CN103474609B - A kind of folded painting composite lithium battery membrane - Google Patents
A kind of folded painting composite lithium battery membrane Download PDFInfo
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- CN103474609B CN103474609B CN201310450186.6A CN201310450186A CN103474609B CN 103474609 B CN103474609 B CN 103474609B CN 201310450186 A CN201310450186 A CN 201310450186A CN 103474609 B CN103474609 B CN 103474609B
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Abstract
The invention discloses a kind of folded painting composite lithium battery membrane and preparation method thereof, folded painting composite lithium battery membrane, be compounded with grafting PTFE microporous film layers and ceramic coating all successively in the upper and lower surface of grafting PE microporous film layers, the thick of ceramic coating is 0.001 ~ 7 μm; The thick of grafting PTFE microporous film layers is 1 ~ 10 μm; The thick of grafting PE microporous film layers is 5 ~ 25 μm.Prepared by barrier film, comprise the following steps that order connects: the upper and lower surface of grafting PE microporous barrier is all stacked grafting PTFE microporous barrier, and hot pressing makes them be complex as a whole, obtain original membrane, hot pressing temperature is 100 ~ 350 DEG C, and pressure is 0.3 ~ 6kg, and linear velocity is 0.5 ~ 50 m/min; After original membrane being flooded in ceramic suspension liquid, dry, solidification, to obtain final product; Gained barrier film being folded without breaking intensity is high, porosity is high, high temperature shutoff property is good.
Description
Technical field
The present invention relates to a kind of folded painting composite lithium battery membrane and preparation method thereof.
Background technology
Lithium battery has that specific energy is high, volume is little, lightweight, self discharge is few, long circulation life, the advantage such as pollution-free, obtain and apply more and more widely, market extends to the numerous areas such as cell phone, laptop computer, digital vedio recording, electric tool, electric bicycle, battery-operated motor cycle, electric motor car, energy storage, Aero-Space, military vehicle naval vessel, weapon, is the important component part of New Energy Industry.
Lithium ion battery is made up of positive and negative electrode material, electrolyte, barrier film and battery case.Barrier film, as " the 3rd pole " of battery, is one of layer assembly in the key in lithium ion battery.After barrier film Electolyte-absorptive, can positive and negative electrode be isolated, to prevent short circuit, allow the conduction of lithium ion simultaneously.When overcharging or temperature raises, barrier film intercepts electric current conduction by closed pore, prevents blast.The advantage of membrane properties determines interfacial structure and the internal resistance (lithium film thickness, thermal stability, porosity, Mecmullin number, mechanical strength) of battery, and then affect capacity, the cycle performance of battery, the key characteristics such as charging and discharging currents density, the barrier film of excellent performance plays an important role to the combination property improving battery.
The microporous barrier that current most of lithium ion battery separator adopts polyolefine material to manufacture, especially consumer lithium ion battery barrier film used.Because all trades and professions are to active demand that is high-power, high speed charging-discharging lithium ion battery, in use people recognize that this barrier film exists following defect gradually: promote that dendritic crystal precipitation easily punctures barrier film and causes short circuit; The degree of wetting of electrolyte is low thus cause lithium ion conducting rate low; Heat resistance is poor, and the high temperature often produced when excessive discharge and recharge makes barrier film shrink in a large number even to melt, cause the direct contact short circuit of electrode, thus initiation fire even explodes, the personnel that cause injure.Especially power lithium-ion battery, has higher requirement to the porosity of barrier film, electrolyte degree of wetting, heat resistance, mechanical property, and pure polyalkene diaphragm can not meet lithium battery and use and security needs.It constrains the development of lithium ion battery and relevant industries.
Summary of the invention
The object of this invention is to provide a kind of folded painting composite lithium battery membrane and preparation method thereof.
For solving the problems of the technologies described above, the technical solution adopted in the present invention is as follows:
A kind of folded painting composite lithium battery membrane, be compounded with grafting PTFE microporous film layers and ceramic coating all successively in the upper and lower surface of grafting PE microporous film layers, the thick of ceramic coating is 0.001 ~ 7 μm; The thick of grafting PTFE microporous film layers is 1 ~ 10 μm; The thick of grafting PE microporous film layers is 5 ~ 25 μm.
The blocked up easy stripping of above-mentioned ceramic coating, crosses thin heat resistance bad.The function that above-mentioned ceramic coating has close electrolyte, stops dendrite to generate.
Above-mentioned folded painting composite lithium battery membrane being folded without breaking intensity is high, porosity is high, electrolyte degree of wetting is high, high temperature resistant, Heat stability is good, internal resistance is low, mechanical strength good, stop dendrite generations, long service life, high temperature shutoff property is good, electrolyte permeability rate is high, can be used for dynamic lithium battery.
Described folded painting composite lithium battery membrane total thickness is 7.002 ~ 59 μm; The porosity of grafting PTFE microporous film layers is 40 ~ 80%, and aperture is 0.1 ~ 2 μm; The porosity of grafting PE microporous film layers is 30 ~ 45%, and aperture is 0.01 ~ 0.5 μm.Like this while saving material, can further improve high temperature shutoff property and the electrolyte permeability rate of barrier film.
The preparation method of above-mentioned folded painting composite lithium battery membrane, comprises the following steps that order connects:
A, the upper and lower surface of grafting PE microporous barrier is all stacked grafting PTFE microporous barrier, and hot pressing makes them be complex as a whole, and obtains original membrane, hot pressing temperature is 100 ~ 350 DEG C, and pressure is 0.3 ~ 6kg, and linear velocity is 0.5 ~ 50 m/min;
B, original membrane is flooded in ceramic suspension liquid after, dry, solidification, to obtain final product; Wherein, kiln temperatures is 50 ~ 200 DEG C, and curing temperature is 70 ~ 400 DEG C;
Comprise in ceramic suspension liquid: nanometer scale ceramics particle 10-70 part, polymeric binder 5 ~ 10 parts, increases attached dose 1 ~ 3 part, crosslinking agent 0.1 ~ 0.7 part, solvent 13.95 ~ 43.05 parts, light trigger 0.4 ~ 0.85 part, catalyst 0.15 ~ 0.6 part, 0.3 ~ 0.9 part, curing agent;
The diameter of nanometer scale ceramics particle is 1 ~ 400nm, and ceramic particle contains the inorganic nanoparticles such as Al2O3, TiO2, SiO2 or ZrO2;
Being prepared as of ceramic suspension liquid: by polymeric binder, increase attached dose, crosslinked, the airtight uniform stirring of solvent, light trigger, catalyst and curing agent is after 1 ~ 10 hour, add nanometer scale ceramics particle gradually, after reinforced, airtight stirring 4 ~ 24 hours, defoam, cross 1100-1300 order stainless steel dusting cover, to obtain final product.
Tension force≤the 6kg of above-mentioned original membrane, preferably≤4kg, more preferably≤3kg.
Above-mentioned nanometer scale ceramics particle diameter is too little, then heat resistance declines, and particle diameter is too large, and ceramic coating becomes fragile.In ceramic solution, meter level ceramic particle content is too low, then coating is thin or show-through, can not play good heatproof effect, if too high levels, coating is easily peeled off and become fragile.
In step B, scrape off unnecessary solution and by the press polish of film two sides after dipping, dry run is also the process of the solvent dried in striping.In step B, roller coat, blade coating, block printing, spraying, vapour deposition isotype can be also adopted ceramic solution to be coated in the upper and lower surface of original membrane, then dry at 50 ~ 200 DEG C, ultraviolet curing at 70 ~ 400 DEG C, the speed of a motor vehicle is 1 ~ 30 m/min, and furnace superintendent is 3 ~ 60 meters.
In steps A, during hot pressing, upper and lower hot-rolling hot pressing can be adopted, grafting PE microporous barrier passes in the middle of upper and lower hot-rolling, two-layer grafting PTFE microporous barrier crosses with grafting PE microporous barrier after preheating respectively on upper and lower hot-rolling, and by upper and lower hot-rolling hot pressing, trilamellar membrane is complex as a whole, cornerite >=180 DEG C of grafting PTFE microporous barrier and upper and lower hot-rolling, object carries out preheating, the speed of hot-rolling, the gap of hot-rolling, the temperature of hot-rolling all needs precise hard_drawn tuhes, thus it is high and do not destroy the physical property object of two kinds of films to reach compound fastness, wherein, the gap of hot-rolling is 6.85 ~ 58.5 μm, specifically can determine according to the thickness of stack membrane.
Adopt that the barrier film porosity of above-mentioned preparation method's gained is high, electrolyte degree of wetting is high, high temperature resistant, Heat stability is good, internal resistance is low, mechanical strength good, stop dendrite generations, long service life, high temperature shutoff property is good, electrolyte permeability rate is high, can be used for dynamic lithium battery.
In steps A, being prepared as of grafting PE microporous barrier: first to raw material graft modification, percent grafting is 0.8 ~ 3%, then by wet method bi-directional synchronization stretching film forming or dry method simple tension film forming, to obtain final product; Gained grafting PE micropore thickness is 5 ~ 25 μm, and porosity is 30 ~ 45%, and aperture is 0.01 ~ 0.5 μm;
Graft modification is gas phase graft, light-initiated grafting, high-temperature hot grafting, Suspension Graft, heterogeneous grafting, solution graft copolymerization, fusion-grafting, radiation grafting, solid phase grafting or solid state mechanochemistry grafting;
The monomer of grafting is vinyl silanes, acrylicacidandesters class, methacrylic acid and ester class, acrylonitrile, styrene and homologue thereof, glycidyl methacrylate, maleic anhydride or fumaric acid.
Said method can not only increase the compound fastness of grafting PE microporous barrier and other materials, and can increase the degree of wetting of electrolyte to barrier film.
In steps A, being prepared as of grafting PTFE microporous barrier: first by two-way for raw material asynchronous stretching film forming, and then to film graft modification, obtaining final product, percent grafting is 0.3 ~ 2%; Grafting PTFE micropore thickness is 1 ~ 10 μm, and porosity is 40 ~ 80%, and aperture is 0.1 ~ 2 μm;
Graft modification is low-temperature plasma graft method, radiation graft process or method of chemical treatment;
Grafted monomers is styrene sulfonic acid sodium salt, acrylic acid, propenyl, dimethylacetylamide, glycidyl methacrylate, polyethylene glycol, styrene, fumaric acid or methyl acrylic ester.
Above-mentioned low-temperature plasma graft method grafted monomers can be Sodium styrene sulfonate salt, acrylic acid, propenyl, dimethylacetylamide, glycidyl methacrylate or polyethylene glycol etc., radiation graft process grafted monomers can be styrene, fumaric acid or methyl acrylic ester etc., and method of chemical treatment can use naphthalene sodium tetrahydrofuran solution, the amalgam of alkali-metal or iron pentacarbonyl solution etc.
Said method can not only increase the compound fastness of grafting PTFE microporous barrier and other materials, and can increase the degree of wetting of electrolyte to barrier film further.
In step B, polymeric binder is the mixture of one or more any proportionings in polyvinylidene fluoride, PVDF-HFP, polyethylene glycol oxide, acrylate polymer, polyacrylic acid, polymethylacrylic acid, ethylene acrylic acid co polymer, methacrylic acid copolymer, butadiene propionic acid copolymer, butadiene methacrylic acid copolymer, polyvinyl sulfonate, chlorosulfonic acid polyethylene, perfluorosulfonate ionomer, Polystyrene Sulronate, styrene propionic acid copolymer or sulfonated butyl rubber; Increase the mixture that attached dose is one or more any proportionings in vinyltrimethoxy silane, vinyltriethoxysilane, aminopropyl trimethoxysilane, 3-glycidyl oxygen base trimethoxy silane, perfluorooctylethyl group trichlorosilane or ten trifluoro octyl group trimethoxy silanes; In step B, crosslinking agent is the mixture of one or more any proportionings in divinylbenzene, diacetate, triacrylate, tetraacrylate, dimethacrylate, trimethylamine hydrochloride acrylate, diallyl, triallyl, glycidol ether or polyethylene glycol dimethacrylate; Solvent is the mixture of one or more any proportionings in methyl pyrrolidone, acetone, ethanol water, normal propyl alcohol, isopropyl alcohol, n-butanol, cyclohexanol, diacetone alcohol, n-hexane, benzinum, cyclohexane, ether, dimethyl formamide, dimethylacetylamide, oxolane, dioxane, methyl-sulfoxide, benzene,toluene,xylene, dimethyl carbonate, ethyl acetate, chloroform, carrene or water.
The NM technology of the present invention is prior art.
The present invention is folded is coated with that composite lithium battery membrane being folded without breaking intensity is high, porosity is high, electrolyte degree of wetting is high, high temperature resistant, Heat stability is good, internal resistance is low, mechanical strength good, stop dendrite generations, long service life, high temperature shutoff property is good, electrolyte permeability rate is high, can be used for dynamic lithium battery; It is simple to operation that the present invention folds the preparation method being coated with composite lithium battery membrane.
Accompanying drawing explanation
Fig. 1 is the folded schematic diagram being coated with composite lithium battery membrane preparation method.
Fig. 2 is the folded structural representation being coated with composite lithium battery membrane.
In figure, 1 is grafting PE microporous barrier; 2 is hot-rolling top roll; 3 is hot-rolling lower roll; 4 is grafting PTFE microporous barrier; 5 is original membrane; 6 is ceramic solution; 7 is drying oven; 8 is curing oven; 9 are coated with composite lithium battery membrane for folded; 10 is PE microporous film layers, and 11 is grafting PTFE microporous film layers, and 12 is ceramic coating.
Embodiment
In order to understand the present invention better, illustrate content of the present invention further below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.
Embodiment 1
As shown in Figure 2, folded painting composite lithium battery membrane, is compounded with grafting PTFE microporous film layers and ceramic coating all successively in the upper and lower surface of grafting PE microporous film layers.
Preparation method: as shown in Figure 1, grafting PE, grafting PTFE film are stacked by the order of grafting PTFE/ grafting PE/ grafting PTFE, initiatively unreel, flatten, stack membrane plane strain is 0.85kg, heat roller temperature 320 DEG C, PTFE film is cornerite 180 ° on hot-rolling, hot-rolling pressure 2kg, linear velocity 5 ms/min, is superimposed together grafting PTFE/ grafting PE/ grafting PTFE hot pressing; Adopt dipping technique dual coating ceramic solution, strike off the solution that both sides are unnecessary, heated-air drying, temperature 120 DEG C, speed 5 ms/min; Hot blast solidification at 260 DEG C, Ultraviolet radiation, speed 5 ms/min, rolling film forming, cuts to be detected.
Being prepared as of ceramic solution: ceramic nanoparticles (Xuancheng Jingrui New Material Co., Ltd. VK-L30JY nano-aluminium oxide powder series of products, purity 99.99%, specific area 15 ~ 30m
2/ g) particle diameter 30nm, the percentage by weight accounting for ceramic solution is 20%, by water, ethanol, HCl(5% weight concentration), tetraethoxysilane, 3-aminopropyl triethoxysilane, 3-glycidyl oxygen base trimethoxy silane, methacryloxypropyl trimethoxy silane, PVDF-HFP solvent acetone dilution after solid content 25% binding agent in mass ratio for 20:3:2:2:2:1:1:5 mix, airtight stirring 3 hours, add ceramic nanoparticles gradually, airtight stirring 6 hours again, then cross 1200 order stainless steel dusting covers, foam-expelling, to obtain final product;
The preparation of grafting PE microporous barrier: by PE barrier film raw material maleic anhydride graft, percent grafting 0.9%, then wet method bi-directional synchronization draws film forming, thickness 20 μm, porosity 38%, aperture 300nm; The preparation of grafting PTFE microporous barrier: first by two-way for raw material asynchronous stretching film forming, and then acrylic graft-modified to film low temperature plasma, percent grafting 0.7%, thickness 5 μm, porosity 80%, 1 μm, aperture.The thick of ceramic coating is 1 μm.Other technology is all with reference to prior art.
Embodiment 2
Folded painting composite lithium battery membrane, is compounded with grafting PTFE microporous film layers and ceramic coating all successively in the upper and lower surface of grafting PE microporous film layers.
Preparation method: grafting PE, grafting PTFE film are stacked by the order of grafting PTFE/ grafting PE/ grafting PTFE, initiatively unreel, flatten, stack membrane plane strain is 0.5kg, heat roller temperature 310 DEG C, PTFE film is cornerite 180 ° on hot-rolling, hot-rolling pressure 2kg, linear velocity 5 ms/min, is superimposed together grafting PTFE/ grafting PE/ grafting PTFE hot pressing; Adopt dipping technique dual coating ceramic solution, strike off the solution that both sides are unnecessary, heated-air drying, temperature 120 DEG C, speed 5 ms/min; Hot blast solidification at 280 DEG C, Ultraviolet radiation, speed 5 ms/min, rolling film forming, cuts to be detected.
Being prepared as of ceramic solution: ceramic nanoparticles (Xuancheng Jingrui New Material Co., Ltd. VK-L50Y nano-aluminium oxide powder series of products, purity 99.99%, specific area 100 ~ 150m
2/ g) particle diameter 50nm, the percentage by weight accounting for ceramic solution is 30%, by water, ethanol, HNO3(5% weight concentration), tetraethoxysilane, 3-aminopropyl triethoxysilane, 3-glycidyl oxygen base trimethoxy silane, methacryloxypropyl trimethoxy silane, PVDF-HFP solvent acetone dilution after solid content 25% binding agent in mass ratio for 30:4:3:2:2:1:1:4 mix, airtight stirring 3 hours, add ceramic nanoparticles gradually, airtight stirring 6 hours again, then cross 1200 order stainless steel dusting covers, foam-expelling, to obtain final product;
The preparation of grafting PE microporous barrier: by PE barrier film raw material maleic anhydride graft, percent grafting 0.9%, then wet method bi-directional synchronization draws film forming, thickness 16 μm, porosity 38%, aperture 300nm; The preparation of grafting PTFE microporous barrier: first by two-way for raw material asynchronous stretching film forming, and then acrylic graft-modified to film low temperature plasma, percent grafting 0.7%, thickness 10 μm, porosity 80%, 0.3 μm, aperture.The thick of ceramic coating is 3 μm.Other technology is all with reference to prior art.
Embodiment 3
Folded painting composite lithium battery membrane, is compounded with grafting PTFE microporous film layers and ceramic coating all successively in the upper and lower surface of grafting PE microporous film layers.
Preparation method: grafting PE, grafting PTFE film are stacked by the order of grafting PTFE/ grafting PE/ grafting PTFE, initiatively unreel, flatten, tension force is 1kg, heat roller temperature 300 DEG C, PTFE film is cornerite 180 ° on hot-rolling, hot-rolling pressure 2kg, linear velocity 5 ms/min, is superimposed together grafting PTFE/ grafting PE/ grafting PTFE hot pressing; Adopt dipping technique dual coating ceramic solution, strike off the solution that both sides are unnecessary, heated-air drying, temperature 120 DEG C, speed 5 ms/min; Hot blast solidification at 300 DEG C, Ultraviolet radiation, speed 5 ms/min, rolling film forming, cuts to be detected.
Being prepared as of ceramic solution: ceramic nanoparticles (Xuancheng Jingrui New Material Co., Ltd. VK-L50Y nano-aluminium oxide powder series of products, purity 99.99%, specific area 100 ~ 150m
2/ g) particle diameter 50nm, the percentage by weight accounting for ceramic solution is 40%, by water, ethanol, HCl(5% weight concentration), tetraethoxysilane, 3-aminopropyl triethoxysilane, 3-glycidyl oxygen base trimethoxy silane, methacryloxypropyl trimethoxy silane, PVDF-HFP solvent acetone dilution after solid content 25% binding agent in mass ratio for 36:4:3:3:2:2:1:3 mix, airtight stirring 3 hours, add ceramic nanoparticles gradually, airtight stirring 6 hours again, then cross 1200 order stainless steel dusting covers, foam-expelling, to obtain final product;
The preparation of grafting PE microporous barrier: by PE barrier film raw material maleic anhydride graft, percent grafting 0.9%, then wet method bi-directional synchronization draws film forming, thickness 20 μm, porosity 38%, aperture 260nm; The preparation of grafting PTFE microporous barrier: first by two-way for raw material asynchronous stretching film forming, and then acrylic graft-modified to film low temperature plasma, percent grafting 0.7%, thickness 5 μm, porosity 80%, 0.6 μm, aperture.The thick of ceramic coating is 4 μm.Other technology is all with reference to prior art.
Embodiment 4
Folded painting composite lithium battery membrane, is compounded with grafting PTFE microporous film layers and ceramic coating all successively in the upper and lower surface of grafting PE microporous film layers.
Preparation method: grafting PE, grafting PTFE film are stacked by the order of grafting PTFE/ grafting PE/ grafting PTFE, initiatively unreel, flatten, tension force is 0.6kg, heat roller temperature 320 DEG C, PTFE film is cornerite 180 ° on hot-rolling, hot-rolling pressure 2kg, linear velocity 5 ms/min, is superimposed together grafting PTFE/ grafting PE/ grafting PTFE hot pressing; Adopt dipping technique dual coating ceramic solution, strike off the solution that both sides are unnecessary, heated-air drying, temperature 120 DEG C, speed 5 ms/min; Hot blast solidification at 260 DEG C, Ultraviolet radiation, speed 5 ms/min, rolling film forming, cuts to be detected.
Being prepared as of ceramic solution: ceramic nanoparticles (Xuancheng Jingrui New Material Co., Ltd. VK-L30JY nano-aluminium oxide powder series of products, purity 99.99%, specific area 15 ~ 30m
2/ g) particle diameter 30nm, the percentage by weight accounting for ceramic solution is 50%, by water, ethanol, HCl(5% weight concentration), tetraethoxysilane, 3-aminopropyl triethoxysilane, 3-glycidyl oxygen base trimethoxy silane, methacryloxypropyl trimethoxy silane, PVDF-HFP solvent acetone dilution after solid content 25% binding agent in mass ratio for 25:3.5:2.5:2.5:2:1:1:6 mix, airtight stirring 3 hours, add ceramic nanoparticles gradually, airtight stirring 6 hours again, then cross 1200 order stainless steel dusting covers, foam-expelling, to obtain final product;
The preparation of grafting PE microporous barrier: by PE barrier film raw material maleic anhydride graft, percent grafting 0.9%, then wet method bi-directional synchronization draws film forming, thickness 9 μm, porosity 38%, aperture 240nm; The preparation of grafting PTFE microporous barrier: first by two-way for raw material asynchronous stretching film forming, and then acrylic graft-modified to film low temperature plasma, percent grafting 0.7%, thickness 5 μm, porosity 80%, 1.2 μm, aperture.The thick of ceramic coating is 2 μm.Other technology is all with reference to prior art.
Can find in preparation process, the tension force of three layers of lamination process film is larger, and film is more wrinkling, affects the superimposed of film, and tension force is suitable≤1kg; The temperature of hot-rolling is higher, and larger on the impact of superimposed film, temperature is suitable≤and 320 DEG C; The tension force that stack membrane is less is convenient to the coating of ceramic solution, and higher baking temperature can improve the fastness of ceramic coating.The too high ceramic layer of ceramic content is blocked up, embrittlement, has obscission.
PE barrier film, PTFE microporous barrier are all ZhongCai Science membrane material Products, and the detection perform of the three layers of barrier film and embodiment 1 ~ 4 that are not coated with pottery in embodiment 4 compares as table 1.Temperature tolerance represents (120 DEG C, under 1 hour condition) with shrinkage, and Macmullin number (MacMullin number) refers to the ratio of the resistance after barrier film imbibition and bath resistance, has reacted the size of pick up, resistivity, has been worth the smaller the better.1. Macmullin number method of testing: barrier film to be immersed in lithium hexafluorophosphate electrolyte solution 1 hour, room temperature (25 DEG C), takes out and measures its resistance value, the resistance value of the electrolyte of measurement is done denominator, and the resistance value of leaching electrolyte barrier film does molecule, calculates its ratio; 2. closed pore temperature method of testing: be immersed in by barrier film in lithium hexafluorophosphate electrolyte solution, electrolyte of heating, releases corresponding closed pore temperature (maximum is completely closed) according to different temperature, different resistances.
Table 1
Claims (8)
1. a folded painting composite lithium battery membrane, it is characterized in that: be compounded with grafting PTFE microporous film layers and ceramic coating all successively in the upper and lower surface of grafting PE microporous film layers, the thick of ceramic coating is 0.001 ~ 7 μm; The thick of grafting PTFE microporous film layers is 1 ~ 10 μm; The thick of grafting PE microporous film layers is 5 ~ 25 μm;
The preparation method of above-mentioned folded painting composite lithium battery membrane, comprises the following steps that order connects:
A, the upper and lower surface of grafting PE microporous barrier is all stacked grafting PTFE microporous barrier, and hot pressing makes them be complex as a whole, and obtains original membrane, hot pressing temperature is 100 ~ 350 DEG C, and pressure is 0.3 ~ 6kg, and linear velocity is 0.5 ~ 50 m/min;
B, original membrane is flooded in ceramic suspension liquid after, dry, solidification, to obtain final product; Wherein, kiln temperatures is 50 ~ 200 DEG C, and curing temperature is 70 ~ 400 DEG C;
Comprise in ceramic suspension liquid: nanometer scale ceramics particle 10-70 part, polymeric binder 5 ~ 10 parts, increases attached dose 1 ~ 3 part, crosslinking agent 0.1 ~ 0.7 part, solvent 13.95 ~ 83.05 parts, light trigger 0.4 ~ 0.85 part, catalyst 0.15 ~ 0.6 part, 0.3 ~ 0.9 part, curing agent;
The diameter of nanometer scale ceramics particle is 1 ~ 400nm;
The preparation method of ceramic suspension liquid is: by polymeric binder, increase attached dose, crosslinking agent, solvent, light trigger, catalyst and the airtight uniform stirring of curing agent be after 1 ~ 10 hour, add nanometer scale ceramics particle gradually, after reinforced, airtight stirring 4 ~ 24 hours, defoam, cross 1100-1300 order stainless steel dusting cover, to obtain final product.
2. folded painting composite lithium battery membrane as claimed in claim 1, is characterized in that: described folded painting composite lithium battery membrane total thickness is 7.002 ~ 59 μm; The porosity of grafting PTFE microporous film layers is 40 ~ 80%, and aperture is 0.1 ~ 2 μm; The porosity of grafting PE microporous film layers is 30 ~ 45%, and aperture is 0.01 ~ 0.5 μm.
3. folded painting composite lithium battery membrane as claimed in claim 1 or 2, it is characterized in that: in steps A, being prepared as of grafting PE microporous barrier: first to raw material graft modification, percent grafting is 0.8 ~ 3%, then by wet method bi-directional synchronization stretching film forming or dry method simple tension film forming, to obtain final product; Gained grafting PE micropore thickness is 5 ~ 25 μm, and porosity is 30 ~ 45%, and aperture is 0.01 ~ 0.5 μm;
Graft modification is gas phase graft, light-initiated grafting, high-temperature hot grafting, Suspension Graft, heterogeneous grafting, solution graft copolymerization, fusion-grafting, radiation grafting, solid phase grafting or solid state mechanochemistry grafting;
The monomer of grafting is vinyl silanes, acrylicacidandesters class, methacrylic acid and ester class, acrylonitrile, styrene and homologue thereof, glycidyl methacrylate, maleic anhydride or fumaric acid.
4. folded painting composite lithium battery membrane as claimed in claim 1 or 2, is characterized in that: in steps A, being prepared as of grafting PTFE microporous barrier: first by two-way for raw material asynchronous stretching film forming, and then to film graft modification, obtaining final product, percent grafting is 0.3 ~ 2%; Grafting PTFE micropore thickness is 1 ~ 10 μm, and porosity is 40 ~ 80%, and aperture is 0.1 ~ 2 μm;
Graft modification is low-temperature plasma graft method, radiation graft process or method of chemical treatment;
Grafted monomers is styrene sulfonic acid sodium salt, acrylic acid, propenyl, dimethylacetylamide, glycidyl methacrylate, polyethylene glycol, styrene, fumaric acid or methyl acrylic ester.
5. folded painting composite lithium battery membrane as claimed in claim 1 or 2, it is characterized in that: in step B, polymeric binder is the mixture of one or more any proportionings in polyvinylidene fluoride, PVDF-HFP, polyethylene glycol oxide, acrylate polymer, polyacrylic acid, polymethylacrylic acid, ethylene acrylic acid co polymer, methacrylic acid copolymer, butadiene propionic acid copolymer, butadiene methacrylic acid copolymer, polyvinyl sulfonate, chlorosulfonic acid polyethylene, perfluorosulfonate ionomer, Polystyrene Sulronate, styrene propionic acid copolymer or sulfonated butyl rubber.
6. folded painting composite lithium battery membrane as claimed in claim 1 or 2, it is characterized in that: in step B, increase the attached dose of mixture for one or more any proportionings in vinyltrimethoxy silane, vinyltriethoxysilane, aminopropyl trimethoxysilane, 3-glycidyl oxygen base trimethoxy silane, perfluorooctylethyl group trichlorosilane or ten trifluoro octyl group trimethoxy silanes.
7. folded painting composite lithium battery membrane as claimed in claim 1 or 2, it is characterized in that: in step B, crosslinking agent is the mixture of one or more any proportionings in divinylbenzene, diacetate, triacrylate, tetraacrylate, dimethacrylate, trimethylamine hydrochloride acrylate, diallyl, triallyl, glycidol ether or polyethylene glycol dimethacrylate.
8. folded painting composite lithium battery membrane as claimed in claim 1 or 2, it is characterized in that: in step B, solvent is the mixture of one or more any proportionings in methyl pyrrolidone, acetone, ethanol water, normal propyl alcohol, isopropyl alcohol, n-butanol, cyclohexanol, diacetone alcohol, n-hexane, benzinum, cyclohexane, ether, dimethyl formamide, dimethylacetylamide, oxolane, dioxane, methyl-sulfoxide, benzene,toluene,xylene, dimethyl carbonate, ethyl acetate, chloroform, carrene or water.
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Effective date of registration: 20171227 Address after: Shandong province Zaozhuang River Road 277500 Tengzhou City Economic Development Zone No. 368 Patentee after: Zhong wood lithium film Co., Ltd. Address before: Jiangning District of Nanjing City, Jiangsu province 210012 Jiangning Science Park Tong Road No. 99 Patentee before: Zhongcai Science & Technology Co., Ltd. |