CN104157819A - Ceramic-gel polymer multilayer composite lithium battery diaphragm and preparation method thereof - Google Patents

Ceramic-gel polymer multilayer composite lithium battery diaphragm and preparation method thereof Download PDF

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Publication number
CN104157819A
CN104157819A CN201410445356.6A CN201410445356A CN104157819A CN 104157819 A CN104157819 A CN 104157819A CN 201410445356 A CN201410445356 A CN 201410445356A CN 104157819 A CN104157819 A CN 104157819A
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diaphragm
lithium battery
ceramic
water
multilayer composite
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吴术球
杨佳富
苗发成
何方波
陈秀峰
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Shenzhen Senior Technology Material Co Ltd
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Shenzhen Senior Technology Material Co Ltd
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Priority to CN201410445356.6A priority Critical patent/CN104157819A/en
Publication of CN104157819A publication Critical patent/CN104157819A/en
Priority to PCT/CN2015/084122 priority patent/WO2016034020A1/en
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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
    • 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
    • H01M50/409—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
    • H01M50/409—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
    • H01M50/491—Porosity
    • 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
    • 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)

Abstract

The invention discloses a preparation method of a ceramic-gel polymer multilayer composite lithium battery diaphragm. The preparation method comprises the following steps: 1, preparing aqueous PVDF (polyvinylidene fluoride) slurry and aqueous ceramic slurry; 2, thermally compounding a polypropylene diaphragm and a polyethylene diaphragm at 50-100 DEG C to obtain PP/ PE (polypropylene/ polyethylene) composite diaphragm; 3, with the PP/ PE composite diaphragm obtained in the step 2 as a coating substrate, coating the aqueous slurry prepared in the step 1 onto the PE surface of the substrate: coating the aqueous ceramic slurry to form a ceramic layer first and then coating the aqueous PVDF slurry to form a gel polymer layer, with the coating speed of 5-100m/min, and drying in a drying box with the temperature of 30-100 DEG C to obtain a final four-layer composite diaphragm. The invention further discloses a ceramic-gel polymer multilayer composite lithium battery diaphragm prepared by the preparation method. The prepared ceramic-gel polymer multilayer composite lithium battery diaphragm has the advantages of high thermal safety and high capability of keeping electrolyte.

Description

Lithium battery diaphragm of pottery and gelatin polymer MULTILAYER COMPOSITE and preparation method thereof
Technical field
The present invention relates to lithium ion battery separator, especially relate to a kind of thermal safety high and keep pottery that the ability of electrolyte is strong and lithium battery diaphragm of gelatin polymer MULTILAYER COMPOSITE and preparation method thereof.
Background technology
As the barrier film of one of lithium battery four large materials, although do not participate in the electrochemical reaction in battery, but the interior layer assembly of key in lithium battery.The key performances such as capacity, cycle performance and the charging and discharging currents density of battery all have direct relation with barrier film, and the improvement of membrane properties plays an important role to the combination property that improves lithium battery.In lithium battery, after barrier film Electolyte-absorptive, can isolate positive and negative electrode, to prevent short circuit, but also to allow the conduction of lithium ion simultaneously.And in the time overcharging or temperature raises, barrier film also will have the self-closing performance of high temperature, to intercept electric current conduction prevent exploding.Moreover, lithium battery diaphragm also to have that intensity is high, fire prevention, chemical-resistant reagent, acid-alkali-corrosive-resisting, good biocompatibility, the feature such as nontoxic.
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, lower closed pore temperature and keep the ability of shape at 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 of preparing high and keep the method for the lithium battery diaphragm of pottery that the ability of electrolyte is strong and gelatin polymer MULTILAYER COMPOSITE
The object of the invention is to realize by following technical measures, the preparation method of the lithium battery diaphragm of a kind of pottery and gelatin polymer MULTILAYER COMPOSITE, comprises the steps:
Step 1: configuration water-based PVDF slurry and water-based ceramic size;
Step 2: polypropylene diaphragm and polyethylene barrier film are compound, by compound to one deck polypropylene diaphragm and layer of polyethylene barrier film heat at 50～100 DEG C, obtains PP/PE composite diaphragm;
Step 3: coating, in step 2, obtain PP/PE composite diaphragm as coated substrate, be coated on the PE face of base material preparing water paste in step 1, first be coated with after fabric aqueous ceramic size forms ceramic layer and be coated with again fabric aqueous PVDF slurry formation gel polymer layer, application rate is 5～100m/min, through 30～100 DEG C of oven for drying, obtain final four layers of composite diaphragm.Wherein in PE face coating, be because easily modification at high temperature of PE layer mainly plays hot closing function in composite diaphragm.Be conducive to like this improve in the time making battery, apply barrier film dry linting phenomenon.(1) vistanex, lubricant and other additives are stirred by stir mixing machine, obtain mixture;
As a kind of optimal way, in described step 1, water-based PVDF slurry preparation method is:
Using deionized water as solvent, add deionized water for stirring to dissolve at normal temperature water-soluble gluing agent, surfactant, dispersant, thickener, wiring solution-forming; Add again polymer powder particle, stir, be 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; The weight average molecular weight of polymer powder particle is 12-16 ten thousand, and particle diameter is 100-300nm.
As a kind of optimal way, in described step 1, water-based ceramic size compound method is:
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% ceramic powders particle, 67%～83% deionized water, above-mentioned is all mass fraction.
As a kind of optimal way, the thickness range of described polypropylene porous membrane 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 ceramic powders 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 invention also discloses pottery prepared by a kind of said method and the lithium battery diaphragm of gelatin polymer MULTILAYER COMPOSITE, comprise the polypropylene supporting layer, polyethylene insulating course, ceramic coating layer and the polymer-coated layer that stack gradually.
As a kind of optimal way, the thickness range of described polypropylene supporting layer 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, the thickness of described polyethylene insulating course is 7 μ m～30 μ m, and porosity is 30%～60%; In the time that temperature is greater than 125 DEG C, the bore closure of PE layer.
As a kind of optimal way, the thickness of described ceramic coating layer and polymer-coated layer is 1 μ m-10 μ m altogether.
The present invention has the following advantages:
1) inorganic particulate 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 particulate 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) the PE layer in composite diaphragm has lower melt temperature, makes composite diaphragm have lower closed pore temperature, can effectively prevent the thermal runaway of lithium battery under abnormal conditions, and the fail safe of high lithium battery is provided.
4) 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;
Fig. 3 is the embodiment of the present invention and comparative example closed pore broken film temperature curve chart.
Embodiment
Below the present invention is described in further detail.
A lithium battery diaphragm for pottery and gelatin polymer MULTILAYER COMPOSITE, with reference to figure 2, comprises the polypropylene supporting layer 1, polyethylene insulating course 2, ceramic coating layer 3 and the polymer-coated layer 4 that stack gradually.Its preparation method comprises the steps:
Step 1: configuration water-based PVDF slurry and water-based ceramic size;
Step 2: polypropylene diaphragm and polyethylene barrier film are compound, by compound to one deck polypropylene diaphragm and layer of polyethylene barrier film heat at 50～100 DEG C, obtains PP/PE composite diaphragm;
Step 3: coating, in step 2, obtain PP/PE composite diaphragm as coated substrate, be coated on the PE face of base material preparing water paste in step 1, first be coated with after fabric aqueous ceramic size forms ceramic layer and be coated with again fabric aqueous PVDF slurry formation gel polymer layer, application rate is 5～100m/min, through 30～100 DEG C of oven for drying, obtain final four layers of composite diaphragm.Wherein in PE face coating, be because easily modification at high temperature of PE layer mainly plays hot closing function in composite diaphragm.Be conducive to like this improve in the time making battery, apply barrier film dry linting phenomenon.(1) vistanex, lubricant and other additives are stirred by stir mixing machine, obtain mixture;
The preparation method of the lithium battery diaphragm of pottery of the present invention and gelatin polymer MULTILAYER COMPOSITE, on the basis of previous technique scheme, in step 1, water-based PVDF slurry preparation method is:
Using deionized water as solvent, add deionized water for stirring to dissolve at normal temperature water-soluble gluing agent, surfactant, dispersant, thickener, wiring solution-forming; Add again polymer powder particle, stir, be 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; The weight average molecular weight of polymer powder particle is 12-16 ten thousand, and particle diameter is 100-300nm.
The preparation method of the lithium battery diaphragm of pottery of the present invention and gelatin polymer MULTILAYER COMPOSITE, on the basis of previous technique scheme, in step 1, water-based ceramic size compound method is:
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% ceramic powders particle, 67%～83% deionized water, above-mentioned is all mass fraction.
The preparation method of the lithium battery diaphragm of pottery of the present invention and gelatin polymer MULTILAYER COMPOSITE, on the basis of previous technique scheme, the thickness range of polypropylene porous membrane 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.
The preparation method of the lithium battery diaphragm of pottery of the present invention and gelatin polymer MULTILAYER COMPOSITE, on the basis of previous technique scheme, polymer powder 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 poly-described polymer powder particle is 0.01 μ m-10 μ m,, preferably 0.1 μ m-2 μ m.
The preparation method of the lithium battery diaphragm of pottery of the present invention and gelatin polymer MULTILAYER COMPOSITE, on the basis of previous technique scheme, ceramic powders particle is SiO 2, Al 2o 3, CaO, TiO 2, MgO, ZnO, SnO 2, ZrO 2in any one or multiple, preferably SiO 2and Al 2o 3; Particle size range is 0.01 μ m～10 μ m, preferably 0.1 μ m～3 μ m.
The preparation method of the lithium battery diaphragm of pottery of the present invention and gelatin polymer MULTILAYER COMPOSITE, on the basis of previous technique scheme, the thickness range of propylene porous membrane 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.This layer is supporting layer in composite diaphragm, and heat resistance is better than PE layer.
The preparation method of the lithium battery diaphragm of pottery of the present invention and gelatin polymer MULTILAYER COMPOSITE, on the basis of previous technique scheme, the thickness of polyethene microporous membrane is 7 μ m～30 μ m, porosity is 30%～60%.When temperature higher (being greater than 125 DEG C), the hole of PE layer is slowly closed, and this layer mainly plays the effect that heat is closed in composite membrane, prevents thermal runaway, improves the fail safe of lithium battery.
The preparation method of the lithium battery diaphragm of pottery of the present invention and gelatin polymer MULTILAYER COMPOSITE, on the basis of previous technique scheme, the thickness of ceramic coating layer and polymer-coated layer is 1 μ m-10 μ m, preferably 1 μ m～4 μ m altogether.
Below in conjunction with specific embodiment and comparative example, such scheme is described further, in following examples and comparative example, polypropylene diaphragm adopts S company dry method simple tension film, thickness 16 μ, and porosity is 42%.Polyethylene barrier film adopts S company wet method barrier film, thickness 12 μ, porosity 44%.Two kinds of barrier films are carried out to heat at 80 DEG C compound, obtain PE/PP composite diaphragm, as the base material of preparing coat film.In embodiment and comparative example, select 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
The preparation of water-based PVDF slurry
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 Al2O3 in slurry: 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, Al2O3 powder D50=1.0 μ m.
3) implement coating
First carry out the coating of water-based ceramic size, with nick roller coat cloth, application rate is 20m/min; 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, three layers of composite diaphragm of PP/PE/ ceramic layer by the time, wherein the thickness of ceramic coating is 4 μ.And then taking above-mentioned three layers of composite diaphragm as base material, on ceramic layer, be coated with one deck water-based PVDF coating, and coating layer thickness is 2 μ, and coating speed is 20m/min, and baking process is the same, finally obtains four layers of composite diaphragm of PP/PE/ ceramic layer/PVDF layer.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 other coating process conditions, with embodiment 1, finally make three layers of composite diaphragm of PP/ ceramic layer/PVDF layer.
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.
Comparative example 3
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.
Table 1
Barrier film percent thermal shrinkage method of testing: every kind of barrier film cuts 3 100mm × 100mm samples, measure MD direction length and be designated as L0, 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-L0)/L0×100％
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 and comparative example 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 and 2 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.
Table 2 is the closed pore broken film temperature of sample segment.
Diaphragm closed pore broken film temperature method of testing: adopt from molding jig, prepare an easy lithium battery, the two poles of the earth link internal resistance instrument, there is temperature probe inside.This simple and easy battery is put into 250 DEG C of insulating boxs, record the variation relation of the internal resistance of cell and internal temperature.First temperature flex point is diaphragm closed pore temperature, and second broken film temperature that temperature flex point is barrier film, refers to Fig. 3.
Associative list 2 and Fig. 3 can find out, and embodiment 1 sample with PE layer has lower closed pore temperature with respect to comparative example, can effectively prevent the thermal runaway of lithium battery under abnormal conditions, and the fail safe of high lithium battery is provided.
More than that lithium battery diaphragm to the present invention's pottery and gelatin polymer MULTILAYER COMPOSITE 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 (10)

1. a preparation method for the lithium battery diaphragm of pottery and gelatin polymer MULTILAYER COMPOSITE, is characterized in that comprising the steps:
Step 1: configuration water-based PVDF slurry and water-based ceramic size;
Step 2: polypropylene diaphragm and polyethylene barrier film are compound, by compound to one deck polypropylene diaphragm and layer of polyethylene barrier film heat at 50～100 DEG C, obtains PP/PE composite diaphragm;
Step 3: coating, in step 2, obtain PP/PE composite diaphragm as coated substrate, be coated on the PE face of base material preparing water paste in step 1, first be coated with after fabric aqueous ceramic size forms ceramic layer and be coated with again fabric aqueous PVDF slurry formation gel polymer layer, application rate is 5～100m/min, through 30～100 DEG C of oven for drying, obtain final four layers of composite diaphragm.
2. the preparation method of the lithium battery diaphragm of pottery according to claim 1 and gelatin polymer MULTILAYER COMPOSITE, is characterized in that: in described step 1, water-based PVDF slurry preparation method is:
Using deionized water as solvent, add deionized water for stirring to dissolve at normal temperature water-soluble gluing agent, surfactant, dispersant, thickener, wiring solution-forming; Add again polymer powder particle, stir, be 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; The weight average molecular weight of polymer powder particle is 12-16 ten thousand, and particle diameter is 100-300nm.
3. the preparation method of the lithium battery diaphragm of pottery according to claim 1 and gelatin polymer MULTILAYER COMPOSITE, is characterized in that: in described step 1, water-based ceramic size compound method is:
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% ceramic powders particle, 67%～83% deionized water, above-mentioned is all mass fraction.
4. the preparation method of the lithium battery diaphragm of pottery according to claim 1 and gelatin polymer MULTILAYER COMPOSITE, it is characterized in that: the thickness range of described polypropylene porous membrane 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.
5. the preparation method of the lithium battery diaphragm of pottery according to claim 2 and gelatin polymer MULTILAYER COMPOSITE, 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.
6. the preparation method of the lithium battery diaphragm of pottery according to claim 3 and gelatin polymer MULTILAYER COMPOSITE, is characterized in that: described ceramic powders 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.
7. a lithium battery diaphragm for pottery and gelatin polymer MULTILAYER COMPOSITE, is characterized in that: comprise the polypropylene supporting layer, polyethylene insulating course, ceramic coating layer and the polymer-coated layer that stack gradually.
8. the lithium battery diaphragm of pottery according to claim 7 and gelatin polymer MULTILAYER COMPOSITE, is characterized in that: the thickness range of described polypropylene supporting layer 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.
9. the lithium battery diaphragm of pottery according to claim 7 and gelatin polymer MULTILAYER COMPOSITE, is characterized in that: the thickness of described polyethylene insulating course is 7 μ m～30 μ m, and porosity is 30%～60%; In the time that temperature is greater than 125 DEG C, the bore closure of PE layer.
10. the lithium battery diaphragm of pottery according to claim 7 and gelatin polymer MULTILAYER COMPOSITE, is characterized in that: the thickness of described ceramic coating layer and polymer-coated layer is 1 μ m-10 μ m altogether.
CN201410445356.6A 2014-09-02 2014-09-02 Ceramic-gel polymer multilayer composite lithium battery diaphragm and preparation method thereof Pending CN104157819A (en)

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CN114142160B (en) * 2021-11-27 2023-07-28 上海比杰科技有限公司 Nano ceramic-polypropylene composite battery diaphragm and preparation method thereof
CN115312967A (en) * 2022-08-19 2022-11-08 南木纳米科技(北京)有限公司 Multilayer structure composite diaphragm and preparation method and application thereof

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Application publication date: 20141119