CN103078075B - Composite film with high-temperature resistance layer, preparation method thereof and battery - Google Patents
Composite film with high-temperature resistance layer, preparation method thereof and battery Download PDFInfo
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- CN103078075B CN103078075B CN201210593471.9A CN201210593471A CN103078075B CN 103078075 B CN103078075 B CN 103078075B CN 201210593471 A CN201210593471 A CN 201210593471A CN 103078075 B CN103078075 B CN 103078075B
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- 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
Abstract
The application relates to the field of lithium batteries, and particularly discloses a composite film with a high-temperature resistance layer, a preparation method thereof and a battery. The composite film disclosed by the application comprises a base film and the high-temperature resistance layer, wherein the base film is a porous thermoplastic resin film; the high-temperature resistance layer is an inorganic ceramic layer containing ceramic particles; the inorganic ceramic layer is fixed on at least one surface of the porous thermoplastic resin film by polymerization; and the peel strength of the porous thermoplastic resin film and the inorganic ceramic layer is larger than or equal to 25 N/m under the condition of 180 DEG C. The invention further discloses the preparation method and the application of the composite film and the battery adopting the composite film. According to the application, the peel strength of inorganic ceramic layer and the porous thermoplastic resin film is greatly improved so as to effectively avoid a powder falling phenomenon of the inorganic ceramic particles in the composite film. Meanwhile, the composite film has excellent high temperature resistance performance, and can reduce battery short circuit phenomena caused by heat shrinkage of the composite film in the application.
Description
Technical field
The application relates to lithium ion battery field, is specifically related to a kind of composite membrane with high-temperature-resistant layer and preparation method thereof and a kind of battery.
Background technology
Lithium ion battery is the advantages such as energy density is large, output voltage is high, have extended cycle life, environmental pollution is little owing to having, and in small size digital electronic product, are applied widely, and in fields such as electric automobile, Aero-Space, also have broad application prospects.But be accompanied by the fast development of lithium ion battery and the expansion of application, lithium rechargeable battery security incident takes place frequently, little of battery-heating, greatly to the automobile that ignites, the whole world has been transferred to secure context to the focal point of lithium ion battery.The safety problem of lithium battery is mainly the short circuit contact between positive and negative electrode, thereby causes violent chemical reaction.Based on this, require barrier film at high temperature to there is good dimensional stability, the both positive and negative polarity of energy split cell.
The barrier film using is at present mainly the polyalkene diaphragm of porous, comprises polypropylene diaphragm, polyethylene barrier film, polypropylene, polyethylene/polypropylene diaphragm.External main manufacturer comprises Celgard, Tonen, Ube, Asahi, and domestic main manufacturer comprises star source material, Jin Hui, Ge Ruien etc.One large shortcoming of this class porous polyolefin barrier film is its poor heat stability, the thermally-stabilised limit is lower than 150 ℃, even if the temperature of interior battery of short time reaches the fusing point of polyalkene diaphragm, also can cause barrier film to produce serious thermal contraction, and then cause the contact short circuit between both positive and negative polarity.
For the battery short circuit that prevents from causing because of thermal contraction, there have been a lot of companies to start to attempt at the various high-temperaure coatings of polyalkene diaphragm surface-coated.As Chinese patent CN101689624A proposes the heat stable resin that the polyalkene diaphragm surface-coated in porous contains inorganic filler; Chinese patent CN1717821B proposes at flexible nonwoven surface coating inorganic ceramic coating.But the barrier film that these technology are produced, inorganic ceramic filler all easily comes off from membrane surface, and not only heat-resisting quantity declines, and affects the performance of battery.
Summary of the invention
For the problems referred to above, the application's object is to provide composite membrane of a kind of high-temperature-resistant layer with excellent specific property and preparation method thereof.
Another object of the application is to provide above-mentioned composite membrane in the application of field of batteries and comprises the battery of the composite membrane of above-mentioned high-temperature-resistant layer.
For solving the problems of the technologies described above, the application provides a kind of composite membrane with high-temperature-resistant layer, this composite membrane comprises basement membrane and high-temperature-resistant layer, wherein, basement membrane is thermoplastic resin perforated membrane, high-temperature-resistant layer is the inorganic, ceramic layer that contains inorganic ceramic particle, and inorganic, ceramic layer is fixed at least one surface of thermoplastic resin perforated membrane by polymerization.
In this composite membrane, above-mentioned thermoplastic resin perforated membrane and above-mentioned inorganic, ceramic layer peel strength under 180 ℃ of conditions is more than or equal to 25N/m.
Further, above-mentioned basement membrane is polyolefin individual layer perforated membrane or polyolefin multi-layer perforated membrane.
Above-mentioned inorganic ceramic particle is selected from least one in silicon dioxide, alundum (Al2O3), titanium dioxide, zirconium dioxide, zinc oxide, magnesium oxide, aluminium hydroxide, magnesium hydroxide and boehmite.
The particle diameter of above-mentioned inorganic ceramic particle is preferably 0.01 μ m≤D50≤5 μ m, and more preferably 0.5 μ m≤D50≤3 μ m, most preferably is 0.1 μ m≤D50≤1 μ m.
Meanwhile, the application provides the above-mentioned preparation method with the composite membrane of high-temperature-resistant layer, and the method comprises: amino in the grafting of inorganic ceramic particle surface, at thermoplastic resin porous film surface carboxyl grafting; There is amino inorganic ceramic particle to be prepared into coating slurry surface grafting, be applied at least one surface that surface grafting has the thermoplastic resin perforated membrane of carboxyl.
Concrete, above-mentionedly at inorganic ceramic particle surface grafting amino, comprise: inorganic ceramic particle is joined to alcohol dispersion liquid and stir, in alcohol dispersion liquid, add amino silicane coupling agent again, reaction is by the dry inorganic ceramic particle that obtains surface grafting amino silicane coupling agent of washing.
Preferably, above-mentioned reaction temperature is 40 ~ 60 ℃.
Preferably, in above-mentioned steps, the pH value that regulates above-mentioned alcohol dispersion liquid is 6-8, keeps in reaction, and the pH value of alcohol dispersion liquid reaction system is 6-8.
The preparation of above-mentioned coating slurry comprises: by weight, have amino inorganic ceramic particle, 0.3-1.5 part condensing agent, 5-25 part binding agent to join in the organic solvent of 30-50 part 30-50 part surface grafting, stir and make coating slurry.
Preferably, above-mentioned condensing agent is 1-1.5 part.
Preferably, above-mentioned condensing agent can be selected from EDC(1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride), CDMT(2-is chloro-4,6-dimethoxy-1,3,5-, tri-azepines) and NHS(N-HOSu NHS) at least one.
Above-mentioned at least one surface that applies slurry and be applied to basement membrane is comprised: at least one surface that applies slurry and be coated in thermoplastic resin perforated membrane is dried again to amino and carboxyl polymerization reaction take place in dry run.Its coating thickness is 1-15 μ m, and bake out temperature is 50-80 ℃.
Preferably, bake out temperature is 60 ~ 80 ℃.
Preferably, coating thickness is 1-3 μ m.
The composite membrane with high-temperature-resistant layer being prepared by above-mentioned preparation method, its thermoplastic resin perforated membrane and inorganic, ceramic layer peel strength under 180 ℃ of conditions is more than or equal to 25N/m.
The application also provides the application of above-mentioned composite membrane in field of batteries.
Concrete, the application discloses a kind of battery, and this battery comprises the above-mentioned composite membrane with high-temperature-resistant layer.
The invention has the beneficial effects as follows: the application's composite membrane, comprise thermoplastic resin perforated membrane and the inorganic, ceramic layer with resistance to elevated temperatures, its inorganic, ceramic layer and thermoplastic resin perforated membrane combine by polymerization, the peel strength of inorganic, ceramic layer and thermoplastic resin perforated membrane is improved greatly, can effectively avoid the dry linting phenomenon of inorganic ceramic particle in composite membrane.
Composite membrane in the application has excellent high temperature resistance performance, can reduce the battery short circuit that the thermal contraction due to composite membrane causes in application.Meanwhile, inorganic, ceramic layer has also improved puncture intensity and the wetting property of composite membrane.
Adopt the method that the application provides to prepare above-mentioned composite membrane, the method by polymerization is fixed on inorganic ceramic particle on the surface of basement membrane, has improved the peel strength of inorganic, ceramic layer and thermoplastic resin perforated membrane; And by solvent evaporates, form surface micropore, guaranteed porosity and the gas permeability of composite membrane.
Embodiment
The disclosed composite membrane with high-temperature-resistant layer of the application, comprises basement membrane and is positioned at least one lip-deep high-temperature-resistant layer of basement membrane.Wherein, basement membrane is for take the thermoplastic resin perforated membrane that thermoplastic resin is main component, and high-temperature-resistant layer is the inorganic, ceramic layer that contains inorganic ceramic particle, and its inorganic, ceramic layer is fixed at least one surface of thermoplastic resin perforated membrane by polymerization.In composite membrane in the application, thermoplastic resin perforated membrane and inorganic, ceramic layer peel strength under 180 ℃ of conditions is more than or equal to 25N/m.
Thermoplastic resin perforated membrane in the application is to take thermoplastic resin as its main component, and this thermoplastic resin can be polyolefin, includes but not limited to polyethylene, polypropylene, poly 1-butene, polypenthylene etc.In addition, this thermoplastic resin perforated membrane can be monofilm, for example polyolefin individual layer perforated membrane; Or multilayer film, for example duplicature or trilamellar membrane, if multilayer film, the composition of each layer of multilayer film can be the same or different, for example the polyolefin multi-layer perforated membrane of polypropylene, polyethylene/polypropylene structure.
In the application, inorganic ceramic particle can be selected from least one in silicon dioxide, alundum (Al2O3), titanium dioxide, zirconium dioxide, zinc oxide, magnesium oxide, aluminium hydroxide, magnesium hydroxide and boehmite, in the application's a embodiment, inorganic ceramic particle is preferably alundum (Al2O3).In addition, the particle diameter of inorganic ceramic particle is 0.01 μ m≤D50≤5 μ m preferably, and more preferably 0.5 μ m≤D50≤3 μ m, most preferably is 0.1 μ m≤D50≤1 μ m.
The application provides the above-mentioned preparation method with the composite membrane of high-temperature-resistant layer, and the method comprises: amino in the grafting of inorganic ceramic particle surface, at thermoplastic resin porous film surface carboxyl grafting; There is amino inorganic ceramic particle to be prepared into coating slurry surface grafting, be applied at least one surface that surface grafting has the thermoplastic resin perforated membrane of carboxyl.The amino polymerization reaction take place of the carboxyl of thermoplastic resin porous film surface grafting and the grafting of inorganic ceramic particle surface in preparation process, thus inorganic, ceramic layer is fixed at least one surface of thermoplastic resin perforated membrane by polymerization.
In the application's a embodiment, above-mentioned is to adopt amino silicane coupling agent to modify inorganic ceramic particle surface at inorganic ceramic particle surface grafting amino.Concrete, inorganic ceramic particle is added in alcohol dispersion liquid and is heated with stirring to 40-60 ℃, regulating the PH of alcohol dispersion liquid is 6-8, in alcohol dispersion liquid, add again the amino silicane coupling agent of the 5%-20% of inorganic ceramic granular mass, keeping the temperature of alcohol dispersion liquid is 40-60 ℃, and pH value is 6-8, after stirring reaction 0.5-2 hour, wash the inorganic ceramic particle of centrifugal, dry surface grafting amino silicane coupling agent.Above-mentioned alcohol dispersion liquid can be alcohol dispersion liquid, but is not limited in ethanol, and other alcohol dispersion liquids are also applicable to the application.At least one of the optional 3-aminopropyl trimethoxysilane of above-mentioned amino silicane coupling agent, 3-aminopropyl dimethylsilane, 3-aminopropyl triethoxysilane, 3-aminopropyl ethyoxyl dimethylsilane, N-methyl-3-aminopropyl triethoxysilane and N-methyl-3-aminopropyl trimethoxysilane.
At thermoplastic resin porous film surface carboxyl grafting, can adopt ultraviolet radiation graft polymerization, in the application's a embodiment, above-mentionedly at thermoplastic resin porous film surface carboxyl grafting, specifically comprise: by sensitising agent by 1.0-10wt%(weight ratio) be dissolved in acetone or oxolane, the sensitising agent solution that must apply, then immerses thermoplastic resin perforated membrane in this sensitising agent solution.The thermoplastic resin perforated membrane of invading containing after the mixed solution of sensitising agent is immersed in grafted monomers solution again, and after taking out, ultraviolet lighting obtains the thermoplastic resin perforated membrane that surface grafting has carboxyl.Sensitising agent can be selected benzophenone, but is not limited in this, and other sensitising agents are also applicable to the application.Grafted monomers solution can adopt one or both in acrylic acid and methacrylic acid, and one or more in employing acetone, deionized water and oxolane are solvent, the dissolubility of the selective basis grafted monomers of solvent and determining, the concentration of grafted monomers is 10-30wt%.
In the application's a embodiment, above-mentioned surface grafting is had amino inorganic ceramic particle to be prepared into apply slurry specifically comprise: by weight, there are amino inorganic nano-particle, 0.3-1.5 part condensing agent, 5-25 part binding agent to join in the organic solvent of 30-50 part 30-50 part surface grafting, adopt sand mill, high-speed turbine mixer or ball mill etc. to stir, make coating slurry.Preferably, condensing agent is 1-1.5 part.Wherein, condensing agent can be selected from EDC(1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride), CDMT(2-chloro-4,6-dimethoxy-1,3,5-tri-azepines) and NHS(N-HOSu NHS) at least one, but be not limited in this, in this application preferred EDC.The optional PVDF of binding agent, but be not limited in this, other binding agents are also applicable to the application.
In the application's a embodiment, above-mentionedly specifically can adopt the methods such as roller coat, dip-coating, blade coating, spraying, brushing on the surface that is grafted with the thermoplastic resin perforated membrane of carboxyl, to apply again in drying in oven applying slurry at least one surface that applies slurry and be applied to surface grafting and have the thermoplastic resin perforated membrane of carboxyl, amino and carboxyl polymerization reaction take place in this dry run.Concrete, bake out temperature is 50 ~ 80 ℃, further preferred, bake out temperature is 60 ~ 70 ℃.Its coating thickness is 1-15 μ m, further preferred, and coating thickness is 1-3 μ m.
The composite membrane with high-temperature-resistant layer in the application is applicable to field of batteries, specifically can be used as battery diaphragm and is applied in battery.
Below by embodiment, the application is described in further detail.
Embodiment 1
It is the polypropylene screen of 16 μ m that thermoplastic resin perforated membrane is selected thickness
(1) amino silicane coupling agent is modified inorganic ceramic particle surface
The alundum (Al2O3) that is 300nm by 6.0g average grain diameter joins and in alcohol dispersion liquid, is heated with stirring to 45 ℃ of left and right, regulating pH value is 6.5 left and right, in alcohol dispersion liquid, slowly add again 1.2g3-aminopropyl triethoxysilane, keep the temperature of alcohol dispersion liquid 45 ℃ of left and right, pH value, in 6.5 left and right, reacts 1 hour, acetone washing, obtain the alundum (Al2O3) of surface grafting coupling agent, room temperature vacuumize.
(2) thermoplastic resin porous film surface carboxyl grafting
The benzophenone of 2wt% weight portion is dissolved in to the sensitising agent solution that is mixed with coating in oxolane, polypropylene screen is placed in to this sensitising agent solution and soaks after 2min, take out and dry, ultraviolet lighting 5min.Again polypropylene screen is immersed to acrylic acid concentration and be in 20% deionized water solution and take out after 2min, ultraviolet lighting 5min post-drying.
(3) thermoplastic resin porous film surface applies
The inorganic ceramic particle that 30 parts of steps (1) make, 1 part of EDC, 15 parts of PVDF join in the acetone of 45 parts, and sand mill stirs 1h must apply slurry 1.
Adopt the mode of dip-coating to carry out surface-coated, the polypropylene screen making in step (2) is immersed and applied in slurry 1, take out rear 80 ℃ of oven for drying, make composite membrane 1.
Embodiment 2
It is the polyethylene film of 12 μ m that thermoplastic resin perforated membrane is selected thickness
(1) amino silicane coupling agent is modified inorganic ceramic particle surface
The alundum (Al2O3) that is 500nm by 8.0g average grain diameter adds and in alcohol dispersion liquid, is heated with stirring to 55 ℃ of left and right, regulate PH7.5 left and right, slowly add 1g3-aminopropyl triethoxysilane, keep the temperature of alcohol dispersion liquid 55 ℃ of left and right, pH value, in 7.5 left and right, reacts 1 hour, acetone washing, obtain the alundum (Al2O3) of surface grafting coupling agent, room temperature vacuumize.
(2) thermoplastic resin porous film surface carboxyl grafting
The benzophenone of 2wt% weight portion is dissolved in oxolane, is mixed with the sensitising agent solution of coating, polyethylene film is placed in to this sensitising agent solution and soaks after 2min, take out and dry, ultraviolet lighting 5min.Again polyethylene film is immersed to acrylic acid concentration and be in 15% deionized water solution and take out after 2min, ultraviolet lighting 5min post-drying.
(3) thermoplastic resin porous film surface applies
The inorganic ceramic particle that 49 parts of steps (1) make, 1.5 parts of EDC, 20 parts of PVDF join in the acetone of 30 parts, and sand mill stirs 1h must apply slurry 2.
Adopt the mode of dip-coating to carry out surface-coated, the polyethylene film making in step (2) is immersed and applied in slurry 2, take out rear 65 ℃ of oven for drying, make composite membrane 2.
Comparative example 1
Selecting uncoated thickness is the polypropylene screen of the 16 μ m example 1 of making comparisons
Comparative example 2
Selecting uncoated thickness is the polyethylene film of the 12 microns example 2 of making comparisons
Comparative example 3
It is the polypropylene screen of 16 μ m that basement membrane is selected thickness, 30 parts of alumina particles that average grain diameter is 300nm, and 15 parts of PVDF join in the acetone of 45 parts, and sand mill stirs 1h must apply slurry 3.Adopt the mode of dip-coating to carry out surface-coated, polypropylene screen is immersed in this coating slurry 3, take out rear 80 ℃ of oven for drying, make contrast composite membrane.
Polypropylene screen, polyethylene film and contrast composite membrane in composite membrane in above-described embodiment 1-2 1 and composite membrane 2 and comparative example 1-3 are detected respectively.
Wherein, peel strength assay method under 180 ℃ of conditions: 5, the sample that above-mentioned each film is cut out to the wide 10mm of long 80mm*, coat side is fixed on the stainless steel substrates of smooth cleaning with double faced adhesive tape, and corrosion resistant plate one end is fixed on omnipotent puller system, constant speed with 10mm/min, peel off for 180 ℃, experiment repeats to average for 5 times.
Ventilation characteristic measuring method: above-mentioned each film is cut into 5, the sample of 10cm*10cm, with reference to GB/T5402-2003 standard, measures under 1.22KPa pressure sample by the needed time of 100ml gas.
Thermal contraction performance method of testing: above-mentioned each film is cut into 5, the sample of 10cm*10cm, sample is placed in to heat treatment 0.5h in the baking oven of 150 ℃.
Test result is as follows:
Table 1 test result
Known by above-mentioned testing result, the composite membrane that embodiment 1 and 2 prepares is obviously better than comparative example 3 in peel strength, and the composite membrane that embodiment 1 and 2 prepares is also obviously better than comparative example 1-3 on thermal contraction performance, in this external puncture intensity, also compared with comparative example 1-3, increase.
Above content is in conjunction with concrete execution mode further description made for the present invention, can not assert that specific embodiment of the invention is confined to these explanations.For general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, can also make some simple deduction or replace.
Claims (16)
1. a composite membrane with high-temperature-resistant layer, comprise basement membrane and high-temperature-resistant layer, it is characterized in that, described basement membrane is thermoplastic resin perforated membrane, described high-temperature-resistant layer is the inorganic, ceramic layer that contains inorganic ceramic particle, and described inorganic, ceramic layer is fixed at least one surface of described thermoplastic resin perforated membrane by the carboxyl of thermoplastic resin porous film surface grafting and the amino polymerization reaction take place of inorganic ceramic particle surface grafting.
2. composite membrane as claimed in claim 1, is characterized in that, described thermoplastic resin perforated membrane and described inorganic, ceramic layer peel strength under 180 ℃ of conditions is more than or equal to 25N/m.
3. composite membrane according to claim 1 and 2, is characterized in that: described basement membrane is polyolefin individual layer perforated membrane or polyolefin multi-layer perforated membrane,
Described inorganic ceramic particle is selected from least one in silicon dioxide, alundum (Al2O3), titanium dioxide, zirconium dioxide, zinc oxide, magnesium oxide, aluminium hydroxide, magnesium hydroxide and boehmite,
The particle diameter of described inorganic ceramic particle is 0.01 μ m≤D50≤5 μ m.
4. composite membrane according to claim 3, is characterized in that: the particle diameter of described inorganic ceramic particle is 0.5 μ m≤D50≤3 μ m.
5. composite membrane according to claim 3, is characterized in that: the particle diameter of described inorganic ceramic particle is 0.1 μ m≤D50≤1 μ m.
6. the preparation method of the composite membrane described in claim 1～5 any one, it comprises: amino in the grafting of inorganic ceramic particle surface, at thermoplastic resin porous film surface carboxyl grafting; There is amino inorganic ceramic particle to be prepared into coating slurry surface grafting, described coating slurry is applied to at least one surface that surface grafting has the thermoplastic resin perforated membrane of carboxyl.
7. method as claimed in claim 6, it is characterized in that, describedly at inorganic ceramic particle surface grafting amino, comprise: during inorganic ceramic particle is joined to alcohol dispersion liquid, stir, in alcohol dispersion liquid, add amino silicane coupling agent again, reaction is by the dry inorganic ceramic particle that obtains surface grafting amino silicane coupling agent of washing.
8. method as claimed in claim 7, is characterized in that, reaction temperature is 40～60 ℃.
9. method as claimed in claim 7, is characterized in that, regulating the pH value of alcohol dispersion liquid is 6-8.
10. method as claimed in claim 6, it is characterized in that, the preparation of described coating slurry comprises: by weight, there are amino inorganic ceramic particle, 0.3-1.5 part condensing agent, 5-25 part binding agent to join in the organic solvent of 30-50 part 30-50 part surface grafting, stir and make coating slurry.
11. methods as claimed in claim 10, is characterized in that, described condensing agent is 1-1.5 part.
12. methods as claimed in claim 10, is characterized in that, it is chloro-4 that described condensing agent is selected from 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride, 2-, 6-dimethoxy-1, at least one in 3,5-, tri-azepines and N-hydroxy-succinamide.
13. methods as claimed in claim 6, it is characterized in that, described at least one surface that applies slurry and be applied to basement membrane is comprised: at least one surface that applies slurry and be coated in thermoplastic resin perforated membrane is dried again, and coating thickness is 1-15 μ m, and bake out temperature is 50-80 ℃.
14. methods as claimed in claim 13, is characterized in that, described bake out temperature is 60～80 ℃.
15. as claimed in any one of claims 1 to 5, wherein composite membrane in the application of field of batteries.
16. 1 kinds of batteries, is characterized in that, described battery comprises composite membrane as claimed in any one of claims 1 to 5, wherein.
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| CN103915591A (en) * | 2014-04-09 | 2014-07-09 | 深圳市星源材质科技股份有限公司 | Water-based ceramic coating lithium ion battery diaphragm and processing method thereof |
| CN104269507B (en) * | 2014-09-19 | 2017-04-05 | 国家电网公司 | A kind of lithium ion battery composite separation membrane 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 |
| JP6380307B2 (en) * | 2015-09-09 | 2018-08-29 | トヨタ自動車株式会社 | Battery separator |
| CN105957994A (en) * | 2016-04-29 | 2016-09-21 | 宁德卓高新材料科技有限公司 | Manufacturing method for ceramic diaphragm with low water absorbency |
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| CN108305972B (en) * | 2017-12-29 | 2021-08-17 | 深圳中兴新材技术股份有限公司 | Ceramic coating diaphragm and preparation method and application thereof |
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| CN111916619A (en) * | 2020-07-06 | 2020-11-10 | 华南师范大学 | Lithium ion battery composite diaphragm containing modified inorganic particles and preparation method thereof |
| CN114335904B (en) * | 2022-02-28 | 2022-07-12 | 湖南中锂新材料科技有限公司 | Lithium battery composite diaphragm and preparation method and application thereof |
| CN115275514B (en) * | 2022-09-30 | 2023-03-24 | 宁德卓高新材料科技有限公司 | Battery diaphragm, preparation method thereof and battery |
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| KR101125013B1 (en) * | 2009-07-29 | 2012-03-27 | 한양대학교 산학협력단 | Cross-linked ceramic-coated separators containing ionic polymers and rechargeable lithium batteries using them |
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| CN107851762B (en) * | 2015-07-10 | 2021-06-25 | 株式会社Lg化学 | Separator and electrochemical device comprising the same |
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