CN105449142A - Polyimide/nano-silica composite porous film containing carboxyl structure and preparation method thereof - Google Patents

Polyimide/nano-silica composite porous film containing carboxyl structure and preparation method thereof Download PDF

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CN105449142A
CN105449142A CN201511018083.8A CN201511018083A CN105449142A CN 105449142 A CN105449142 A CN 105449142A CN 201511018083 A CN201511018083 A CN 201511018083A CN 105449142 A CN105449142 A CN 105449142A
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polyimide
carboxyl structure
containing carboxyl
porous film
polymer
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CN105449142B (en
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白迪
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JILIN JUKEGAO NEW MATERIALS CO Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403Manufacturing processes of separators, membranes or diaphragms
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409Separators, membranes or diaphragms characterised by the material
    • H01M50/446Composite material consisting of a mixture of organic and inorganic materials
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Manufacturing & Machinery (AREA)
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  • Inorganic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
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Abstract

The invention discloses a polyimide/nano-silica composite porous film containing a carboxyl structure and a preparation method thereof, belonging to the technical field of polymeric membrane materials. The preparation method comprises the following steps of firstly, preparing soluble polyimide containing the carboxyl structure, utilizing strong hydrogen-bond interaction of a large amount of carboxyl functional groups on the surface of the nano-silica and carboxyl functional groups in a polyimide structure to uniformly disperse nano-silica particles in polyimide polymer solution, and then preparing a silica-doped polyimide film through a film scraping method; and secondly, preparing the polyimide/nano-silica composite porous film containing the carboxyl structure, which has high porosity and ordered porous structures, through a phase separation method. The heat resistance is kept while the electrolyte resistance and the chemical stability of the porous film are further enhanced and improved. The material has very important significance and wide application prospect for improving the overall performance of a lithium ion battery, in particular safety.

Description

A kind of containing carboxyl structure Polyimide/Nano silicon dioxide composite porous film and preparation method thereof
Technical field
The invention belongs to macromolecule member material technical field, be specifically related to a kind of containing carboxyl structure Polyimide/Nano silicon dioxide composite porous film and preparation method thereof.
Background technology
Along with the development of high-tech industry, the research and development of polymer porous membrane have become one of current important front line science problem, mainly have very important application in fields such as UF membrane, catalysis, biomedicine, lithium ion battery separators.Lithium ion battery separator is a kind of high added value material that in lithium electric material, technology barriers are the highest, and the quality of membrane properties directly has influence on the fail safe of lithium battery, capacity, cycle life and cost.Barrier film should have suitable pore size and distribution, good chemical stability, thermal dimensional stability and thermo-chemical stability, ionic conductivity, electrolyte wettability, electronic isolation and certain mechanical strength.The requirement of electrokinetic cell to barrier film is higher, usually adopts composite membrane.The most popular two kinds of techniques preparing barrier film are dry process and wet processing at present, two kinds of techniques all adopt extruder, stretch in one or two direction, increase porosity and improve hot strength, adopt these two kinds of processes to produce lithium battery diaphragm mainly polyethylene (PE), polypropylene (PP) microporous barrier and polypropylene, polyethylene/polypropylene (PP/PE/PP) three-layer composite microporous membrane, be used widely.But it is lower to there is porosity, gas permeability and the poor shortcoming of lyophily.The more important thing is, the fusing point of polyolefine material is low, and high temperature dimensional stability is poor, at battery high power discharge, to be punctured or in the situation such as shock, battery temperature raises and barrier film may be caused to melt, and therefore there is serious potential safety hazard.The method preparing polymer porous membrane also has phase separation method, thermally induced phase separation, polymer assists phase inversion method etc., there is large area preparation in these methods, defect, pore size and pore-size distribution uneven, the problem that bore hole size is relatively large, therefore researcher is devoted to the research and development adopting different diaphragm matrix material and barrier film pore-creating engineering always, to developing, there is high porosity, even aperture distribution, good wetting property, mechanical property, thermal dimensional stability, the new types of diaphragm of chemical stability, improve battery performance, particularly improve the security performance of battery.
Polyimides (PI) is the high polymer containing imide ring structure in molecular backbone, this base polymer has outstanding heat resistance, excellent mechanical performance, electric property and chemical stability, has been widely used in Aeronautics and Astronautics, microelectronics, diffusion barrier, light wave communication, field of petrochemical industry.Polyimides can be divided into insolubility polyimides and soluble polyimide according to dissolubility, insolubility polyimides is prepared in regular porous structural film process, because of the impact of its insolubility and imidization condition, machine-shaping difficulty, is difficult to accurate control hole structure and aperture size.Structural design and modification are carried out to polyimides, in molecular backbone, introduce side base or destroyed regularity and the symmetry of segment by the method for copolymerization, interaction between effective reduction strand, keeping colleague's raising dissolubility in organic solvent of polyimides heat resistance, the method processing that solution can be adopted to process, is conducive to the preparation of polyimide film and polyimide porous film.
Summary of the invention
The object of the invention is to provide a kind of containing carboxyl structure Polyimide/Nano silicon dioxide composite porous film and preparation method thereof.This film has good electrolyte resistance corrosive power, has enough chemistry and electrochemical stability, and colleague has the features such as high porosity, good wetting property, excellent thermal endurance concurrently.For achieving the above object, the technical solution used in the present invention is as follows: first, the soluble polyimide of preparation containing carboxyl structure, carboxyl functional group strong hydrogen bonding effect in the hydroxy functional group utilizing nano-silica surface a large amount of and polyimide structures, realize dispersed in polyimides Polymer Solution of nano-silicon dioxide particle, then prepared the polyimide film of doping silicon dioxide by the method for knifing.Then, by phase separation method preparation have high porosity, regular ordered porous structural containing carboxyl structure Polyimide/Nano silicon dioxide composite porous film.While maintenance heat resistance, improve and improve electrolyte resistance ability and the chemical stability of perforated membrane further.This material is for the combination property, particularly fail safe that improve lithium ion battery, and tool is of great significance and wide application prospect.
Of the present invention containing carboxyl structure Polyimide/Nano silicon dioxide composite porous film preparation method, its step is as follows:
A) preparation is containing carboxyl structure polyimide polymer: under nitrogen protection condition, with 3,5-diaminobenzoic acid (DABA), hexafluoro acid anhydrides (6FDA), 4,4 '-diaminourea-2,2 '-bis trifluoromethyl biphenyl (TFMB) is raw material, and the mol ratio of anhydride monomers and diamine monomer (TFMB) is 1 ~ 1.02:1; Control carboxyl structure molar content 10 ~ 50%, namely [3,5-diaminobenzoic acid/(3,5-diaminobenzoic acid+4,4 '-diaminourea-2,2 '-bis trifluoromethyl biphenyl)] mol ratio is 10 ~ 50%; With DMA or DMF for solvent, reaction system solid content is 20 ~ 30%; Polymerization reaction 20 ~ 24 hours under room temperature condition, obtains the polyamic acid solution of high viscosity containing carboxyl structure; Then chemical imidization reagent acetic anhydride and triethylamine that volume ratio is 2:1 is added, 40 ~ 60 DEG C are reacted 2 ~ 3 hours, 110 ~ 120 DEG C are reacted 1 ~ 2 hour, discharging in distilled water, product, after pulverizer is pulverized, washs 5 ~ 7 times with ethanol and deionized water respectively, 50 ~ 80 DEG C of vacuumize 20 ~ 30 hours, what obtain white contains carboxyl structure polyimide polymer sample, and productive rate is 96 ~ 98%, and its structural formula is as follows:
Wherein m, n represent the percentage composition of each repeating unit, m+n=1, and 0.5≤m≤0.9;
B) with N, N-dimethylacetylamide is solvent, what step a) obtained is configured to containing carboxyl structure polyimide polymer the Polymer Solution that mass percent concentration is 15 ~ 25%, adding is the nano silicon of particle size range 200 ~ 300nm containing carboxyl structure polyimide polymer quality 2 ~ 5% again, through ultrasonic wave dispersion, obtain being dispersed with nano silicon containing carboxyl structure polyimide solution;
C) by step b) obtain be dispersed with nano silicon containing carboxyl structure polyimide solution, with the scraper knifing of 20 ~ 80 μm on the glass plate of level, leave standstill, after 10 ~ 30 seconds, polymeric membrane is at the uniform velocity immersed in n-butanol and N at ambient temperature together with glass plate, in the mixed solvent (n-butanol accounts for 70 ~ 90% of mixed solvent volume) of N-dimethylacetylamide, solidify 5 ~ 20 minutes, take out the composite membrane of polymer of solidification, by its washing by soaking 4 ~ 6 times in ethanol, the N that removing is residual, N-dimethylacetylamide and n-butanol, finally by composite membrane of polymer vacuumize under 40 ~ 60 DEG C of conditions, obtain of the present invention containing carboxyl structure Polyimide/Nano silicon dioxide composite porous film.
A kind of containing carboxyl structure Polyimide/Nano silicon dioxide composite porous film, it is prepared by as above method, perforated membrane thickness is 20 ~ 80 μm, porosity 60 ~ 70% (n-butanol method mensuration), pore structure is mutually through spongy hole, and aperture size is between 500nm ~ 1 μm.
The Advantageous Effects that the present invention produces:
1, the present invention adopt phase separation method to prepare containing carboxyl structure Polyimide/Nano silicon dioxide composite porous film have pore structure evenly and mutually through, pore-size distribution is narrower, the advantage of high porosity etc.
2, containing carboxyl structure Polyimide/Nano silicon dioxide composite porous film, there is excellent resistance to elevated temperatures and heat resistanceheat resistant shrinkage, from the angle of lithium battery diaphragm, the security performance of lithium battery can be ensured.
3, the existence of Nano particles of silicon dioxide improves electrolyte resistance ability and the chemical stability of perforated membrane effectively.
What the present invention obtained can be applied in field of lithium ion battery containing carboxyl structure Polyimide/Nano silicon dioxide composite porous film, particularly obtains fail safe for raising lithium ion battery and has important function.
Accompanying drawing explanation
Fig. 1 for containing carboxyl structure polyimides infrared spectrogram (in Fig. 1 a curve to be carboxyl molar content be 10% polyimides infrared spectrum, in Fig. 1 b curve to be carboxyl molar content be 50% polyimides infrared spectrum);
Fig. 2 for containing carboxyl structure polyimides thermogravimetric curve (in Fig. 1 a curve to be carboxyl molar content be 10% polyimides thermogravimetric curve, in Fig. 1 b curve to be carboxyl molar content be 50% polyimides thermogravimetric curve, in Fig. 1 c curve to be carboxyl molar content be 100% polyimides thermogravimetric curve);
Fig. 3 is the stress-strain diagram curve containing carboxyl structure polyimide polymer prepared by embodiment 1;
Fig. 4 be the embodiment of the present invention 1 prepare containing carboxyl structure Polyimide/Nano silicon dioxide composite porous film surface SEM photo;
Fig. 5 be the embodiment of the present invention 1 prepare containing carboxyl structure Polyimide/Nano silicon dioxide composite porous film section SEM photo.
Embodiment
Below in conjunction with specific embodiments and the drawings, further explanation is set forth to the present invention.
Embodiment 1
In the 250mL there-necked flask that stirrer, thermometer, nitrogen protection are housed; add 0.3313g (0.0022mol) 3; 5-diaminobenzoic acid (DABA), 9.8192g (0.022mol) hexafluoro acid anhydrides (6FDA), 6.3330g (0.020mol) 4; 4 '-diaminourea-2; 2 '-bis trifluoromethyl biphenyl (TFMB); [3; 5-diaminobenzoic acid/(3; 5-diaminobenzoic acid+4; 4 '-diaminourea-2,2 '-bis trifluoromethyl biphenyl)] mol ratio is 10%.Add 120mLN, N-dimethylacetylamide (solid content 15%), stir 20 hours under condition under room temperature, obtain the polyamic acid solution of thickness.Add 14mL acetic anhydride and 7mL triethylamine chemical imidization reagent, 40 DEG C of reactions 2 hours, raised temperature to 110 DEG C continued reaction response 1 hour.Discharging in cold water.After pulverizer is pulverized, wash 5 times with ethanol and deionized water respectively, 50 DEG C of vacuumize 24 hours.Obtain the white polyimide powder sample that carboxyl molar content is 10%, productive rate is 98%.Infra-red sepectrometry characterize polymers structure is shown in a curve in Fig. 1, and in polymer formulae, the infrared absorption peak of carboxyl, amido link, trifluoromethyl well can be belonged on infrared spectrum, illustrates and has successfully prepared containing carboxyl structure polyimide polymer.The temperature of polymer thermal weight loss 5% is 540 DEG C, and (Fig. 2 a), illustrates that polymer has excellent heat resistance.The hot strength 100MPa of thin polymer film, stretch modulus 2600MPa, elongation at break 10%, illustrates that polymer has excellent mechanical property (Fig. 3).
Embodiment 2
As embodiment 1, change 3, the molar content of 5-diaminobenzoic acid is 50%, add 1.6737g (0.011mol) 3,5-diaminobenzoic acid (DABA), 9.8192g (0.022mol) hexafluoro acid anhydrides (6FDA), 3.5225g (0.011mol) 4,4 '-diaminourea-2,2 '-bis trifluoromethyl biphenyl (TFMB), namely [3,5-diaminobenzoic acid/(3,5-diaminobenzoic acid+4,4 '-diaminourea-2,2 '-bis trifluoromethyl biphenyl)] mol ratio is 50%.Course of reaction and last handling process carry out according to embodiment 1, and finally obtain the white polyimide powder sample that carboxyl molar content is 50%, productive rate is 97%.Infra-red sepectrometry characterize polymers structure is shown in b curve in Fig. 1.
Embodiment 3
As embodiment 1, change 3, the molar content of 5-diaminobenzoic acid is 30%, add 1.0048g (0.0066mol) 3,5-diaminobenzoic acid (DABA), 9.8192g (0.022mol) hexafluoro acid anhydrides (6FDA), 4.9315g (0.0154mol) 4,4 '-diaminourea-2,2 '-bis trifluoromethyl biphenyl (TFMB), namely [3,5-diaminobenzoic acid/(3,5-diaminobenzoic acid+4,4 '-diaminourea-2,2 '-bis trifluoromethyl biphenyl)] mol ratio is 30%.Course of reaction and last handling process carry out as embodiment 1, and finally obtain the white polyimide powder sample that carboxyl molar content is 30%, productive rate is 98%.
Embodiment 4
As embodiment 1 to embodiment 3, DMF can be selected to be organic solvent.Preparation is containing carboxyl structure polyimide polymer according to the method described above, and productive rate is 98%.
Embodiment 5
What embodiment 1 obtained is configured to containing carboxyl structure polyimide polymer the N that mass percent concentration is 15%, (2g polymer is dissolved in the N of 14.24mL to N-dimethylacetamide solution, N-dimethylacetylamide), add the silicon dioxide (0.04g silicon dioxide) of the particle size range 200 ~ 300nm of polymer quality 2%, after ultrasonic wave dispersion, the glass plate of level carries out even blade coating with the scraper of 20 μm, leaves standstill 10 seconds.Polymeric membrane is at the uniform velocity immersed in together with glass plate the n-butanol and N that volume ratio is 90:10 at ambient temperature, in N-dimethylacetylamide mixed solvent, solidify 5 minutes, take out the composite membrane of polymer of solidification, by its washing by soaking 6 times in ethanol, the DMA that removing is residual and n-butanol, finally by composite membrane of polymer vacuumize under 40 DEG C of conditions, obtain containing carboxyl structure Polyimide/Nano silicon dioxide composite porous film.Film upper and lower surface and section hole morphological consistency good.Section and surface pore structure fully expose, and pore structure is mutually through spongy hole, even aperture distribution, aperture size between 500nm ~ 1 μm (Fig. 4, Fig. 5), porosity about 70%.This Polyimide/Nano silicon dioxide composite porous film can improve electrolyte resistance ability, even aperture distribution, can be used as lithium ion battery separator material and separation membrane material.
Embodiment 6
As embodiment 5, prolongation film was prepared according to the condition that embodiment 5 is identical contain carboxyl structure Polyimide/Nano silicon dioxide composite porous film by 10 minute and 30 minutes the curing time in n-butanol/dimethylacetylamide mixed solvent respectively.Pore structure is still mutually through spongy hole, aperture size between 500nm ~ 1 μm, porosity about 65%.
Embodiment 7
As embodiment 5, change the addition of nano silicon, add the silicon dioxide of the particle size range 200 ~ 300nm being polymer quality 5%, the method identical according to embodiment 5 and step preparation are containing carboxyl structure Polyimide/Nano silicon dioxide composite porous film.Film prepared by membrane pores structure and pore size and embodiment 5 relatively.
Embodiment 8
As embodiment 7, the volume ratio changing n-butanol and dimethylacetylamide mixed solvent is 80:20, and the method identical according to embodiment 7 and step preparation are containing carboxyl structure Polyimide/Nano silicon dioxide composite porous film.Compared with the film prepared with embodiment 7, membrane pore size slightly reduces.
Embodiment 9
As embodiment 8, the volume ratio changing n-butanol and dimethylacetylamide mixed solvent is 70:30, and the process preparation identical according to embodiment 8 contains carboxyl structure Polyimide/Nano silicon dioxide composite porous film.Compared with the film prepared with embodiment 8, membrane pores structure and pore size are without significant change.
Embodiment 10
As embodiment 5 to embodiment 9, changing polyimides DMA solution quality volume by volume concentration is 20%, (2g polymer is dissolved in the DMA of 10.68mL).Preparation is containing carboxyl structure Polyimide/Nano silicon dioxide composite porous film.Along with the increase of polymer concentration, there is the trend of reduction in aperture.
Embodiment 11
As embodiment 5 to embodiment 9, changing polyimides DMA solution quality percent concentration is 25% (2.5g polymer is dissolved in the DMA of 10.68mL).Preparation is containing carboxyl structure Polyimide/Nano silicon dioxide composite porous film.Along with the increase of polymer concentration, there is the trend of reduction in aperture.
Embodiment 12
As embodiment 5 to embodiment 11, adjustment scraper gap is 40 μm, 60 μm, 80 μm, preparation is containing carboxyl structure Polyimide/Nano silicon dioxide composite porous film, the film thickness obtained is respectively close to 40 μm, 60 μm, 80 μm, hole shape looks are mutually through spongy micropore, and size distribution is between 400nm ~ 1 μm.

Claims (2)

1., containing a preparation method for carboxyl structure Polyimide/Nano silicon dioxide composite porous film, its step is as follows:
A) preparation is containing carboxyl structure polyimide polymer: under nitrogen protection condition, with 3,5-diaminobenzoic acid, hexafluoro acid anhydrides, 4,4 '-diaminourea-2,2 '-bis trifluoromethyl biphenyl is raw material, anhydride monomers and diamine monomer 4, the mol ratio of 4 '-diaminourea-2,2 '-bis trifluoromethyl biphenyl is 1 ~ 1.02:1; The molar content controlling carboxyl structure is 10 ~ 50%, and namely [3,5-diaminobenzoic acid/(3,5-diaminobenzoic acid+4,4 '-diaminourea-2,2 '-bis trifluoromethyl biphenyl)] mol ratio is 10 ~ 50%; With DMA or DMF for solvent, reaction system solid content is 20 ~ 30%; Polymerization reaction 20 ~ 24 hours under room temperature condition, obtains the polyamic acid solution of high viscosity containing carboxyl structure; Then chemical imidization reagent acetic anhydride and triethylamine that volume ratio is 2:1 is added, 40 ~ 60 DEG C are reacted 2 ~ 3 hours, 110 ~ 120 DEG C are reacted 1 ~ 2 hour, discharging in distilled water, and product is after pulverizer is pulverized, wash 5 ~ 7 times with ethanol and deionized water respectively, 50 ~ 80 DEG C of vacuumize 20 ~ 30 hours, obtain white containing carboxyl structure polyimide polymer sample, productive rate is 96 ~ 98%, its structural formula is as follows
Wherein m, n represent the percentage composition of each repeating unit, m+n=1, and 0.5≤m≤0.9;
B) with N, N-dimethylacetylamide is solvent, what step a) obtained is configured to containing carboxyl structure polyimide polymer the Polymer Solution that mass percent concentration is 15 ~ 25%, adding is the nano silicon containing carboxyl structure polyimide polymer quality 2 ~ 5%, particle size range 200 ~ 300nm again, through ultrasonic wave dispersion, obtain being dispersed with nano silicon containing carboxyl structure polyimide solution;
C) by step b) obtain be dispersed with nano silicon containing carboxyl structure polyimide solution, with the scraper knifing of 20 ~ 80 μm on the glass plate of level, leave standstill, after 10 ~ 30 seconds, polymeric membrane is at the uniform velocity immersed in n-butanol and N at ambient temperature together with glass plate, solidify 5 ~ 20 minutes in the mixed solvent of N-dimethylacetylamide, n-butanol accounts for 70 ~ 90% of mixed solvent volume; Take out the composite membrane of polymer of solidification, by its washing by soaking 4 ~ 6 times in ethanol, the DMA that removing is residual and n-butanol, finally by composite membrane of polymer vacuumize under 40 ~ 60 DEG C of conditions, obtain containing carboxyl structure Polyimide/Nano silicon dioxide composite porous film.
2. one kind contains carboxyl structure Polyimide/Nano silicon dioxide composite porous film, it is characterized in that: be prepared by method according to claim 1, and perforated membrane thickness is 20 ~ 80 μm, porosity 60 ~ 70%, pore structure is mutually through spongy hole, and aperture size is between 500nm ~ 1 μm.
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Cited By (4)

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Publication number Priority date Publication date Assignee Title
WO2018163203A1 (en) 2017-03-06 2018-09-13 Council Of Scientific And Industrial Research Porous polybenzimidazole as separator for lithium ion batteries
CN109411680A (en) * 2018-10-29 2019-03-01 东莞理工学院 A kind of aramid fiber resin base micropore lithium electric separator and preparation method thereof
CN112521853A (en) * 2020-11-10 2021-03-19 泗县钧科新材料科技有限公司 High-performance powder coating and preparation method thereof
CN114243203A (en) * 2021-12-01 2022-03-25 远景动力技术(江苏)有限公司 High-elongation diaphragm, preparation method thereof and lithium ion battery

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CN103012821A (en) * 2011-09-20 2013-04-03 达胜科技股份有限公司 Polyimide film
CN103554533A (en) * 2013-10-27 2014-02-05 福建师范大学 Corona-resistant polyimide/silica nano composite film and preparation method thereof
KR20150093030A (en) * 2014-02-06 2015-08-17 현대중공업 주식회사 Hybrid ion exchange membrane for secondary battery

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Publication number Priority date Publication date Assignee Title
CN102417604A (en) * 2010-09-28 2012-04-18 中国科学院兰州化学物理研究所 Preparation method of polyimide porous film
CN103012821A (en) * 2011-09-20 2013-04-03 达胜科技股份有限公司 Polyimide film
CN103554533A (en) * 2013-10-27 2014-02-05 福建师范大学 Corona-resistant polyimide/silica nano composite film and preparation method thereof
KR20150093030A (en) * 2014-02-06 2015-08-17 현대중공업 주식회사 Hybrid ion exchange membrane for secondary battery

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018163203A1 (en) 2017-03-06 2018-09-13 Council Of Scientific And Industrial Research Porous polybenzimidazole as separator for lithium ion batteries
EP3592799A4 (en) * 2017-03-06 2020-12-30 Council of Scientific and Industrial Research Porous polybenzimidazole as separator for lithium ion batteries
CN109411680A (en) * 2018-10-29 2019-03-01 东莞理工学院 A kind of aramid fiber resin base micropore lithium electric separator and preparation method thereof
CN112521853A (en) * 2020-11-10 2021-03-19 泗县钧科新材料科技有限公司 High-performance powder coating and preparation method thereof
CN114243203A (en) * 2021-12-01 2022-03-25 远景动力技术(江苏)有限公司 High-elongation diaphragm, preparation method thereof and lithium ion battery

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