CN103474609A - Overlapped coating composite lithium battery diaphragm and preparation method thereof - Google Patents
Overlapped coating composite lithium battery diaphragm and preparation method thereof Download PDFInfo
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- CN103474609A CN103474609A CN2013104501866A CN201310450186A CN103474609A CN 103474609 A CN103474609 A CN 103474609A CN 2013104501866 A CN2013104501866 A CN 2013104501866A CN 201310450186 A CN201310450186 A CN 201310450186A CN 103474609 A CN103474609 A CN 103474609A
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Abstract
The invention discloses an overlapped coating composite lithium battery diaphragm and a preparation method of the overlapped coating composite lithium battery diaphragm. According to the overlapped coating composite lithium battery diaphragm, the upper surface and the lower surface of a graft PE microporous membrane layer are provided with a graft PTFE microporous membrane layer and a ceramic coating in a compounded mode respectively and sequentially, the thickness of the ceramic coating is 0.001-7 micrometers, the thickness of the graft PTFE microporous membrane layer is 1-10 micrometers, and the thickness of the graft PE microporous membrane layer is 5-25 micrometers. The preparation method of the overlapped coating composite lithium battery diaphragm comprises the following steps that the graft PTFE microporous membrane layers are overlapped on the upper surface and the lower surface of the graft PE microporous membrane layer respectively, then the graft PTFE microporous membrane layers and the graft PE microporous membrane layer are compounded together in a hot pressing mode to obtain an initial diaphragm, the hot pressing temperature is 100-350 DEG C, the pressure is 0.3-6 kg, and the linear velocity is 0.5-50 m/min; after the initial diaphragm is dipped into ceramic suspension liquid, the overlapped coating composite lithium battery diaphragm is obtained through drying and solidification; the obtained diaphragm is high in puncture-resistant strength, high in porosity and good in high-temperature turn-off performance.
Description
Technical field
The present invention relates to compound lithium battery diaphragm of a kind of folded painting 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, obtained application 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 comprised of positive and negative electrode material, electrolyte, barrier film and battery case.Barrier film, as " the 3rd utmost point " of battery, is one of layer assembly in the key in lithium ion battery.After the barrier film Electolyte-absorptive, can isolate positive and negative electrode, to prevent short circuit, allow the conduction of lithium ion simultaneously.Overcharging or temperature while raising, barrier film intercepts electric current conduction, prevent exploding by closed pore.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 that improves battery.
The microporous barrier that the most lithium ion battery separator adopts polyolefine material to manufacture, especially consumer lithium ion battery barrier film used.Due to all trades and professions, to active demand high-power, the high speed charging-discharging lithium ion battery, in use people recognize that there is following defect in this barrier film gradually: promote dendritic crystal to separate out easily to puncture barrier film to cause short circuit; Thereby the low lithium ion conducting rate that causes of the degree of wetting of electrolyte is low; Heat resistance is poor, and the high temperature often produced when excessively discharging and recharging melts a large amount of the contraction even of barrier film, causes the direct contact short circuit of electrode, thereby initiation fire even explodes, the personnel that cause injure.Especially power lithium-ion battery, have higher requirement to porosity, electrolyte degree of wetting, heat resistance, the mechanical property of barrier film, and pure polyalkene diaphragm can not meet lithium battery to be used and security needs.It has restricted the development of lithium ion battery and relevant industries.
Summary of the invention
The purpose of this invention is to provide compound lithium battery diaphragm of a kind of folded painting and preparation method thereof.
For solving the problems of the technologies described above, the technical solution adopted in the present invention is as follows:
The compound lithium battery diaphragm of a kind of folded painting, all be compounded with grafting PTFE microporous film layers and ceramic coating successively in the upper and lower surface of grafting PE microporous film layers, and the thick of ceramic coating is 0.001～7 μ m; The thick of grafting PTFE microporous film layers is 1～10 μ m; The thick of grafting PE microporous film layers is 5～25 μ m.
Above-mentioned ceramic coating is blocked up easily to be peeled off, and crosses thin heat resistance bad.The function that above-mentioned ceramic coating has close electrolyte, stops dendrite to generate.
The compound lithium battery diaphragm of above-mentioned folded painting is anti-pierces through that intensity is high, porosity is high, the electrolyte degree of wetting is high, high temperature resistant, Heat stability is good, internal resistance is low, mechanical strength good, stop the dendrite generation, long service life, high temperature turn-off that property is good, the electrolyte permeability rate is high, can be used for dynamic lithium battery.
The compound lithium battery diaphragm total thickness of described folded painting is 7.002～59 μ m; The porosity of grafting PTFE microporous film layers is 40～80%, and aperture is 0.1～2 μ m; The porosity of grafting PE microporous film layers is 30～45%, and aperture is 0.01～0.5 μ m.When saving material, can further improve high temperature shutoff property and the electrolyte permeability rate of barrier film like this.
The preparation method of the compound lithium battery diaphragm of above-mentioned folded painting comprises the following steps that order is joined:
A, the upper and lower surface of grafting PE microporous barrier is all stacked to grafting PTFE microporous barrier, and hot pressing is complex as a whole them, obtains original membrane, hot pressing temperature is 100～350 ℃, 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, solidify, obtain; Wherein, kiln temperatures is 50～200 ℃, and curing temperature is 70～400 ℃;
In ceramic suspension liquid, comprise: nanometer scale ceramics particle 10-70 part, 5～10 parts of polymeric binder, increase attached dose 1～3 part, 0.1～0.7 part of crosslinking agent, 13.95～43.05 parts of solvents, 0.4～0.85 part of light trigger, 0.15～0.6 part of catalyst, 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, solvent, light trigger, catalyst and the airtight uniform stirring of curing agent after 1～10 hour, add gradually the nanometer scale ceramics particle, after reinforced, airtight stirring 4～24 hours, defoam, cross 1100-1300 order stainless steel dusting cover, obtain.
Tension force≤the 6kg of above-mentioned original membrane, preferably≤4kg, more preferably≤3kg.
Above-mentioned nanometer scale ceramics particle diameter is too little, and heat resistance descends, and particle diameter is too large, and ceramic coating becomes fragile.In pottery solution, meter level ceramic particle content is too low, and coating is thin or show-through, can not play good heatproof effect, if too high levels coating are easily peeled off and become fragile.
In step B, scrape off unnecessary solution after dipping and by the press polish of film two sides, dry run is also the process of drying the solvent in striping.In step B, can also adopt roller coat, blade coating, block printing, spraying, vapour deposition isotype ceramic solution to be coated in to the upper and lower surface of original membrane, then dry under 50～200 ℃, 70～400 ℃ of lower ultraviolet curings, the speed of a motor vehicle is 1～30 m/min, and furnace superintendent is 3～60 meters.
In steps A, during hot pressing, can adopt upper and lower hot-rolling hot pressing, 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, the cornerite of grafting PTFE microporous barrier and upper and lower hot-rolling >=180 ℃, purpose is to carry out preheating, the speed of hot-rolling, the gap of hot-rolling, the temperature of hot-rolling all needs accurate control, thereby it is high and do not destroy the physical property purpose of two kinds of films to reach compound fastness, wherein, the gap of hot-rolling is 6.85～58.5 μ m, specifically can determine according to the thickness of stack membrane.
Adopt the barrier film porosity of above-mentioned preparation method's gained high, the electrolyte degree of wetting is high, high temperature resistant, Heat stability is good, internal resistance is low, mechanical strength good, stop the dendrite generation, long service life, high temperature turn-off that property is good, the 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 the 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, obtains; Gained grafting PE micropore thickness is 5～25 μ m, and porosity is 30～45%, and aperture is 0.01～0.5 μ m;
Graft modification is gas phase grafting, light-initiated grafting, high temperature hot joining branch, 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 the two-way asynchronous stretching film forming of raw material, and then, to the film graft modification, obtain, percent grafting is 0.3～2%; Grafting PTFE micropore thickness is 1～10 μ m, and porosity is 40～80%, and aperture is 0.1～2 μ m;
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., the radiation graft process grafted monomers can be styrene, fumaric acid or methyl acrylic ester etc., and method of chemical treatment can be used 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 further increase the degree of wetting of electrolyte to barrier film.
In step B, the mixture that polymeric binder is 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, perfluorinated sulfonic acid ionomer, Polystyrene Sulronate, styrene propionic acid copolymer or sulfonated butyl rubber; Increase the attached dose of mixture for one or more any proportionings in vinyltrimethoxy silane, vinyltriethoxysilane, aminopropyl trimethoxysilane, 3-glycidyl oxygen base trimethoxy silane, perfluoro capryl ethyl trichlorosilane or ten trifluoro octyl group trimethoxy silanes; In step B, the mixture that crosslinking agent is one or more any proportionings in divinylbenzene, diacetate, triacrylate, tetraacrylate, dimethacrylate, trimethylamine hydrochloride acrylate, diallyl, triallyl, glycidol ether or polyethylene glycol dimethacrylate; The mixture that solvent is 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 compound lithium battery diaphragm anti-ly pierces through that intensity is high, porosity is high, the electrolyte degree of wetting is high, high temperature resistant, Heat stability is good, internal resistance is low, mechanical strength good, stop the dendrite generation, long service life, high temperature turn-off that property is good, the electrolyte permeability rate is high, can be used for dynamic lithium battery; The preparation method of the compound lithium battery diaphragm of the folded painting of the present invention is simple to operation.
The accompanying drawing explanation
Fig. 1 is the folded schematic diagram that is coated with compound lithium battery diaphragm preparation method.
Fig. 2 is the folded structural representation that is coated with compound lithium battery diaphragm.
In figure, 1 is grafting PE microporous barrier; 2 is the hot-rolling top roll; 3 is the 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 is the compound lithium battery diaphragm of folded painting; 10 is the PE microporous film layers, and 11 is grafting PTFE microporous film layers, and 12 is ceramic coating.
Embodiment
In order to understand better the present invention, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to the following examples.
As shown in Figure 2, folded be coated with compound lithium battery diaphragm, in the upper and lower surface of grafting PE microporous film layers, all be compounded with successively grafting PTFE microporous film layers and ceramic coating.
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, the stack membrane plane strain is 0.85kg, 320 ℃ of heat roller temperatures, PTFE film 180 ° of cornerites on hot-rolling, hot-rolling pressure 2kg, 5 m/mins of linear velocities, be superimposed together grafting PTFE/ grafting PE/ grafting PTFE hot pressing; Adopt dipping technique dual coating pottery solution, strike off the unnecessary solution in both sides, heated-air drying, 120 ℃ of temperature, 5 m/mins of speed; At 260 ℃ of lower hot blasts, solidify, ultraviolet ray is irradiated, 5 m/mins of speed, and the rolling film forming, cut to be detected.
Being prepared as of pottery solution: ceramic nano particle (VK-L30JY of Xuancheng Jingrui New Material Co., Ltd. nano-aluminium oxide powder series of products, purity 99.99%, specific area 15～30m
2/ g) particle diameter 30nm, the percentage by weight that accounts 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 be the 20:3:2:2:2:1:1:5 mixing with the binding agent of the solid content 25% after the solvent acetone dilution in mass ratio, airtight stirring 3 hours, add gradually the ceramic nano particle, airtight stirring is 6 hours again, then cross 1200 order stainless steel dusting covers, foam-expelling, obtain;
The preparation of grafting PE microporous barrier: by PE barrier film raw material maleic anhydride graft, percent grafting 0.9%, then the wet method bi-directional synchronization draws film forming, thickness 20 μ m, porosity 38%, aperture 300nm; The preparation of grafting PTFE microporous barrier: first by the two-way asynchronous stretching film forming of raw material, and then acrylic graft-modified to the film low temperature plasma, percent grafting 0.7%, thickness 5 μ m, porosity 80%, aperture 1 μ m.The thick of ceramic coating is 1 μ m.Other technology is all with reference to prior art.
Embodiment 2
Folded be coated with compound lithium battery diaphragm, in the upper and lower surface of grafting PE microporous film layers, all be compounded with successively grafting PTFE microporous film layers and ceramic coating.
Preparation method: grafting PE, grafting PTFE film are stacked by the order of grafting PTFE/ grafting PE/ grafting PTFE, initiatively unreel, flatten, the stack membrane plane strain is 0.5kg, 310 ℃ of heat roller temperatures, PTFE film 180 ° of cornerites on hot-rolling, hot-rolling pressure 2kg, 5 m/mins of linear velocities, be superimposed together grafting PTFE/ grafting PE/ grafting PTFE hot pressing; Adopt dipping technique dual coating pottery solution, strike off the unnecessary solution in both sides, heated-air drying, 120 ℃ of temperature, 5 m/mins of speed; At 280 ℃ of lower hot blasts, solidify, ultraviolet ray is irradiated, 5 m/mins of speed, and the rolling film forming, cut to be detected.
Being prepared as of pottery solution: ceramic nano particle (VK-L50Y of Xuancheng Jingrui New Material Co., Ltd. nano-aluminium oxide powder series of products, purity 99.99%, specific area 100～150m
2/ g) particle diameter 50nm, the percentage by weight that accounts 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 be the 30:4:3:2:2:1:1:4 mixing with the binding agent of the solid content 25% after the solvent acetone dilution in mass ratio, airtight stirring 3 hours, add gradually the ceramic nano particle, airtight stirring is 6 hours again, then cross 1200 order stainless steel dusting covers, foam-expelling, obtain;
The preparation of grafting PE microporous barrier: by PE barrier film raw material maleic anhydride graft, percent grafting 0.9%, then the wet method bi-directional synchronization draws film forming, thickness 16 μ m, porosity 38%, aperture 300nm; The preparation of grafting PTFE microporous barrier: first by the two-way asynchronous stretching film forming of raw material, and then acrylic graft-modified to the film low temperature plasma, percent grafting 0.7%, thickness 10 μ m, porosity 80%, aperture 0.3 μ m.The thick of ceramic coating is 3 μ m.Other technology is all with reference to prior art.
Embodiment 3
Folded be coated with compound lithium battery diaphragm, in the upper and lower surface of grafting PE microporous film layers, all be compounded with successively grafting PTFE microporous film layers and ceramic coating.
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, 300 ℃ of heat roller temperatures, PTFE film 180 ° of cornerites on hot-rolling, hot-rolling pressure 2kg, 5 m/mins of linear velocities, be superimposed together grafting PTFE/ grafting PE/ grafting PTFE hot pressing; Adopt dipping technique dual coating pottery solution, strike off the unnecessary solution in both sides, heated-air drying, 120 ℃ of temperature, 5 m/mins of speed; At 300 ℃ of lower hot blasts, solidify, ultraviolet ray is irradiated, 5 m/mins of speed, and the rolling film forming, cut to be detected.
Being prepared as of pottery solution: ceramic nano particle (VK-L50Y of Xuancheng Jingrui New Material Co., Ltd. nano-aluminium oxide powder series of products, purity 99.99%, specific area 100～150m
2/ g) particle diameter 50nm, the percentage by weight that accounts 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 be the 36:4:3:3:2:2:1:3 mixing with the binding agent of the solid content 25% after the solvent acetone dilution in mass ratio, airtight stirring 3 hours, add gradually the ceramic nano particle, airtight stirring is 6 hours again, then cross 1200 order stainless steel dusting covers, foam-expelling, obtain;
The preparation of grafting PE microporous barrier: by PE barrier film raw material maleic anhydride graft, percent grafting 0.9%, then the wet method bi-directional synchronization draws film forming, thickness 20 μ m, porosity 38%, aperture 260nm; The preparation of grafting PTFE microporous barrier: first by the two-way asynchronous stretching film forming of raw material, and then acrylic graft-modified to the film low temperature plasma, percent grafting 0.7%, thickness 5 μ m, porosity 80%, aperture 0.6 μ m.The thick of ceramic coating is 4 μ m.Other technology is all with reference to prior art.
Folded be coated with compound lithium battery diaphragm, in the upper and lower surface of grafting PE microporous film layers, all be compounded with successively grafting PTFE microporous film layers and ceramic coating.
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, 320 ℃ of heat roller temperatures, PTFE film 180 ° of cornerites on hot-rolling, hot-rolling pressure 2kg, 5 m/mins of linear velocities, be superimposed together grafting PTFE/ grafting PE/ grafting PTFE hot pressing; Adopt dipping technique dual coating pottery solution, strike off the unnecessary solution in both sides, heated-air drying, 120 ℃ of temperature, 5 m/mins of speed; At 260 ℃ of lower hot blasts, solidify, ultraviolet ray is irradiated, 5 m/mins of speed, and the rolling film forming, cut to be detected.
Being prepared as of pottery solution: ceramic nano particle (VK-L30JY of Xuancheng Jingrui New Material Co., Ltd. nano-aluminium oxide powder series of products, purity 99.99%, specific area 15～30m
2/ g) particle diameter 30nm, the percentage by weight that accounts 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 be the 25:3.5:2.5:2.5:2:1:1:6 mixing with the binding agent of the solid content 25% after the solvent acetone dilution in mass ratio, airtight stirring 3 hours, add gradually the ceramic nano particle, airtight stirring is 6 hours again, then cross 1200 order stainless steel dusting covers, foam-expelling, obtain;
The preparation of grafting PE microporous barrier: by PE barrier film raw material maleic anhydride graft, percent grafting 0.9%, then the wet method bi-directional synchronization draws film forming, thickness 9 μ m, porosity 38%, aperture 240nm; The preparation of grafting PTFE microporous barrier: first by the two-way asynchronous stretching film forming of raw material, and then acrylic graft-modified to the film low temperature plasma, percent grafting 0.7%, thickness 5 μ m, porosity 80%, aperture 1.2 μ m.The thick of ceramic coating is 2 μ m.Other technology is all with reference to prior art.
In preparation process, can find, the three stacked tension force that close the process film are larger, and film is more wrinkling, affects the superimposed of film, and tension force is suitable≤1kg; The temperature of hot-rolling is higher, larger on the impact of superimposed film, and temperature is suitable≤and 320 ℃; 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, and obscission is arranged.
PE barrier film, PTFE microporous barrier are all ZhongCai Science membrane material company product, are coated with the detection Performance Ratio of three layers of barrier film of pottery and embodiment 1～4 in embodiment 4 as table 1.Temperature tolerance means (120 ℃, under 1 hour condition) with shrinkage, Macmullin number (MacMullin number) refers to resistance after the barrier film imbibition and the ratio of bath resistance, has reacted the size of pick up, resistivity, is worth the smaller the better.1. Macmullin counts method of testing: barrier film is immersed in lithium hexafluorophosphate electrolyte solution to 1 hour, and room temperature (25 ℃), take out and measure its resistance value, and the resistance value of the electrolyte of measurement is done to denominator, soaks the resistance value of electrolyte barrier film and do molecule, calculates its ratio; 2. closed pore temperature method of testing: barrier film is immersed in lithium hexafluorophosphate electrolyte solution, and the electrolyte of heating, release corresponding closed pore temperature (maximum is fully closed) according to different temperature, different resistances.
Table 1
Claims (9)
1. fold the compound lithium battery diaphragm of painting for one kind, it is characterized in that: the upper and lower surface in grafting PE microporous film layers all is compounded with grafting PTFE microporous film layers and ceramic coating successively, and the thick of ceramic coating is 0.001～7 μ m; The thick of grafting PTFE microporous film layers is 1～10 μ m; The thick of grafting PE microporous film layers is 5～25 μ m.
2. the compound lithium battery diaphragm of folded painting as claimed in claim 1, it is characterized in that: the compound lithium battery diaphragm total thickness of described folded painting is 7.002～59 μ m; The porosity of grafting PTFE microporous film layers is 40～80%, and aperture is 0.1～2 μ m; The porosity of grafting PE microporous film layers is 30～45%, and aperture is 0.01～0.5 μ m.
3. the preparation method of the compound lithium battery diaphragm of the described folded painting of claim 1 or 2 is characterized in that: comprise the following steps that order is joined:
A, the upper and lower surface of grafting PE microporous barrier is all stacked to grafting PTFE microporous barrier, and hot pressing is complex as a whole them, obtains original membrane, hot pressing temperature is 100～350 ℃, 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, solidify, obtain; Wherein, kiln temperatures is 50～200 ℃, and curing temperature is 70～400 ℃;
In ceramic suspension liquid, comprise: nanometer scale ceramics particle 10-70 part, 5～10 parts of polymeric binder, increase attached dose 1～3 part, 0.1～0.7 part of crosslinking agent, 13.95～83.05 parts of solvents, 0.4～0.85 part of light trigger, 0.15～0.6 part of catalyst, 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 after 1～10 hour, add gradually the nanometer scale ceramics particle, after reinforced, airtight stirring 4～24 hours, defoam, cross 1100-1300 order stainless steel dusting cover, obtain.
4. method as claimed in claim 3 is characterized in that: in steps A, being prepared as of grafting PE microporous barrier: first to the 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, obtains; Gained grafting PE micropore thickness is 5～25 μ m, and porosity is 30～45%, and aperture is 0.01～0.5 μ m;
Graft modification is gas phase grafting, light-initiated grafting, high temperature hot joining branch, 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.
5. method as claimed in claim 3 is characterized in that: in steps A, being prepared as of grafting PTFE microporous barrier: first by the two-way asynchronous stretching film forming of raw material, and then, to the film graft modification, obtain, percent grafting is 0.3～2%; Grafting PTFE micropore thickness is 1～10 μ m, and porosity is 40～80%, and aperture is 0.1～2 μ m;
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.
6. as the described method of claim 3-5 any one, it is characterized in that: in step B, the mixture that polymeric binder is 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, perfluorinated sulfonic acid ionomer, Polystyrene Sulronate, styrene propionic acid copolymer or sulfonated butyl rubber.
7. as the described method of claim 3-5 any one, 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, perfluoro capryl ethyl trichlorosilane or ten trifluoro octyl group trimethoxy silanes.
8. as the described method of claim 3-5 any one, it is characterized in that: in step B, the mixture that crosslinking agent is one or more any proportionings in divinylbenzene, diacetate, triacrylate, tetraacrylate, dimethacrylate, trimethylamine hydrochloride acrylate, diallyl, triallyl, glycidol ether or polyethylene glycol dimethacrylate.
9. as the described method of claim 3-5 any one, it is characterized in that: in step B, the mixture that solvent is 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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| CN104201308A (en) * | 2014-09-09 | 2014-12-10 | 深圳市信宇人科技有限公司 | Cast coated ultraviolet curing all-ceramic battery diaphragm and cast coating method thereof |
| CN104638220A (en) * | 2015-02-11 | 2015-05-20 | 中材科技股份有限公司 | Environment-friendly high-performance ceramic coating lithium ion battery diaphragm and preparation method thereof |
| CN104835931A (en) * | 2015-03-30 | 2015-08-12 | 东华大学 | Nonwoven fabric lithium ion battery composite diaphragm and preparation method thereof |
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| CN104638220A (en) * | 2015-02-11 | 2015-05-20 | 中材科技股份有限公司 | Environment-friendly high-performance ceramic coating lithium ion battery diaphragm and preparation method thereof |
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| CN104835931A (en) * | 2015-03-30 | 2015-08-12 | 东华大学 | Nonwoven fabric lithium ion battery composite diaphragm and preparation method thereof |
| CN104835931B (en) * | 2015-03-30 | 2017-03-22 | 东华大学 | Nonwoven fabric lithium ion battery composite diaphragm and preparation method thereof |
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| CN111615759B (en) * | 2017-12-27 | 2023-05-16 | 日本碍子株式会社 | LDH separator and zinc secondary battery |
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| CN108847467A (en) * | 2018-06-29 | 2018-11-20 | 安徽省徽腾智能交通科技有限公司 | A kind of preparation method of lithium battery diaphragm |
| CN108682775A (en) * | 2018-06-29 | 2018-10-19 | 安徽省徽腾智能交通科技有限公司 | A kind of lithium battery diaphragm and its application |
| CN108933219A (en) * | 2018-09-29 | 2018-12-04 | 杨晓丽 | A kind of preparation method of lithium battery diaphragm |
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| CN111834582A (en) * | 2019-04-15 | 2020-10-27 | 旭化成株式会社 | Polyolefin laminated microporous membrane |
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| CN112635914A (en) * | 2020-12-21 | 2021-04-09 | 中材锂膜有限公司 | Lithium ion battery diaphragm with heat resistance and high mechanical strength and preparation method thereof |
| CN114142160A (en) * | 2021-11-27 | 2022-03-04 | 周菊青 | Nano ceramic-polypropylene composite battery diaphragm and preparation method thereof |
| 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 |
| CN114335904A (en) * | 2022-02-28 | 2022-04-12 | 湖南中锂新材料科技有限公司 | Lithium battery composite diaphragm and preparation method and application thereof |
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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. |