring solution-forming；Above-mentioned polymer particle and inorganic particulate is added, high-speed stirred is uniform, is made into aqueous
Slurry；The mass percent of each material is in slurry：0.1%~2% water soluble polymer thickener, 0.01%~2% it is aqueous
Dispersant, 0.01%~2% surfactant, 0.1%~5% Aqueous Adhesives, 5%~50% polymer particle and inorganic grain
Son, 50%~83% deionized water；
2）, using micro- gravure roller coating, water paste prepared by the first step is coated on supporting layer barrier film, application rate is
5~100m/min；
3）, by coat film obtained in the previous step by 50~100 DEG C of oven for drying, obtain final composite membrane.
As a kind of preferred embodiment, the polymer particle and inorganic particulate mass percent in the slurry is 15%~
45%。
Used as a kind of preferred embodiment, the Aqueous Adhesives are polyvinyl alcohol, polyethylene glycol oxide, acrylic compounds water solubility
At least one in glue, styrene-butadiene latex；The surfactant is fluorocarbon surfactant, silane surface active agent, polyalcohol
At least one in class surfactant；The dispersant is polyoxyethylene dioleate, poly- TEG monostearate, gathers
TEG monoleate, polyoxypropylene mannitol dioleate, polyoxypropylene stearate, polyoxyethylene fatty acid, alkyl
At least one in benzene sulfonate, polyoxyethylene alkylether, polyvinylpyrrolidone；The thickener is carboxymethyl cellulose
At least one in element, sodium carboxymethylcellulose, polyvinyl alcohol；The speed of the high-speed stirred is 2000~5000r/min；Every
The application rate of film is 10~70m/min, and oven temperature is 50~80 DEG C, and drying time is 3~120s.
The present invention is added with resistant to elevated temperatures inorganic particulate in coat, improves the thermal safety of barrier film；Composite membrane exists
Placed 1 hour at a high temperature of 135 DEG C, percent thermal shrinkage is less than 3%.Meanwhile, inorganic particulate improves infiltration of the electrolyte to barrier film
Property, it is easy to the absorption of electrolyte；Organic filler, can be swelling in the electrolytic solution, has good absorption and keeps the ability of electrolyte,
With electrical conductivity higher, so that lithium battery has good service life cycle；Meanwhile, battery plus-negative plate is glued well
Knot laminating, improves battery core hardness and body holding capacity.Coating sizing-agent solvent for use is water, organic without acetone, DMF, NMP etc.
Solvent, will not pollute to environment, will not endanger the health of workman.As the product of industrialized production, using water as molten
Agent significantly reduces production cost, makes product more competitive.
The present invention has the thermal safety for improving conventional polyolefins barrier film poor and poor to the absorption holding capacity of electrolyte
Shortcoming；The advantage of low cost and low stain is realized simultaneously.
Brief description of the drawings
Fig. 1 illustrates for the cross section of the embodiment of the present invention；
Fig. 2 schemes for the modified layer composite membrane apparent form SEM of the embodiment of the present invention；
Fig. 3 is the electrolyte retention curve map of the embodiment of the present invention.
Specific embodiment
With reference to embodiment and compare accompanying drawing the present invention is described in further detail.
With reference to Fig. 1, a kind of composite diaphragm, including the supporting layer 1 and organic/inorganic particle of stacking are blended coat 2, its system
Preparation Method comprises the following steps：
1）, using deionized water as solvent, Aqueous Adhesives, surfactant, dispersant, thickener etc. is high in normal temperature
Speed stirring lower dissolving, wiring solution-forming；Polymer particle and inorganic particulate are added, high-speed stirred is uniform, is made into water paste；Slurry
The mass percent of each material is in material：0.1%~2% water soluble polymer thickener, 0.01%~2% aqueous dispersion,
0.01%~2% surfactant, 0.1%~5% Aqueous Adhesives, 5%~50% polymer particle and inorganic particulate, 50%
~83% deionized water；
2）, using micro- gravure roller coating, water paste prepared by the first step is coated on supporting layer barrier film, application rate is
5~100m/min；
3）, by coat film obtained in the previous step by 50~100 DEG C of oven for drying, obtain final composite membrane.
The coating processes selection in each embodiment of lower example：Micro- gravure roller coating is used, application rate is 40m/min；Coating basement membrane
It is the 16 μ dry method microporous polypropylene membranes of Shenzhen Senior Material Technology Co., Ltd., porosity is 42%；Entered using three-level baking oven
Row drying, oven temperatures at different levels are respectively 50~57 DEG C, 55~63 DEG C, 63~70 DEG C.The thickness of coat is 3 μ, is coated with caudacoria
Thickness be 19 μ.
Hereinafter the formula and technique again in detail in several embodiments to slurry are illustrated.
Embodiment 1
Weight proportion organic/inorganic stuff and other stuff in slurry: deionized water=100: 200, PVDF-HFP: Al2O3=20∶80。
First in adhesive PVA and tackifier CMC addition deionized waters, at normal temperatures with 300r/min stirring 20min until completely
Dissolving, the weight proportion of wherein PVA and CMC is respectively PVA: organic/inorganic stuff and other stuff=4.5: 100, CMC: organic/inorganic
Stuff and other stuff=1.5: 100.Then fluorocarbon surfactant, aqueous dispersion polyoxypropylene are sequentially added in above-mentioned solution sweet
Dew alcohol dioleate and organic/inorganic stuff and other stuff powder, continue to stir 10min with 300r/min, finally high in 5000r/min
The lower stirring 5min of speed, slurry preparation is completed.Wherein fluorocarbon surfactant: organic/inorganic stuff and other stuff=0.2: 100, polyoxy third
Alkene mannitol dioleate: organic/inorganic stuff and other stuff=0.6: 100.PVDF-HFP weight average molecular weight is about 370,000, and particle diameter is
100~300nm, Al2O3D50=1.0 μm of powder.
Embodiment 2
Weight proportion organic/inorganic stuff and other stuff in slurry: deionized water=100: 200, PVDF-HFP: Al2O3=38∶62。
First in adhesive PVA and tackifier CMC addition deionized waters, at normal temperatures with 300r/min stirring 20min until completely
Dissolving, the weight proportion of wherein PVA and CMC is respectively PVA: organic/inorganic stuff and other stuff=4.5: 100, CMC: organic/inorganic
Stuff and other stuff=1.5: 100.Then fluorocarbon surfactant, aqueous dispersion polyoxypropylene are sequentially added in above-mentioned solution sweet
Dew alcohol dioleate and organic/inorganic stuff and other stuff powder, continue to stir 10min with 300r/min, finally high in 5000r/min
The lower stirring 5min of speed, slurry preparation is completed.Wherein fluorocarbon surfactant: organic/inorganic stuff and other stuff=0.2: 100, polyoxy third
Alkene mannitol dioleate: organic/inorganic stuff and other stuff=0.6: 100.PVDF-HFP weight average molecular weight is about 370,000, and particle diameter is
100~300nm, Al2O3D50=1.0 μm of powder.
Embodiment 3
Weight proportion organic/inorganic stuff and other stuff in slurry: deionized water=100: 200, PVDF-HFP: Al2O3=47∶53。
First in adhesive PVA and tackifier CMC addition deionized waters, at normal temperatures with 300r/min stirring 20min until completely
Dissolving, the weight proportion of wherein PVA and CMC is respectively PVA: organic/inorganic stuff and other stuff=4.5: 100, CMC: organic/inorganic
Stuff and other stuff=1.5: 100.Then fluorocarbon surfactant, aqueous dispersion polyoxypropylene are sequentially added in above-mentioned solution sweet
Dew alcohol dioleate and organic/inorganic stuff and other stuff powder, continue to stir 10min with 300r/min, finally high in 5000r/min
The lower stirring 5min of speed, slurry preparation is completed.Wherein fluorocarbon surfactant: organic/inorganic stuff and other stuff=0.2: 100, polyoxy third
Alkene mannitol dioleate: organic/inorganic stuff and other stuff=0.6: 100.PVDF-HFP weight average molecular weight is about 370,000, and particle diameter is
100~300nm, Al2O3D50=1.0 μm of powder.
Embodiment 4
Weight proportion organic/inorganic stuff and other stuff in slurry: deionized water=100: 200, PVDF-HFP: Al2O3=20∶80。
First in adhesive PVA and tackifier CMC addition deionized waters, at normal temperatures with 300r/min stirring 20min until completely
Dissolving, the weight proportion of wherein PVA and CMC is respectively PVA: organic/inorganic stuff and other stuff=4.5: 100, CMC: organic/inorganic
Stuff and other stuff=1.5: 100.Then fluorocarbon surfactant, polyethylene of dispersing agent pyrrolidones are sequentially added in above-mentioned solution
（PVP）With organic/inorganic stuff and other stuff powder, continue to stir 10min with 300r/min, finally stirred under 5000r/min high speeds
5min is mixed, slurry preparation is completed.Wherein fluorocarbon surfactant: organic/inorganic stuff and other stuff=0.2: 100, PVP: organic/nothing
Machine stuff and other stuff=0.6: 100.PVDF-HFP weight average molecular weight is about 370,000, and particle diameter is 100~300nm, Al2O3Powder D50=
1.0μm。
Embodiment 5
Weight proportion organic/inorganic stuff and other stuff in slurry: deionized water=100: 200, PVDF-HFP: Al2O3=20∶80。
During acrylic compounds adhesive and tackifier CMC are added deionized water first, at normal temperatures with 300r/min stirring 20min until
It is completely dissolved, the weight proportion of wherein adhesive and CMC is respectively acrylic compounds adhesive: organic/inorganic stuff and other stuff=4.5:
100, CMC: organic/inorganic stuff and other stuff=1.5: 100.Then fluorocarbon surfactant, dispersion are sequentially added in above-mentioned solution
Agent polyvinylpyrrolidone（PVP）With organic/inorganic stuff and other stuff powder, continue to stir 10min with 300r/min, finally exist
5000r/min is lower at a high speed to stir 5min, and slurry preparation is completed.Wherein fluorocarbon surfactant: organic/inorganic stuff and other stuff=0.2
: 100, PVP: organic/inorganic stuff and other stuff=0.6: 100.PVDF-HFP weight average molecular weight is about 370,000, and particle diameter is 100~
300nm, Al2O3D50=1.0 μm of powder.
The following is the formula and technique of the slurry in several comparative examples for illustrating effect of the present invention.
Comparative example 1
Weight proportion Al in slurry2O3: deionized water=100: 200.Adhesive PVA and tackifier CMC is added first is gone
In ionized water, at normal temperatures with 300r/min stirring 20min until being completely dissolved, the weight proportion of wherein PVA and CMC is respectively
PVA∶Al2O3=4.5: 100, CMC: Al2O3=1.5∶100.Then polyethylene of dispersing agent pyrrolidines is sequentially added in above-mentioned solution
Ketone（PVP）And Al2O3, continue to stir 10min with 300r/min, finally stir 5min, slurry preparation under 5000r/min high speeds
Complete.Wherein PVP: Al2O3=0.6: 100, Al2O3D50=1.0 μm of powder.
Comparative example 2
Weight proportion PVDF-HFP in slurry: deionized water=100: 500.First acrylic compounds adhesive and tackifier
CMC is added in deionized water, stirs 20min with 300r/min until being completely dissolved at normal temperatures, wherein acrylic compounds adhesive
Weight proportion with CMC is respectively adhesive: PVDF-HFP=5: 100, CMC: PVDF-HFP=1: 100.Then in above-mentioned solution
In sequentially add fluorocarbon surfactant, polyethylene of dispersing agent pyrrolidones（PVP）With PVDF-HFP powder, continue with 300r/
Min stirs 10min, and 5min is finally stirred under 5000r/min high speeds, and slurry preparation is completed.Wherein fluorocarbon surfactant:
PVDF-HFP=0.1: 100, PVP: PVDF-HFP=0.3: 100.PVDF-HFP weight average molecular weight is about 370,000, and particle diameter is 100~
300nm。
Comparative example 3
This comparative example is the 16 μ microporous polypropylene membranes of Shenzhen Senior Material Technology Co., Ltd., porosity 42%, surface
Any coating is not coated with, other any surfaces is not done yet and is modified.
Table 1 is the barrier film prepared according to embodiment 1~5 and the method for comparative example 1~3.As can be seen from the table embodiment 1,
4th, 5 and comparative example 1 have preferable heat resistance, the heat resistance influence of a small amount of PVDF-HFP on barrier film is little in this explanation figure layer.
But as the increase barrier film heat resistance of PVDF-HFP ratios decreases, such as embodiment 2 and 3.Simultaneously from the data in table I
Also know, the ability for adding appropriate PVDF-HFP effectively to improve barrier film Electolyte-absorptive in the coating.
Table 1：
Fig. 3 is the embodiment of the present invention 5 and the barrier film of the method for comparative example 1 preparation to electrolyte retention correlation curve.Tool
Body examination method for testing：All it is the barrier film of 100mm × 100mm above two size, 1h is soaked in the electrolytic solution；Surface is dried in taking-up
Electrolyte, weighs the amount of Electolyte-absorptive；Then allow its exposure in atmosphere, the electrolyte for once retaining was recorded every 10 minutes
Quality；Finally make the amount and the graph of a relation for exposing the time in atmosphere for retaining electrolyte.Fig. 2 changes for the embodiment of the present invention
Property after layer composite membrane apparent form SEM figure.
Be can be seen that under suitable organic-inorganic particle proportion from the data of test, stuff and other stuff containing organic/inorganic is applied
The barrier film of layer can both possess the excellent heat resistance of ceramic coated film, while the also good absorption of polymer-coated film keeps electricity
Solution liquid energy power.
Above is being set forth composite diaphragm of the present invention and preparation method thereof, it is used to help understand the present invention, but this
The implementation method of invention is simultaneously not restricted to the described embodiments, it is any without departing from the change made under the principle of the invention, modify, replace
Generation, combination, simplification, should be equivalent substitute mode, be included within protection scope of the present invention.
Claims (6)
1. supporting layer and organic/inorganic the particle blending of a kind of preparation method of composite diaphragm, the composite diaphragm, including stacking
Coat；The coat includes the polymer particle and inorganic particulate that are evenly mixed in adhesive, the coating layer surface
And it is internal with microcellular structure, porosity ranges are 20%-80%, and average pore size is 0.01 μm -10 μm；The polymer particle
It is 1: 10~10: 1 with the mass ratio of inorganic particulate；The polymer particle is Kynoar or Kynoar-hexafluoro
Propylene copolymer；The particle size range of the polymer particle is 0.1 μm~2 μm；The inorganic particulate is SiO2 or Al2O3, institute
The particle size range for stating inorganic particulate is 0.1 μm~3 μm；The thickness of the coat is 1 μm~10 μm；It is characterized in that preparation side
Method comprises the following steps：
1), using deionized water as solvent, Aqueous Adhesives, surfactant, dispersant, thickener in normal temperature high-speed stirred
Lower dissolving, wiring solution-forming；Mentioned kind, particle diameter and mass ratio being pressed again and adding polymer particle and inorganic particulate, high-speed stirred is equal
It is even, it is made into water paste；The mass percent of each material is in slurry：0.1%~2% water soluble polymer thickener,
0.01%~2% aqueous dispersion, 0.01%~2% surfactant, 0.1%~5% Aqueous Adhesives, 5%~
50% polymer particle and inorganic particulate, 50%~83% deionized water；
2), using micro- gravure roller coating, water paste prepared by the first step is coated into porosity for 42%, 16 μ dry method polypropylene
On microporous barrier, application rate is 40m/min；
3), coat film obtained in the previous step is dried by three-level baking oven, oven temperatures at different levels are respectively 50~57 DEG C,
55~63 DEG C, 63~70 DEG C；The thickness of coat is 3 μ, and the thickness for being coated with caudacoria is 19 μ, obtains final composite membrane.
2. preparation method according to claim 1, it is characterised in that：The supporting layer is polyethylene porous film, poly- third
Alkene porous membrane or polypropylene, polyethylene/polypropylene composite materials porous membrane, the thickness range of supporting layer 8 μm~100 μm, hole
Gap rate scope is 30%~80%, and average pore size is 0.01 μm~10 μm.
3. preparation method according to claim 2, it is characterised in that：The thickness range of the supporting layer is 8 μm~25 μm,
Porosity ranges are 30%~50%, and average pore size is 100nm~150nm.
4. preparation method according to claim 1, it is characterised in that：The thickness of the coat is 1 μm~4 μm.
5. preparation method according to claim 1, it is characterised in that：The polymer particle and inorganic particulate are in the slurry
Mass percent be 15%~45%.
6. preparation method according to claim 1, it is characterised in that：The Aqueous Adhesives are polyvinyl alcohol, polyoxygenated
At least one in ethene, acrylic compounds water-soluble glue, styrene-butadiene latex；The surfactant is fluorocarbon surfactant, silicon
At least one in alkane surfactant, polyol surfactant；The dispersant is polyoxyethylene dioleate, poly- four
Ethylene glycol monostearate, poly- TEG monoleate, polyoxypropylene mannitol dioleate, polyoxypropylene stearate,
At least one in polyoxyethylene fatty acid, alkylbenzenesulfonate, polyoxyethylene alkylether, polyvinylpyrrolidone；It is described
Thickener is at least one in carboxymethylcellulose calcium, sodium carboxymethylcellulose, polyvinyl alcohol；The speed of the high-speed stirred is
2000~5000r/min；The application rate of barrier film is 10~70m/min, and the oven for drying time is 3~120s.
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