CN103943804B - A kind of temperature tolerance safety lithium ion cell barrier film and preparation method thereof - Google Patents
A kind of temperature tolerance safety lithium ion cell barrier film and preparation method thereof Download PDFInfo
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- CN103943804B CN103943804B CN201410159510.3A CN201410159510A CN103943804B CN 103943804 B CN103943804 B CN 103943804B CN 201410159510 A CN201410159510 A CN 201410159510A CN 103943804 B CN103943804 B CN 103943804B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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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
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a kind of temperature tolerance safety lithium ion cell barrier film, comprise basal layer and be compounded in the ceramic coating on basal layer; The raw material of described basal layer comprises: nano-dispersing agent, inorganic nanoparticles, antioxidant, PTFE dispersion liquid, polyethylene powder and paraffin oil, and the quality consumption of described antioxidant is 0.1 ~ 0.5% of polyethylene powder quality; The quality consumption of inorganic nanoparticles is 1 ~ 6% of polyethylene powder quality; The quality consumption of PTFE dispersion liquid is 0 ~ 30% of polyethylene powder quality; The quality consumption of polyethylene powder is 5 ~ 40% of paraffin oil quality; The mass ratio of nano-dispersing agent and inorganic nanoparticles is (1:20) ~ (1:90); The solid content of PTFE dispersion liquid is 50 ~ 60%.Present invention efficiently solves that existing lithium battery diaphragm ceramic coating comes off, the not safety problem that causes because of barrier film of heatproof and lithium ion battery.
Description
Technical field
The present invention relates to a kind of temperature tolerance safety lithium ion cell barrier film and preparation method thereof.
Background technology
In recent years due to the main flow that polyolefin diaphragm of lithium ion battery is market, its material itself the not performance of heatproof and manufacturing defect makes the usage safety performance of lithium ion battery be under suspicion.Therefore, the safety issue being improved lithium ion battery by the performance improving lithium ion battery separator receives increasing concern, domestic and international Ge great universities and colleges and correlative study institute, lithium ion battery separator manufacturing enterprise and lithium ion battery manufacturer have started the upsurge that one breaks through lithium ion battery separator fail safe, various inner lithium ion battery separator emerges in an endless stream: ceramic coating polyalkene diaphragm, heat resistance polymer fabric nonwoven cloth ceramic-coated separator, PVDF coating of polyolefins barrier film, PVDF barrier film etc., except ceramic-coated separator large-scale production, remaining is all in experiment development, but the coating process of ceramic-coated separator is: utilize existing dry method lithium ion battery separator (simple tension PP, PE and two-way asynchronous stretching PP) directly apply water-soluble or oiliness nano ceramics solution thereon, low temperature drying (40 ~ 60 DEG C), its result is: ceramic coating and base material polyolefin micropore barrier diaphragm can not form an organic whole, especially pottery is very weak with the combination interface intensity of polyolefin film, cause ceramic coating partial exfoliation (coating hole) or large area comes off.And this ceramic coating lithium ion battery separator is because interface cohesion loosely produces a lot of powder when cutting.Problem the most serious is, after such barrier film is assembled into inside battery, coating shedding, does not only improve the fail safe of lithium ion battery separator, have impact on the electrical property of lithium ion battery on the contrary because of the ceramic nano powder sheet come off.So up to this point, the lithium ion battery safety problem caused because of the performance of lithium ion battery separator own does not still solve, and this is a technical bottleneck of restriction lithium ion battery manufacture level.
Summary of the invention
The object of this invention is to provide a kind of temperature tolerance safety lithium ion cell barrier film 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 temperature tolerance safety lithium ion cell barrier film, comprises basal layer and the ceramic coating being compounded in the upper and lower surface of basal layer; The raw material of described basal layer comprises: nano-dispersing agent, inorganic nanoparticles, antioxidant, PTFE dispersion liquid, polyethylene powder and paraffin oil, and the quality consumption of described antioxidant is 0.1 ~ 0.5% of polyethylene powder quality; The quality consumption of inorganic nanoparticles is 1 ~ 6% of polyethylene powder quality; The quality consumption of PTFE dispersion liquid is 0 ~ 30% of polyethylene powder quality; The quality consumption of polyethylene powder is 5 ~ 40% of paraffin oil quality; The mass ratio of nano-dispersing agent and inorganic nanoparticles is (1:20) ~ (1:90); The solid content of PTFE dispersion liquid is 50 ~ 60%.
Applicant finds after deliberation: by adding nano-dispersing agent in the raw material of basal layer and PTFE dispersion liquid can make the raw material of basal layer be disperseed more fully, unexpected cooperative effect is served between each material, etc. obtaining uniform and stable dispersion, good basis is laid for preparing basal layer, and gained basal layer and ceramic coating have good adhesion effect, the two can form a stable entirety, there is not obscission in use procedure, effectively extend the useful life of barrier film.
The uniform and complete more of disperseing in order to feedstock portions can be made, strengthen the cooperative effect between each material further, nano-dispersing agent is the mixture of one or more any proportionings in perfluorocarboxylic acid, PFPE, stearic acid, dodecylic acid, sodium pyrophosphate, sodium metaphosphate, waterglass, alcohols, LCFA, softex kw, the basic sodium sulfonate of dodecane, polymer dielectric or macromolecule dispersing agent simultaneously.
In order to strengthen dispersion effect further, above-mentioned macromolecule dispersing agent is the mixture of one or more any proportionings in sodium silicate nanahydrate, polyacrylamide, polymethylacrylic acid, ammonium polymethacrylate, methyl methacrylate or butyl acrylate.
Inorganic nanoparticles is the mixture of one or more any proportionings in alundum (Al2O3), titanium dioxide, zirconia, silica, cerium oxide, calcium carbonate or zeolite, inorganic nanoparticles diameter is 30 ~ 600nm, be preferably 40 ~ 500nm, it is preferred that 40 ~ 400nm.
Described polyethylene powder is the mixture of high density polyethylene (HDPE) or ultra-high molecular weight polyethylene or both any proportionings; Antioxidant particle diameter≤150 μm.
Described polyethylene powder particle diameter≤100 μm, be preferably≤80 μm, it is preferred that≤60 μm, molecular weight is 100 ~ 4,000,000, is preferably 110 ~ 3,800,000, it is preferred that 130 ~ 3,600,000; Antioxidant particle diameter≤120 μm, it is preferred that≤100 μm.
In order to reach better dispersion effect, the particle diameter of PTFE dispersion liquid is 100 ~ 500nm, is preferably 100 ~ 400nm, it is preferred that 100 ~ 300nm.
The preparation method of above-mentioned temperature tolerance safety lithium ion cell barrier film, comprise the following steps that order connects: adopt the method for ultrasonic wave dispersion and interpolation nano-dispersing agent to be dispersed in paraffin oil by inorganic nanoparticles, antioxidant, PTFE dispersion liquid and polyethylene powder, form uniform suspension; Utilize wet method bi-directional synchronization drawing process that gained suspension is drawn film forming; Gained film prepares ceramic coating, to obtain final product.
Above-mentioned ultrasonic wave dispersion refers to adopt high-speed stirred or the equipment such as high shear dispersion or colloid mill in conjunction with ultrasonic dispersion technique, during film forming, utilize existing PE lithium ion battery separator wet method bidirectional synchronous drawing equipment and process drawing film forming, and then utilize existing lithium ion battery separator ceramic coating equipment and process to carry out ceramic coating, form the barrier film that the present invention is final.
In order to ensure the quality of products obtained therefrom further, above-mentioned preparation method, comprises the following steps that order connects:
A, pour paraffin oil into ultrasonic disperse machine, setting parameter scope is: ultrasonic wave is frequency 20 ~ 50HZ, and power is 100 ~ 6000W, and temperature is 5 ~ 100 DEG C;
B, in steps A gained material, add nano-dispersing agent, stir 5 ~ 40 minutes;
C, in step B gained material, add inorganic nanoparticles, stir 5 ~ 40 minutes;
D, in step C gained material, add PTFE dispersion liquid, stir 5 ~ 40 minutes;
E, in step D gained material, add antioxidant, stir 5 ~ 40 minutes;
F, in step e gained material, add polyethylene powder, stir 5 ~ 40 minutes;
G, by the material of step F gained, utilize existing PE wet method bidirectional synchronous drawing equipment and technique stretching film forming;
I, by step G gained film, adopt existing lithium battery diaphragm ceramic coating equipment and technology to carry out ceramic coating, to obtain final product.
Applicant finds after deliberation, and the process of above-mentioned even batch mixing also can adopt the nano-dispersed equipment such as the various high shear dispersion machine of combination of ultrasound, grinder, colloid mill to complete.
Above-mentioned steps G, inputs the high-order batch can of double screw extruder by mixing suspension, quantitatively conveying dual-screw-stem machine extruder, flat plate mold are extruded, extruder temperature 130 ~ 250 DEG C; The fluid-mixing extruded by flat plate mold forms the thin slice of certain thickness, cleanliness factor, mechanical strength through six roller slab machines, mold temperature 150 ~ 260 DEG C; Above-mentioned thin slice pulls into the diaphragm of desired thickness through bi-directional synchronization stretching-machine, and longitudinal stretching ratio is 3 ~ 12, and cross directional stretch ratio is 5 ~ 18; Eventually pass extraction, drying becomes certain porosity and the film in aperture; Above-mentioned steps I, becomes ceramic coating micropore lithium ion battery separator by special-purpose nanometer ceramic coating formula, production equipment with manufacture technics again by gained finished film.
Relative to prior art ceramic diaphragm, still there is more excellent performance without the barrier film of final step ceramic coating in the present invention, may be used in all kinds of lithium ion battery.
In above-mentioned steps G, bi-directional synchronization draw ratio is: longitudinal stretching ratio is 3 ~ 12, is preferably 3 ~ 11, it is preferred that 3 ~ 10; Cross directional stretch ratio is 5 ~ 18, is preferably 5 ~ 16, it is preferred that 5 ~ 13; The thickness of gained film 6 ~ 30 μm, is preferably 6 ~ 20 μm, it is preferred that 6 ~ 15 μm; In step I, thickness of ceramic coating 1 ~ 10 μm, is preferably 1 ~ 8 μm, it is preferred that 1 ~ 6 μm.
The gross thickness of above-mentioned gained barrier film is 8 ~ 50 μm, is preferably 8 ~ 36 μm, it is preferred that 8 ~ 32 μm.
The NM technology of the present invention is prior art.
Adopt the lithium ion battery of temperature tolerance safety lithium ion cell barrier film of the present invention manufacture to have good fail safe, efficiently solve that existing lithium battery diaphragm ceramic coating comes off, the not safety problem that causes because of barrier film of heatproof and lithium ion battery; This lithium ion battery separator porosity is high, there is good electrolyte wetability, mechanical property and heat resistance, also there is high temperature turn-off performance simultaneously, thickness is thin, utilize the battery of lithium ion battery separator manufacture of the present invention to have higher capacity and fast charging and discharging function, preferably usage safety performance, consumer lithium ion battery and power lithium-ion battery can be widely used in; Preparation method of the present invention is easy, easy to operate, repeatable high.
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.
In following embodiment, Suzhou Sai Pahan specialty oil Co., Ltd SPH-400# environmentally friendly machine selected by paraffin oil, and ultra-high molecular weight polyethylene is ZhongCai Science membrane material company research customed product (particle diameter 40 μm, molecular weight 1,500,000); Antioxidant adopts through Tian Wei Chemical Co., Ltd. 1010 type product; Nano aluminium oxide adopts Haitai Nano Material Co., Ltd., Nanjing HTAI-03 product (particle diameter 60nm); Ptfe emulsion (solid content 60%, viscosity 25mmPa.S, granularity 0.5 ~ 1.5 μm, glass textile is special) adopt the concentrated dispersion liquid product of Zhong Hao Chenguang Research Institute of Chemical Industry Co., Ltd weaving; Difference according to embodiment is changed kind, supplier and consumption by nano-dispersing agent; Ultrasonic dispersing machine adopts Shanghai Yi Ken plant equipment Co., Ltd EDC115 type product.
Preparation technology:
Weigh up paraffin oil in proportion and add ultrasonic dispersing machine, ultrasonic parameters is: frequency 36HZ, power 800W, temperature 40 DEG C.Open ultrasonic wave and stirring system, add nano-dispersing agent homogenizing 10 minutes; Add antioxidant homogenizing 5 minutes; Add nanoparticulate dispersed 20 minutes; Add PTFE dispersion emulsion homogenizing 10 minutes; Add polyethylene powders, homogenizing 20 minutes; Being transported to the second stirred tank continuation stirs stand-by; Ultrasonic dispersing machine continues to start batching dispersion; Suspension in second stirred tank is sent to the head tank of double screw extruder, extrudes, the stretching of slab, bi-directional synchronization, extraction, drying, heat treatment, rolling etc. produce by the existing wet method bi-directional synchronization stretching lithium ion battery separator technological process of production.Longitudinal stretching ratio is 3.5, and cross directional stretch is than 5.4;
Carry out barrier film coating by existing ceramic coating technology, select comparatively ripe patent ceramic coating preparing process as follows: Al
2o
3nano particle selects Haitai Nano Material Co., Ltd., Nanjing HTAI-01 product (particle diameter 80nm); Polyvinylidene fluoride hexafluoropropylene (PVDF-HFP), Dongguan City, Guangdong Province Jin Hu plastic material Co., Ltd product; 3-(ethoxymethyl) base silane propyl methacrylate selects Shanghai Liu Shi Pharmaceutical Technology Co., Ltd product; Dimethylbenzene, Nanjing Hu Ruihang Chemical Co., Ltd. product; Acetone, the melt and dissolved Chemical Co., Ltd. in Shanghai product; Ethanol, Kunshan Shen Bang Chemical Co., Ltd. product.The xylene solvent containing 3-(ethoxymethyl) base silane propyl methacrylate is utilized to process Al at 130 DEG C
2o
3nano particle 24 hours, filters rear dimethylbenzene and ethanol purge; Al
2o
3be: 80:20 that in acetone, high speed agitator stirs 5 hours in dispersion with PVDF-HFP ratio.The solution prepared is transported in the solution tank of lithium ion battery separator ceramic coating equipment, adopts the flow processs such as the coating of stamp anilox roll, drying, solidification, rolling to complete coating procedure.
Embodiment 1
Nano-dispersing agent adopts Shenzhen Mai Ruier chemical technology Co., Ltd model to be the perfluor dodecylic acid product of CAS307-55-1; The quality consumption of antioxidant is 0.4% of polyethylene powder quality, the quality consumption of nano-ceramic particle is 5% of polyethylene quality, the quality consumption of polyethylene powder is 25% of paraffin oil quality, the mass ratio of nano-dispersing agent and nano particle is the quality consumption of 1:50, PTFE dispersion emulsion is 6% of polyethylene powder quality.The thickness of bi-directional synchronization stretched film 8 μm, thick 4 μm of ceramic coating, film gross thickness 16 μm.
Embodiment 2
Nano-dispersing agent selects Shanghai Aitken Chinese workers Science and Technology Ltd. PFPE F106 product, the mass ratio of nano-dispersing agent and nano particle is 1:40, the quality consumption of antioxidant is 0.5% of polyethylene powder quality, the quality consumption of nano-ceramic particle is 4% of polyethylene quality, the quality consumption of PTFE dispersion liquid is 5% of polyethylene quality, and the quality consumption of polyethylene powder is 30% of paraffin oil quality.The thickness of bi-directional synchronization stretched film is 10 μm, and thickness of ceramic coating is 3 μm, and film gross thickness is 16 μm.
Embodiment 3
Nano-dispersing agent adopts reception room or parlour, Jiangsu bio tech ltd absolute ethyl alcohol product, the mass ratio of nano-dispersing agent and nano particle is 1:30, the quality consumption of nano-ceramic particle is 3% of polyethylene quality, the quality consumption of PTFE dispersion liquid is 4% of polyethylene quality, the quality consumption of antioxidant is 0.3% of polyethylene powder quality, and the quality consumption of polyethylene powder is 20% of paraffin oil quality.The thickness of bi-directional synchronization stretched film is 12 μm, and thickness of ceramic coating is 2 μm, and film gross thickness is 16 μm.
Embodiment 4
Nano-dispersing agent adopts Ju Sen chemical industry (Shanghai) Co., Ltd. isopropyl alcohol 67-63-0 type product, the mass ratio of nano-dispersing agent and nano particle is 1:60, the quality consumption of nano-ceramic particle is 2% of polyethylene quality, the quality consumption of PTFE dispersion liquid is 3% of polyethylene quality, the quality consumption of antioxidant is 0.5% of polyethylene powder quality, and the quality consumption of polyethylene powder is 28% of paraffin oil quality.The thickness of bi-directional synchronization stretched film is 14 μm, and thickness of ceramic coating is 1 μm, and film gross thickness is 16 μm.
Embodiment 5
Nano-dispersing agent adopts following composite Nano dispersant: isopropyl alcohol is Ju Sen chemical industry (Shanghai) Co., Ltd. 67-63-0 type product, butanols is Shanghai Jian Yuan Chemical Co., Ltd. n-butanol product, isopropyl alcohol: butanols=1:3, the mass ratio of dispersant and nano particle is 1:40, quality 3% of the weight northylen quality of nano-ceramic particle, the quality consumption of PTFE dispersion liquid is 2% of polyethylene quality, the quality consumption of antioxidant is 0.4% of polyethylene powder quality, and the quality consumption of polyethylene powder is 25% of paraffin oil quality.The thickness of bi-directional synchronization stretched film is 16 μm.No longer carry out ceramic coating process.
The performance of all embodiment lithium ion battery separators of the present invention sees the following form:
1. porosity detection method:
Sampling standard presses GB/T6673-2001 and GB/T6672-2001,
Computing formula:
In formula:
The surface density of ρ 1---sample, unit is a gram/cm (g/cm
2);
The quality of m---sample, unit of gram (g);
The length of L---sample, unit is centimetre (cm);
The width of b---sample, unit is centimetre (cm).
The porosity of p---sample, represents with %;
The thickness of d---sample, unit is centimetre (cm);
The density of ρ 0---raw material, unit is a gram/cm (g/cm
3).
2. Macmullin number method of testing:
Barrier film to be immersed in lithium hexafluorophosphate electrolyte solution 1 hour, room temperature (25 DEG C), to take out and measure its resistance value, the resistance value of the electrolyte of measurement is done denominator, the resistance value of leaching electrolyte barrier film does molecule, calculates its ratio;
3. closed pore temperature method of testing:
Barrier film is immersed in lithium hexafluorophosphate electrolyte solution, electrolyte of heating, releases corresponding closed pore temperature (maximum is completely closed) according to different temperature, different resistances.
Claims (7)
1. a preparation method for temperature tolerance safety lithium ion cell barrier film, is characterized in that:
Temperature tolerance safety lithium ion cell barrier film comprises basal layer and is compounded in the ceramic coating on the upper and lower surface of basal layer; The raw material of described basal layer comprises: nano-dispersing agent, inorganic nanoparticles, antioxidant, PTFE dispersion liquid, polyethylene powder and paraffin oil, and the quality consumption of described antioxidant is 0.1 ~ 0.5% of polyethylene powder quality; The quality consumption of inorganic nanoparticles is 1 ~ 6% of polyethylene powder quality; The quality consumption of PTFE dispersion liquid is 0 ~ 30% of polyethylene powder quality; The quality consumption of polyethylene powder is 5 ~ 40% of paraffin oil quality; The mass ratio of nano-dispersing agent and inorganic nanoparticles is (1:20) ~ (1:90); The solid content of PTFE dispersion liquid is 50 ~ 60%;
Nano-dispersing agent is the mixture of one or more any proportionings in perfluorocarboxylic acid, PFPE, stearic acid, dodecylic acid, sodium pyrophosphate, sodium metaphosphate, waterglass, alcohols, LCFA, softex kw, neopelex or macromolecule dispersing agent;
Macromolecule dispersing agent is the mixture of one or more any proportionings in polyacrylamide, polymethylacrylic acid or ammonium polymethacrylate;
The preparation method of above-mentioned temperature tolerance safety lithium ion cell barrier film, comprise the following steps that order connects: adopt the method for ultrasonic wave dispersion and interpolation nano-dispersing agent to be dispersed in paraffin oil by inorganic nanoparticles, antioxidant, PTFE dispersion liquid and polyethylene powder, form uniform suspension; Suspension is extruded, slab; Utilize wet method bi-directional synchronization drawing process that slab resulting sheet is drawn film forming; Gained film prepares ceramic coating, to obtain final product.
2. the preparation method of temperature tolerance safety lithium ion cell barrier film as claimed in claim 1, it is characterized in that: inorganic nanoparticles is the mixture of one or more any proportionings in alundum (Al2O3), titanium dioxide, zirconia, silica, cerium oxide, calcium carbonate or zeolite, inorganic nanoparticles diameter is 30 ~ 600nm.
3. the preparation method of temperature tolerance safety lithium ion cell barrier film as claimed in claim 1 or 2, is characterized in that: described polyethylene powder is the mixture of high density polyethylene (HDPE) or ultra-high molecular weight polyethylene or both any proportionings; Antioxidant particle diameter≤150 μm.
4. the preparation method of temperature tolerance safety lithium ion cell barrier film as claimed in claim 3, it is characterized in that: described polyethylene powder particle diameter≤100 μm, molecular weight is 100 ~ 4,000,000; Antioxidant particle diameter≤120 μm.
5. the preparation method of temperature tolerance safety lithium ion cell barrier film as claimed in claim 1 or 2, is characterized in that: the particle diameter of PTFE dispersion liquid is 100 ~ 500nm.
6. the preparation method of temperature tolerance safety lithium ion cell barrier film as claimed in claim 1 or 2, is characterized in that: the preparation method of temperature tolerance safety lithium ion cell barrier film, comprises the following steps that order connects:
A, pour paraffin oil into ultrasonic disperse machine, setting parameter scope is: ultrasonic wave is frequency 20 ~ 50Hz, and power is 100 ~ 6000W, and temperature is 5 ~ 100 DEG C;
B, in steps A gained material, add nano-dispersing agent, stir 5 ~ 40 minutes;
C, in step B gained material, add inorganic nanoparticles, stir 5 ~ 40 minutes;
D, in step C gained material, add PTFE dispersion liquid, stir 5 ~ 40 minutes;
E, in step D gained material, add antioxidant, stir 5 ~ 40 minutes;
F, in step e gained material, add polyethylene powder, stir 5 ~ 40 minutes;
G, the material of step F gained is extruded, slab, recycle existing PE wet method bidirectional synchronous drawing equipment and technique stretching film forming;
I, by step G gained film, adopt existing lithium battery diaphragm ceramic coating equipment and technology to carry out ceramic coating, to obtain final product.
7. the preparation method of temperature tolerance safety lithium ion cell barrier film as claimed in claim 6, it is characterized in that: in step G, bi-directional synchronization draw ratio is: longitudinal stretching ratio is 3 ~ 12, and cross directional stretch ratio is 5 ~ 18, the thickness of gained film 6 ~ 30 μm; In step I, thickness of ceramic coating 1 ~ 10 μm.
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| CN106531941B (en) * | 2017-01-10 | 2020-08-25 | 天津理工大学 | Ceramic slurry for lithium battery diaphragm and preparation and application methods thereof |
| CN106953052A (en) * | 2017-03-16 | 2017-07-14 | 上海双奥能源技术有限公司 | A kind of preparation method of lithium ion battery separator |
| CN108417759A (en) * | 2018-02-06 | 2018-08-17 | 合肥国轩高科动力能源有限公司 | Preparation method of high-wettability diaphragm for cylindrical lithium titanate battery |
| CN109060595A (en) * | 2018-07-05 | 2018-12-21 | 天津力神电池股份有限公司 | A method of detection lithium ion battery separator ceramic coating surface density |
| CN113451706A (en) * | 2018-07-17 | 2021-09-28 | 河南义腾新能源科技有限公司 | Polyethylene diaphragm for lithium ion battery and preparation method thereof |
| CN111477814A (en) * | 2019-01-30 | 2020-07-31 | 泰州衡川新能源材料科技有限公司 | Wet diaphragm and preparation process thereof |
| CN110165129A (en) * | 2019-05-28 | 2019-08-23 | 大连中比动力电池有限公司 | Anti-oxidant high puncture strength dry method diaphragm of one kind and its preparation method and application |
| CN114204210B (en) * | 2021-11-05 | 2024-01-05 | 东方电气集团科学技术研究院有限公司 | Preparation method of sodium ion battery diaphragm |
| CN115117559A (en) * | 2022-06-30 | 2022-09-27 | 中材锂膜有限公司 | Coating slurry of battery diaphragm, preparation method of coating slurry, battery diaphragm and lithium ion battery |
| CN115449105B (en) * | 2022-10-12 | 2023-08-18 | 嘉兴富瑞邦新材料科技有限公司 | Preparation method and application of polytetrafluoroethylene stretched film |
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Effective date of registration: 20180111 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: 211100 Jiangsu city of Nanjing province Jiangning Science Park Tong Road No. 99 Patentee before: Zhongcai Science & Technology Co., Ltd. |