CN104157818A - Lithium battery diaphragm compounded from aqueous polymer and inorganic nanoparticles and preparation method thereof - Google Patents
Lithium battery diaphragm compounded from aqueous polymer and inorganic nanoparticles and preparation method thereof Download PDFInfo
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- CN104157818A CN104157818A CN201410445320.8A CN201410445320A CN104157818A CN 104157818 A CN104157818 A CN 104157818A CN 201410445320 A CN201410445320 A CN 201410445320A CN 104157818 A CN104157818 A CN 104157818A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 64
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 42
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000000576 coating method Methods 0.000 claims abstract description 53
- 239000011248 coating agent Substances 0.000 claims abstract description 46
- 239000002245 particle Substances 0.000 claims abstract description 35
- 239000000853 adhesive Substances 0.000 claims abstract description 21
- 230000001070 adhesive effect Effects 0.000 claims abstract description 21
- 239000002002 slurry Substances 0.000 claims abstract description 20
- 238000005524 ceramic coating Methods 0.000 claims abstract description 18
- 229920000098 polyolefin Polymers 0.000 claims abstract description 15
- 239000006255 coating slurry Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 77
- 230000004888 barrier function Effects 0.000 claims description 27
- -1 polyethylene Polymers 0.000 claims description 26
- 150000001875 compounds Chemical class 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 16
- 239000004094 surface-active agent Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- 239000000919 ceramic Substances 0.000 claims description 13
- 239000012528 membrane Substances 0.000 claims description 13
- 239000004743 Polypropylene Substances 0.000 claims description 12
- 229920001155 polypropylene Polymers 0.000 claims description 12
- 239000002562 thickening agent Substances 0.000 claims description 12
- 239000002033 PVDF binder Substances 0.000 claims description 11
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 7
- 239000004744 fabric Substances 0.000 claims description 7
- 238000004026 adhesive bonding Methods 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 239000004642 Polyimide Substances 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 5
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 5
- 229920006231 aramid fiber Polymers 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- 229920001721 polyimide Polymers 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 229920003169 water-soluble polymer Polymers 0.000 claims description 3
- 230000008901 benefit Effects 0.000 abstract description 3
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 17
- 210000004379 membrane Anatomy 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 210000002469 basement membrane Anatomy 0.000 description 4
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NKSOSPOXQKNIKJ-CLFAGFIQSA-N Polyoxyethylene dioleate Polymers CCCCCCCC\C=C/CCCCCCCC(=O)OCCOC(=O)CCCCCCC\C=C/CCCCCCCC NKSOSPOXQKNIKJ-CLFAGFIQSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000012360 testing method Methods 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
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
-
- 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
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
-
- 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
- H01M50/443—Particulate 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
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/491—Porosity
-
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Cell Separators (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a lithium battery diaphragm compounded from an aqueous polymer and inorganic nanoparticles. The lithium battery diaphragm comprises a polyolefin supporting layer, wherein one side of the polyolefin supporting layer is polymer coating, and the other side of the polyolefin supporting layer is ceramic coating; the polymer coating and the ceramic coating are compounded by a coating process; coating slurry used by the polymer coating and the ceramic coating is aqueous slurry; the polymer coating at least comprises aqueous adhesive and polymer particles; the ceramic coating at least comprises aqueous adhesive and the inorganic nanoparticles. The invention further discloses a preparation method of the lithium battery diaphragm. The invention has the advantages as follows: the prepared lithium battery diaphragm is high in thermal safety and long in cycle life; environment pollution is low during preparation.
Description
Technical field
The present invention relates to lithium ion battery separator, especially relating to a kind of thermal safety can be high, service life cycle long, the polymer of water-based low in the pollution of the environment and the compound lithium battery diaphragm of inorganic nano-particle and preparation method thereof.
Background technology
Along with the rise of the universal and electric automobile market of 3C Product, increasing to the demand of lithium rechargeable battery.Barrier film is as the critical component of lithium ion battery, and its performance has determined interfacial structure, the internal resistance etc. of battery, directly affects the characteristic such as capacity, circulation and security performance of battery, and the barrier film of excellent performance has important effect to the combination property that improves battery.Therefore, the exploitation of high-performance barrier film has become the important directions of improving lithium battery performance, and especially the fail safe of barrier film becomes the emphasis that we pay close attention to.
The fail safe of lithium ion battery is the emphasis of always paying close attention in the industry, and the fail safe of barrier film is the most important thing wherein.This just requires barrier film to have excellent mechanical property, keeps the ability of shape at lower closed pore temperature and higher temperature.The primary employing polypropylene of lithium battery diaphragm and the polyethylene material of now extensive commercialization, along with people are more and more higher to lithium battery performance requirement, the barrier film thermal safety of simple these two kinds of materials and keep the ability of electrolyte to be difficult to meet the demands, other materials and polyolefinic high-performance composite diaphragm are prepared in research becomes the most important direction of current diagram modification.
Summary of the invention
For overcoming above-mentioned shortcoming, the invention provides a kind of thermal safety can be high, service life cycle long, polymer and the compound lithium battery diaphragm of inorganic nano-particle of water-based low in the pollution of the environment.
The object of the invention is to realize by following technical measures, the lithium battery diaphragm that a kind of polymer of water-based and inorganic nano-particle are compound, comprises polyolefin supporting layer, and described polyolefin supporting layer one side is polymer coating, and opposite side is ceramic coating; Described polymer coating and ceramic coating all adopt coating process compound, described polymer coating and ceramic coating coating sizing-agent used is all water paste, in described polymer coating, at least comprise Aqueous Adhesives and polymer particle, in described ceramic coating, at least comprise Aqueous Adhesives and inorganic nano-particle.
As a kind of optimal way, described polyolefin supporting layer is polyethylene porous membrane, polypropylene porous membrane; The thickness range of described polyolefin supporting layer is between 8 μ m-100 μ m, and porosity ranges is 30%-80%, and average pore size is between 0.01 μ m-10 μ m.
As a kind of optimal way, described polymer particle is that polytetrafluoroethylene, Kynoar, Kynoar-hexafluoropropylene copolymer, polyimides, polypropylene are fine, one or more in aramid fiber resin, preferably Kynoar or Kynoar-hexafluoropropylene copolymer; The particle size range of described polymer particle is 0.01 μ m-10 μ m, preferably 0.1 μ m-2 μ m; The mass fraction (wt%) that described polymer particle accounts for water-based PVDF coating slurry is 2%-40%.
As a kind of optimal way, described inorganic nano-particle is SiO
2, Al
2o
3, CaO, TiO
2, MgO, ZnO, SnO
2, ZrO
2in any one or multiple; The particle size range of described inorganic nano-particle is 0.01 μ m～10 μ m; Described inorganic nano-particle accounts for the mass fraction of water-based ceramic size.
The preparation method who the invention also discloses the compound lithium battery diaphragm of a kind of polymer of water-based and inorganic nano-particle, is divided into two large steps, and first polymerization coating, then carries out pottery at another side and be coated with, and concrete steps are as follows:
A) preparation of waterborne polymeric slurry and coating
A1: using deionized water as solvent, water-soluble gluing agent, surfactant, dispersant, thickener etc. are dissolved under normal temperature high-speed stirred to wiring solution-forming; Add polymer powder particle, high-speed stirred is even again, is made into water paste; In slurry, contain 0.1%～2% water soluble polymer thickener, 0.01%～2% aqueous dispersion, 0.01%～1% surfactant, 0.1%～5% Aqueous Adhesives, 5%～25% polymer powder particle, 67%～83% deionized water, above-mentioned is all mass fraction;
A2: adopt nick roller coat cloth, the water paste of a1 step preparation is coated to a surface of supporting layer barrier film, application rate is 5～100m/min;
A3: a2 is walked to the coat film obtaining through 30～100 DEG C of oven for drying;
B) preparation of water-based ceramic size and coating
B1: using deionized water as solvent, add at normal temperatures deionized water for stirring to dissolve water-soluble gluing agent, thickener, wiring solution-forming; Then in above-mentioned solution, add successively surfactant, aqueous dispersion and inorganic nano-particle, stir, be made into water paste; In slurry, contain 0.1%～2% thickener, 0.01%～2% aqueous dispersion, 0.01%～1% surfactant, 0.1%～5% Aqueous Adhesives, 5%～25% inorganic nano-particle, 67%～83% deionized water, above-mentioned is all mass fraction;
B2: adopt nick roller coat cloth, the water-based ceramic size of b1 step preparation is coated to another surface of supporting layer barrier film, application rate is 5～100m/min;
B3: b2 is walked to the coat film obtaining through 30～100 DEG C of oven for drying, obtain final composite membrane.
As a kind of optimal way, the thickness range of described supporting layer barrier film is at 8 μ m-100 μ m, and porosity ranges is 30%-80%, and average pore size is at 0.01 μ m-10 μ m.
As a kind of optimal way, described polymer powder particle is that polytetrafluoroethylene, Kynoar, Kynoar-hexafluoropropylene copolymer, polyimides, polypropylene are fine, one or more in aramid fiber resin; The particle size range of poly-described polymer powder particle is 0.01 μ m-10 μ m.
As a kind of optimal way, described inorganic nano-particle is SiO
2, Al
2o
3, CaO, TiO
2, MgO, ZnO, SnO
2, ZrO
2in any one or multiple; Particle size range is 0.01 μ m～10 μ m.
The present invention has the following advantages:
1) inorganic nano-particle coating has improved the thermal safety of barrier film, and composite diaphragm is placed 1 hour under the high temperature of 135 DEG C, and percent thermal shrinkage is less than 3%.
2) inorganic nano-particle coating has improved the wettability of electrolyte to barrier film, is convenient to the absorption of electrolyte; Organic filler is PVDF-HFP powder, can be swelling in electrolyte, there is the ability of good absorption and maintenance electrolyte, and there is higher conductivity, thereby make lithium battery there is good service life cycle.Meanwhile, make the battery plus-negative plate laminating that well bonds, improve battery core hardness and body hold facility.
3) coating sizing-agent solvent for use is water,, containing organic solvents such as acetone, DMF, NMP, can, to environment, can not endanger workman's health.As the product of suitability for industrialized production, make water greatly reduce production cost as solvent, make product more competitive.
Brief description of the drawings
Fig. 1 is the apparent shape appearance figure of the embodiment of the present invention 1 polymer coating;
Fig. 2 is the profile of embodiment of the present invention battery diaphragm.
Embodiment
Below the present invention is described in further detail.
The lithium battery diaphragm that the polymer of water-based and inorganic nano-particle are compound, with reference to figure 2, comprises polyolefin supporting layer 2, and described polyolefin supporting layer 2 one sides are polymer coating 1, and opposite side is ceramic coating 3; Described polymer coating 1 and ceramic coating 3 all adopt coating process compound, described polymer coating 1 and ceramic coating 3 coating sizing-agent used is all water paste, in described polymer coating 1, at least comprise Aqueous Adhesives and polymer particle, in described ceramic coating 3, at least comprise Aqueous Adhesives and inorganic nano-particle.
Preparation method, is divided into two large steps, and first polymerization coating, then carries out pottery coating at another side, and concrete steps are as follows:
A) preparation of waterborne polymeric slurry and coating
A1: using deionized water as solvent, water-soluble gluing agent, surfactant, dispersant, thickener etc. are dissolved under normal temperature high-speed stirred to wiring solution-forming; Add polymer powder particle, high-speed stirred is even again, is made into water paste; In slurry, contain 0.1%～2% water soluble polymer thickener, 0.01%～2% aqueous dispersion, 0.01%～1% surfactant, 0.1%～5% Aqueous Adhesives, 5%～25% polymer powder particle, 67%～83% deionized water, above-mentioned is all mass fraction;
A2: adopt nick roller coat cloth, the water paste of a1 step preparation is coated to a surface of supporting layer barrier film, application rate is 5～100m/min;
A3: a2 is walked to the coat film obtaining through 30～100 DEG C of oven for drying;
B) preparation of water-based ceramic size and coating
B1: using deionized water as solvent, add at normal temperatures deionized water for stirring to dissolve water-soluble gluing agent, thickener, wiring solution-forming; Then in above-mentioned solution, add successively surfactant, aqueous dispersion and inorganic nano-particle, stir, be made into water paste; In slurry, contain 0.1%～2% thickener, 0.01%～2% aqueous dispersion, 0.01%～1% surfactant, 0.1%～5% Aqueous Adhesives, 5%～25% inorganic nano-particle, 67%～83% deionized water, above-mentioned is all mass fraction;
B2: adopt nick roller coat cloth, the water-based ceramic size of b1 step preparation is coated to another surface of supporting layer barrier film, application rate is 5～100m/min;
B3: b2 is walked to the coat film obtaining through 30～100 DEG C of oven for drying, obtain final composite membrane.
The lithium battery diaphragm that the polymer of water-based of the present invention and inorganic nano-particle are compound, on the basis of previous technique scheme, polyolefin supporting layer is polyethylene porous membrane, polypropylene porous membrane; The thickness range of described polyolefin supporting layer is between 8 μ m-100 μ m, and porosity ranges is 30%-80%, and average pore size is between 0.01 μ m-10 μ m.
The lithium battery diaphragm that the polymer of water-based of the present invention and inorganic nano-particle are compound, on the basis of previous technique scheme, polymer particle is that polytetrafluoroethylene, Kynoar, Kynoar-hexafluoropropylene copolymer, polyimides, polypropylene are fine, one or more in aramid fiber resin, preferably Kynoar or Kynoar-hexafluoropropylene copolymer; The particle size range of described polymer particle is 0.01 μ m-10 μ m, preferably 0.1 μ m-2 μ m; The mass fraction (wt%) that described polymer particle accounts for water-based PVDF coating slurry is 2%-40%.
The lithium battery diaphragm that the polymer of water-based of the present invention and inorganic nano-particle are compound, on the basis of previous technique scheme, inorganic nano-particle is SiO
2, Al
2o
3, CaO, TiO
2, MgO, ZnO, SnO
2, ZrO
2in any one or multiple; The particle size range of described inorganic nano-particle is 0.01 μ m～10 μ m; Described inorganic nano-particle accounts for the mass fraction of water-based ceramic size.
Below in conjunction with specific embodiment and comparative example, such scheme is described further, in following examples and comparative example, selects the coating of nick version, but be not limited to this coating method, slit extrusion coated, the modes such as dip-coating, spraying can.
Embodiment 1
1) water-based PVDF slurry preparation
Polymer-coated layer is formed by water paste coating, weight proportion PVDF-HFP in slurry: deionized water=100: 500.First acrylic compounds adhesive and tackifier CMC are added in deionized water, stir 20min until dissolve completely with 300r/min at normal temperatures, wherein the weight proportion of acrylic compounds adhesive and CMC is respectively adhesive: PVDF-HFP=5: 100, CMC: PVDF-HFP=1: 100.Then in above-mentioned solution, add successively fluorocarbon surfactant, polyethylene of dispersing agent pyrrolidones (PVP) and PVDF-HFP powder, continue to stir 10min with 300r/min, finally under 5000r/min high speed, stir 5min, slurry has configured.Wherein fluorocarbon surfactant: PVDF-HFP=0.1: 100, PVP: PVDF-HFP=0.3: 100.PVDF-HFP weight average molecular weight is about 140,000, and particle diameter is 100-300nm.
2) ceramic size preparation
Weight proportion Al in slurry
2o
3: deionized water=100: 150.First PVA class adhesive and tackifier CMC are added in deionized water, stir 20min until dissolve completely with 300r/min at normal temperatures, wherein the weight proportion of PVA class adhesive and CMC is respectively adhesive: PVDF-HFP=4: 100, CMC: PVDF-HFP=1: 100.Then add Sodium Polyacrylate dispersant, continue to stir 10min with 300r/min, finally add Al2O3 powder, under 7000r/min high speed, stir 5min, slurry has configured.Wherein Sodium Polyacrylate: Al2O3=0.5: 100, Al
2o
3powder D
50=1.0 μ m.
3) implement coating
First carry out water-based PVDF coating, with nick roller coat cloth, application rate is 40m/min; Coating basement membrane is S company 16 μ dry method microporous polypropylene membranes, and porosity is 42%; Use three grades of baking ovens to dry, oven temperatures at different levels are respectively 50～57 DEG C, and 55～63 DEG C, 63～70 DEG C, the thickness of PVDF coating is 2 μ.Then carry out the coating of water-based ceramic size at basement membrane opposite side, coating speed is 20m/min, and other coating conditions are consistent with water-based PVDF coating, and the thickness of ceramic coating is 4 μ.
Fig. 1 is the apparent shape appearance figure of the present embodiment polymer coating.
Embodiment 2
1) water-based PVDF slurry preparation
Polymer-coated layer is formed by water paste coating, weight proportion PVDF-HFP in water paste: deionized water=100: 500.First adhesive PVA and tackifier CMC are added in deionized water, stir 20min until dissolve completely at normal temperatures with 300r/min, wherein the weight proportion of PVA and CMC is respectively PVA: PVDF-HFP=5: 100, CMC: PVDF-HFP=1: 100.Then in above-mentioned solution, add successively fluorocarbon surfactant, dispersant polyoxyethylene dioleate and PVDF-HFP powder, continue to stir 10min with 300r/min, finally under 5000r/min high speed, stir 5min, slurry has configured.Wherein fluorocarbon surfactant: PVDF-HFP=0.1: 100, polyoxyethylene dioleate: PVDF-HFP=0.3: 100.PVDF-HFP weight average molecular weight is about 140,000, and particle diameter is 100-300nm.
Other are with embodiment 1.
Comparative example 1
Basement membrane is selected S company 16 μ dry method microporous polypropylene membranes, and porosity is 42%, and slurry is selected water-based PVDF slurry in embodiment 1, adopts water-based PVDF coating process in embodiment 1, prepares the two-layer composite diaphragm of one side PVDF coating.
Comparative example 2
Basement membrane is selected S company 16 μ dry method microporous polypropylene membranes, and porosity is 42%, and slurry is selected water-based ceramic size in embodiment 1, adopts water-based pottery coating process in embodiment 1, prepares the two-layer compound barrier film of one side pottery coating.
Table 1
Barrier film percent thermal shrinkage method of testing: every kind of barrier film cuts 3 100mm × 100mm samples, measures MD direction length and is designated as L
0, sample is put into assigned temperature convection oven, take out later the length note L that measures MD direction at official hour, the computing formula of percent thermal shrinkage is as follows:
ΔL＝(L-L
0)/L
0×100％
Measure three sample percent thermal shrinkages, then average is the percent thermal shrinkage of this kind of barrier film.
Wherein MD is the draw direction of dry method simple tension barrier film.
The method of testing of pick up: intercepting barrier film size is 100mm × 100mm, soaks 1h in electrolyte; Surface electrolyte is dried in taking-up, weighs the amount of Electolyte-absorptive; Then the weight that calculates every square metre of barrier film Electolyte-absorptive, is pick up, and unit is g/m
2.
The barrier film of preparing according to embodiment 1, embodiment 2, comparative example 1 and comparative example 2 is the dependence test result of barrier film in table 1.Come as can be seen from Table 1, the thermal endurance that the embodiment of the present invention 1 has had, high pick up and make battery after with the stickiness of pole piece excellence, gather the advantage of ceramic coating membrane and polymer-coated barrier film, the fail safe of the very effective raising battery of energy.
More than that compound lithium battery diaphragm of polymer to water-based of the present invention and inorganic nano-particle and preparation method thereof is set forth; be used for helping to understand the present invention; but embodiments of the present invention are not restricted to the described embodiments; anyly do not deviate from the change done under the principle of the invention, modification, substitute, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (8)
1. the compound lithium battery diaphragm of the polymer of water-based and inorganic nano-particle, is characterized in that: comprise polyolefin supporting layer, described polyolefin supporting layer one side is polymer coating, and opposite side is ceramic coating; Described polymer coating and ceramic coating all adopt coating process compound, described polymer coating and ceramic coating coating sizing-agent used is all water paste, in described polymer coating, at least comprise Aqueous Adhesives and polymer particle, in described ceramic coating, at least comprise Aqueous Adhesives and inorganic nano-particle.
2. the compound lithium battery diaphragm of the polymer of water-based according to claim 1 and inorganic nano-particle, is characterized in that: described polyolefin supporting layer is polyethylene porous membrane, polypropylene porous membrane; The thickness range of described polyolefin supporting layer is between 8 μ m-100 μ m, and porosity ranges is 30%-80%, and average pore size is between 0.01 μ m-10 μ m.
3. the compound lithium battery diaphragm of the polymer of water-based according to claim 1 and inorganic nano-particle, is characterized in that: described polymer particle is that polytetrafluoroethylene, Kynoar, Kynoar-hexafluoropropylene copolymer, polyimides, polypropylene are fine, one or more in aramid fiber resin; The particle size range of described polymer particle is 0.01 μ m-10 μ m; The mass fraction that described polymer particle accounts for water-based PVDF coating slurry is 2%-40%.
4. the compound lithium battery diaphragm of the polymer of water-based according to claim 1 and inorganic nano-particle, is characterized in that: described inorganic nano-particle is SiO
2, Al
2o
3, CaO, TiO
2, MgO, ZnO, SnO
2, ZrO
2in any one or multiple; The particle size range of described inorganic nano-particle is 0.01 μ m～10 μ m; Described inorganic nano-particle accounts for the mass fraction of water-based ceramic size.
5. a preparation method for the compound lithium battery diaphragm of the polymer of water-based and inorganic nano-particle, is characterized in that comprising the steps:
A) preparation of waterborne polymeric slurry and coating
A1: using deionized water as solvent, water-soluble gluing agent, surfactant, dispersant, thickener etc. are dissolved under normal temperature high-speed stirred to wiring solution-forming; Add polymer powder particle, high-speed stirred is even again, is made into water paste; In slurry, contain 0.1%～2% water soluble polymer thickener, 0.01%～2% aqueous dispersion, 0.01%～1% surfactant, 0.1%～5% Aqueous Adhesives, 5%～25% polymer powder particle, 67%～83% deionized water, above-mentioned is all mass fraction;
A2: adopt nick roller coat cloth, the water paste of a1 step preparation is coated to a surface of supporting layer barrier film, application rate is 5～100m/min;
A3: a2 is walked to the coat film obtaining through 30～100 DEG C of oven for drying;
B) preparation of water-based ceramic size and coating
B1: using deionized water as solvent, add at normal temperatures deionized water for stirring to dissolve water-soluble gluing agent, thickener, wiring solution-forming; Then in above-mentioned solution, add successively surfactant, aqueous dispersion and ceramic powders, stir, be made into water paste; In slurry, contain 0.1%～2% thickener, 0.01%～2% aqueous dispersion, 0.01%～1% surfactant, 0.1%～5% Aqueous Adhesives, 5%～25% inorganic nano-particle, 67%～83% deionized water, above-mentioned is all mass fraction;
B2: adopt nick roller coat cloth, the water-based ceramic size of b1 step preparation is coated to another surface of supporting layer barrier film, application rate is 5～100m/min;
B3: b2 is walked to the coat film obtaining through 30～100 DEG C of oven for drying, obtain final composite membrane.
6. the preparation method of the compound lithium battery diaphragm of the polymer of water-based according to claim 5 and inorganic nano-particle, it is characterized in that: the thickness range of described supporting layer barrier film is at 8 μ m-100 μ m, porosity ranges is 30%-80%, and average pore size is at 0.01 μ m-10 μ m.
7. the preparation method of the compound lithium battery diaphragm of the polymer of water-based according to claim 5 and inorganic nano-particle, is characterized in that: described polymer powder particle is that polytetrafluoroethylene, Kynoar, Kynoar-hexafluoropropylene copolymer, polyimides, polypropylene are fine, one or more in aramid fiber resin; The particle size range of poly-described polymer powder particle is 0.01 μ m-10 μ m.
8. the preparation method of the compound lithium battery diaphragm of the polymer of water-based according to claim 5 and inorganic nano-particle, is characterized in that: described inorganic nano-particle is SiO
2, Al
2o
3, CaO, TiO
2, MgO, ZnO, SnO
2, ZrO
2in any one or multiple; Particle size range is 0.01 μ m～10 μ m.
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| CN201410445320.8A CN104157818A (en) | 2014-09-02 | 2014-09-02 | Lithium battery diaphragm compounded from aqueous polymer and inorganic nanoparticles and preparation method thereof |
| PCT/CN2015/084120 WO2016034019A1 (en) | 2014-09-02 | 2015-07-15 | Aqueous polymer and inorganic nanoparticle composite lithium battery separator and preparation method thereof |
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|---|---|---|---|
| CN201410445320.8A CN104157818A (en) | 2014-09-02 | 2014-09-02 | Lithium battery diaphragm compounded from aqueous polymer and inorganic nanoparticles and preparation method thereof |
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| WO (1) | WO2016034019A1 (en) |
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Application publication date: 20141119 |