CN102140734B - Enhanced bi-component nanofiber porous membrane and preparation method thereof - Google Patents
Enhanced bi-component nanofiber porous membrane and preparation method thereof Download PDFInfo
- Publication number
- CN102140734B CN102140734B CN2011100032136A CN201110003213A CN102140734B CN 102140734 B CN102140734 B CN 102140734B CN 2011100032136 A CN2011100032136 A CN 2011100032136A CN 201110003213 A CN201110003213 A CN 201110003213A CN 102140734 B CN102140734 B CN 102140734B
- Authority
- CN
- China
- Prior art keywords
- membrane
- film
- polyurethane
- bicomponent fibers
- component
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Classifications
-
- 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
Landscapes
- Nonwoven Fabrics (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Cell Separators (AREA)
Abstract
The invention relates to an enhanced bi-component nanofiber porous membrane and a preparation method thereof. The porous membrane is a lithium ion battery membrane with two components of polymer resin and polyurethane. The membrane is in a semi-interpenetrating network structure which has a void ratio of 60-80%, and the mechanical property is 2-3 times higher than a single-component porous membrane of polymer resin. The preparation method comprises the steps of: dissolving a polymer resin and polyurethane prepolymer bi-component composition in a solvent, and preparing a nonwoven membrane through an electrospinning technology; and putting the nonwoven membrane at room temperature to make -NCO in the polyurethane prepolymer react with the -OH bond of water in the air to produce polyurethane through crosslinking and autopolymerization. In the invention, the nanofiber in the nonwoven membrane binds to form the polymer resin and polyurethane bi-component compound membrane, and the mechanical strength of the fibrous membrane is improved greatly. The method is easy, and the prepared nonwoven membrane maintains the advantages of high void ratio, and good thermal stability of polymer resin of the membrane prepared by using the electrospinning technology, and the membrane has good ion permeability and electrolyte affinity.
Description
Technical field
The present invention relates to the lithium battery diaphragm field, particularly the good lithium ion battery separator of one type of porosity height, Heat stability is good, mechanical strength with and preparation method thereof.Barrier film of the present invention can also be as the diaphragm material of fuel cell etc.
Technical background
Compare with other rechargeable batteries, lithium ion battery have voltage height, specific energy high, discharge and recharge that life-span length, memory-less effect, environmental pollution are little, advantage such as quick charge, self-discharge rate are low.As one type of important chemical cell, the electric powered motor field by being applied to mobile phone, notebook computer, digital camera, portable small-sized electrical equipment, submarine, space flight, aviation field, is progressively moved towards in the lithium ion battery applications field.Under the more and more severeer situation of global energy and environmental problem, it is the major impetus source that the vehicles are used energy-storage battery one after another instead, so lithium ion battery progressively is widely used.Lithium battery mainly is made up of positive pole, negative pole, electrolyte, barrier film and shell etc.Its septation is the important component part of lithium ion battery, has two main effects: the one, the battery positive and negative electrode is separated, and prevent short circuit between electrodes; The 2nd, the passage of ion transportation is provided in charge and discharge process for battery.The performance of barrier film has significant effects to performances such as the charge-discharge performance of lithium ion battery, current density, cycle performances.Therefore, require characteristics such as battery diaphragm must possess good insulation preformance, porosity is high, mechanical property is good, chemical stability excellence.
At present, diaphragm material is mainly the porous polyolefin, as: polypropylene (PP), polyethylene (PE) individual layer; Or the compound multilayer microporous film of PE and PP etc.; Adopt of its preparation method melt extrudes the TPO material more, makes it form the semi-crystalline polymer film, then film carried out single shaft or biaxial stretch-formed; Make film surface form long and narrow micropore, thereby make battery diaphragm.This production technology is comparatively loaded down with trivial details; The battery diaphragm quality stability that is obtained is relatively poor, and adopts the battery diaphragm aperture of this prepared less, and porosity is lower; Its aperture is about between the 0.1-0.5 μ m; Porosity is merely 40%, and pick up is relatively poor, is unfavorable for the migration of lithium ion in the battery charge and discharge process; In addition, the polyolefin battery separation film surface energy is low, causes film relatively poor to the wetting property of electrolyte, thereby has limited lithium battery in numerous high-tech sectors, the particularly high-power application that charges and discharge the field.
Electrostatic spinning technique is a kind of fiber production technology of rising in recent years, and this techniques make use Polymer Solution or melt polarize under the effect of high voltage electric field, and under the driving of electric field force; Overcome the constraint of solution surface tension; Ejection forms jet from spinneret, and jet moves in electric field, and cracking, refinement constantly take place; Through the cooling of solvent evaporates or melt and fixed, and finally form fabric nonwoven cloth.Adopt the fiber non-woven cloth diaphragm of electrostatic spinning technique preparation to have: fibre diameter is about for a short time that 200-800nm, specific area are big, porosity is up to the characteristics of 60%-80%, porous nickel and low production cost; The TPO diaphragm material porosity that can overcome existing prepared is low, and pick up is few, the shortcoming of wetting property difference.And adopt the barrier film of electric spinning process preparation, can realize regulation and control through to control of process parameters such as spinning solution character, spinning distance, electric-field intensity to the performances such as diameter, pore-size distribution and porosity of non-woven fabrics fiber.
Fluoropolymer resin is one type of resin with good heat resistance and corrosion resistance, can use down and indeformable at-40-150 ℃; Mechanical performance is strong, chemical stability is good, and the corrosion and the swelling of ability antioxidant, acid, alkali, salt, halogen, aromatic hydrocarbons, fat and chloro thing solvent can well adapt to the environment in the lithium battery.
Adopt electric spinning technique can with polymer resin solution prepare fibre diameter evenly, even aperture distribution, ion see through the high-performance lithium battery diaphragm that efficient is high, wetting property is good, temperature resistant grade is high, thermal dimensional stability is excellent.
Although adopt the nanofiber lithium battery diaphragm of electrical spinning method preparation to have ion permeability ability and good wetting property preferably; And obviously improve than TPO barrier film temperature tolerance; Thermal dimensional stability can be improved significantly; But the self closing decreased performance of battery, the mechanical performance of nano fiber porous film is relatively poor simultaneously, does not many times all reach the intensity of assembled battery.For further obtaining the barrier film of high-mechanical property, high security, introduce lower enclosed polyurethane performed polymer (PUR) polymerization reaction take place of fusing point, make it to form half interpenetrating network structure with polymer.Can prepare both had high porosity, good wetting property; The lithium ion battery that has high mechanical properties and self closing performance again concurrently is with fluoropolymer resin and the two component barrier films of polyurethane (PU); Thereby make the lithium ion battery performance be further enhanced, Application Areas obtains expanding.
Summary of the invention
It is high that the object of the invention aims to provide a kind of porosity, and wetting property is good, has lithium ion battery separator of very good mechanical properties and certain self closing performance and preparation method thereof concurrently.
For realizing above-mentioned purpose; The technical scheme that the present invention adopts is: a kind of bicomponent fibers perforated membrane is characterized in that described perforated membrane is fluoropolymer resin and polyurethane two-component film; It is the nano fiber non-woven fabric that the two component systems by enclosed polyurethane performed polymer and fluoropolymer resin are prepared into through electrostatic spinning technique; This nonwoven fabric placed under the high temperature handle, make wherein that the end group deblocking of base polyurethane prepolymer for use as obtains isocyanate groups, in the base polyurethane prepolymer for use as-NCO key and water in air-OH key crosslinked, the auto polymerization generation polyurethane that reacts; Thereby prepare fluoropolymer resin and polyurethane bicomponent fiber multihole film; Its film is a half interpenetrating network structure, and porosity is up to 60%-80%, and the TENSILE STRENGTH of film improves 2-3 doubly than fluoropolymer resin one-component fiber multihole film.
In the scheme of the present invention, described fluoropolymer resin is meant polymethyl methacrylate, Kynoar, Kynoar-hexachloropropylene copolymer, polyester or the fine resin of polypropylene.
Base polyurethane prepolymer for use as of the present invention is meant by methyl diphenylene diisocyanate and the reaction of crystallinity polyester diol and obtains;-NCO group containing ratio surpasses the polymer of 5wt%, again with caprolactam right-the NCO group carries out resulting base polyurethane prepolymer for use as after the termination process.
Crystallinity polyester diol of the present invention is meant gathers adipic acid 1,6-hexylene glycol esterdiol, gathers adipic acid 1,4-butanediol ester glycol, polyethylene glycol adipate glycol or polycaprolactone.
In the scheme of the present invention, the preparation method of described bicomponent fibers perforated membrane comprises the following steps:
1), be that two component systems of 8: 92 are dissolved in the solvent with fluoropolymer resin and enclosed polyurethane performed polymer mass ratio, form the solution system of stable homogeneous, solution concentration is 11wt%-20wt%;
2), step 1) gained solution is packed in the syringe pump of electro-spinning equipment, the solution interface in the syringe pump extremely links to each other with one of high voltage source through lead; At the metal collection unit of placing a ground connection apart from the opposite side of syringe pump 10-25cm; Metal collection unit is a metal plate, or the metal roller electrode;
3), rising supply voltage; And the injection flow stream velocity of adjusting syringe pump, solution penetrates from the flat lancet head nozzle of syringe pump under the effect of high voltage electric field; It is moving and tangle that whip takes place in the motion process, and finally the film with the form of nonwoven fabric is collected on the metal collection unit; Gained nonwoven film is placed vacuum drying chamber, and normal temperature decompression operation 10-16h treats in the film behind the noresidue solvent, takes out;
4), the nanofiber nonwoven film of step 3) preparation be placed in the baking oven 110-180 ℃ handled 10-30 minute, the constant temperature of putting into temperature again and be 90-110 ℃, humidity and be 50%-75% adds wet tank and handles 1-3h, makes composite membrane;
5), the composite membrane of step 4) preparation is placed air humidity is 50%-75%, temperature is under 20-45 ℃ the condition 1-3 days, promptly makes fluoropolymer resin and polyurethane two-component nano fiber porous film;
Wherein, described fluoropolymer resin is meant polymethyl methacrylate, Kynoar, Kynoar-hexachloropropylene copolymer, polyester or the fine resin of polypropylene; Described enclosed polyurethane performed polymer be meant wherein end group separate be honored as a queen-NCO group containing ratio surpasses the base polyurethane prepolymer for use as of 5wt%.
In the scheme of the present invention, the two used solvents of component system of fluoropolymer resin and base polyurethane prepolymer for use as are N, dinethylformamide, or N, the mixture of dinethylformamide and acetone, or N, the mixture of dinethylformamide toluene.
It is following that the bicomponent fibers perforated membrane of preparation carries out measuring mechanical property:
The bicomponent fibers perforated membrane is cut into the rectangle batten of 10mm * 60mm; Every group of sample number is 4-8, sample is fixed in the paper square frame, at electronic tensile machine (M350-20KN; Britain Testometric company) upward sample is carried out tension test; The effective tensile elongation of sample is 40mm, and rate of extension is 10mm/min, and institute uses sensor to be 10N.
Compared with prior art, bicomponent fibers perforated membrane of the present invention (as lithium ion battery separator) has the following advantages:
1, the bicomponent fibers perforated membrane of preparation has higher porosity and good affinity ability, can improve the penetrating rate of ion.
2, the thermal stability of bicomponent fibers perforated membrane is improved, and through introducing among the PUR-cross-linking reaction of NCO group, the nanofiber in the tunica fibrosa is bondd each other, and form inierpeneirating network structure, thereby improved the mechanical strength of tunica fibrosa.
Test shows, the bicomponent fibers perforated membrane of employing the present invention preparation improves 2-3 doubly than the tensile mechanical properties of single polymers resin lithium-ion membrane.
Preparation method of the present invention can make and form half interpenetrating network structure in the nonwoven fabric, and the raising mechanical strength of film has certain self closing performance again simultaneously, and the performance of lithium battery is improved.
Description of drawings
Fig. 1 fluoropolymer resin and base polyurethane prepolymer for use as nanoporous tunica fibrosa SEM figure
Fig. 2 fluoropolymer resin and polyurethane two-component fiber multihole film SEM figure
The specific embodiment
Through embodiment the present invention is detailed below.
Embodiment 1
1, the preparation of PVDF and PUR bicomponent fibers film
Kynoar (PVDF) and PUR are dissolved in N by mass ratio=92: 8; In the mixed solvent of dinethylformamide (DMF) and acetone mass ratio=5: 5; Be mixed with the solution that concentration is 12wt%, at 50-60 ℃ of following heated and stirred 10-20 minute, to reach abundant dissolving.The solution that obtains is injected in the syringe pump that has the flat lancet head of 8#, and syringe needle connects high-voltage output end, is the metal roller electrode with high voltage source ground connection at the other end apart from syringe pump 15cm, as gathering-device.The injection speed of regulating syringe pump is 0.3ml/h, and slowly boosted voltage is to 15kv.Described solution is under the effect of high pressure; Gush out from the syringe needle of syringe pump, be collected on the metal collection unit, gained nonwoven film is placed vacuum drying chamber with the film of the form of nonwoven fabric; Normal temperature decompression operation 12h; Treat in the film behind the noresidue solvent, take out, obtain PVDF and PUR pair of component nano fiber porous films.Its SEM figure is like Fig. 1.
2.PVDF preparation with the PU composite cellulosic membrane
(1) the two component nano fiber porous films of the PVDF for preparing and PUR are placed in the baking oven 150 ℃ and handled 20 minutes, the constant temperature of putting into 110 ℃ of temperature, humidity again and be 50%-75% adds wet tank and handles 2h, makes PVDF and PUR composite membrane;
(2) its composite membrane being placed air humidity is 50%-75%, and temperature is under 20-45 ℃ the condition 1-3 days, promptly prepares PVDF and PU bi-component nano fiber porous film.Its SEM figure is like Fig. 2.
3. the test of tunica fibrosa mechanical performance
Pvdf membrane, PVDF and the PU composite cellulosic membrane of preparation is cut into the rectangle batten of 10mm * 60mm; Every group of sample number is 6, sample is fixed in the paper square frame, at electronic tensile machine (M350-20KN; Britain Testometric company) upward sample is carried out tension test; The effective tensile elongation of sample is 40mm, and rate of extension is 10mm/min, and institute uses sensor to be 10N.
The TENSILE STRENGTH that test shows has been introduced the nano fiber porous film of PUR formation half interpenetrating network structure obviously strengthens, and improves about 2.4 times.(seeing table 1)
Embodiment 2
1, the preparation of PVDF-HFP and PUR bicomponent fibers film
Kynoar-hexachloropropylene (PVDF-HFP) and PUR are dissolved in N by mass ratio=92: 8; In the mixed solvent of dinethylformamide (DMF) and acetone mass ratio=8: 2; Be mixed with the solution that concentration is 16wt%, at 50-60 ℃ of following heated and stirred 10-20 minute, to reach abundant dissolving.Solution is injected in the syringe pump that has the flat lancet head of 8#, and syringe needle connects high-voltage output end, is the metal roller electrode with high voltage source ground connection at the other end apart from syringe pump 15cm, as gathering-device.The injection speed of regulating syringe pump is 0.47ml/h, and slowly boosted voltage is to 15kv.Described solution is under the effect of high pressure; Gush out from the syringe needle of syringe pump, be collected on the metal collection unit, gained nonwoven film is placed vacuum drying chamber with the film of the form of nonwoven fabric; Normal temperature decompression operation 12h; Treat in the film behind the noresidue solvent, take out, obtain PVDF-HFP and PUR pair of component nano fiber porous films.Its SEM figure is like Fig. 1.
2.PVDF-HFP preparation with the PU composite cellulosic membrane
(1) the two component nano fiber porous films of the PVDF-HFP for preparing and PUR are placed in the baking oven 165 ℃ and handled 15 minutes, the constant temperature of putting into 110 ℃ of temperature, humidity again and be 50%-75% adds wet tank and handles about 1h, makes PVDF-HFP and PUR composite membrane;
(2) its composite membrane being placed air humidity is 50%-75%, and temperature is under 20-45 ℃ the condition 1-3 days, promptly prepares PVDF-HFP and PU composite nano fiber perforated membrane.Its SEM figure is like Fig. 2.
3. the test of tunica fibrosa mechanical performance
Test condition and embodiment 1 are together.
The mechanical property that test shows has been introduced the nano fiber porous film of PUR formation half interpenetrating network structure obviously strengthens, and improves about 2 times (seeing table 1).
Embodiment 3
1, the preparation of PMMA and PUR bicomponent fibers film
Polymethyl methacrylate (PMMA) and PUR are dissolved in N by mass ratio=92: 8, in the mixed solvent of dinethylformamide (DMF) and toluene mass ratio=6: 4, are mixed with the solution that concentration is 20wt%, at room temperature stir 24h, to reach abundant dissolving.Solution is injected in the syringe pump that has the flat lancet head of 8#, and syringe needle connects high-voltage output end, is the metal roller electrode with high voltage source ground connection at the other end apart from syringe pump 18cm, as gathering-device.The injection speed of regulating syringe pump is 0.2ml/h, and slowly boosted voltage is to 15kv.Described solution gushes out from the syringe needle of syringe pump under the effect of high pressure, is collected on the metal collection unit with the film of the form of nonwoven fabric; Gained nonwoven film is placed vacuum drying chamber, and normal temperature decompression operation 16h treats in the film behind the noresidue solvent; Take out, get PMMA and PUR bicomponent fibers film.Its SEM figure is like Fig. 1.
2.PMMA preparation with the PU composite cellulosic membrane
(1) the two component nano fiber porous films of the PMMA for preparing and PUR are placed in the baking oven 110 ℃ and handled 30 minutes, the constant temperature of putting into 90 ℃ of temperature, humidity again and be 50%-75% adds wet tank and handles 3h, makes PMMA and PUR composite membrane;
(2) its composite membrane being placed air humidity is 50%-75%, and temperature is under 20-45 ℃ the condition 1-3 days, finally prepares PMMA and PU bi-component nano fiber porous film.Its SEM figure is like Fig. 2.
3. the test of tunica fibrosa mechanical performance
Test condition and embodiment 1 are together.
The mechanical property that test shows has been introduced the nano fiber porous film of PUR formation half interpenetrating network structure obviously strengthens, and improves about 2 times.(seeing table 1).
Embodiment 4
1, the preparation of PAN and PUR bicomponent fibers film
Polypropylene fine (PAN) and PUR by mass ratio=be dissolved in N at 92: 8, in dinethylformamide (DMF) solvent, are mixed with the solution that concentration is 11wt%, at room temperature stir 12h, to reach abundant dissolving.Solution is injected in the syringe pump that has the flat lancet head of 6#, and syringe needle connects high-voltage output end, is the metal roller electrode with high voltage source ground connection at the other end apart from syringe pump 25cm, as gathering-device.The injection speed of regulating syringe pump is 0.3ml/h, and slowly boosted voltage is to 18kv.Described solution gushes out from the syringe needle of syringe pump under the effect of high pressure, is collected on the metal collection unit with the film of the form of nonwoven fabric; Gained nonwoven film is placed vacuum drying chamber, and normal temperature decompression operation 12h treats in the film behind the noresidue solvent; Take out, get PAN and PUR bicomponent fibers film.Its SEM figure is like Fig. 1.
2.PAN preparation with the PU composite membrane
(1) the two component nano fiber porous films of the PAN for preparing and PUR are placed in the baking oven 180 ℃ and handled 10 minutes, the constant temperature of putting into 110 ℃ of temperature, humidity again and be 50%-75% adds wet tank and handles 2h, makes PAN and PUR composite membrane;
(2) PAN and PUR composite membrane being placed air humidity is 50%-75%, and temperature is under 20-45 ℃ the condition 1-3 days, finally prepares PAN and PU bi-component nano fiber porous film.Its SEM figure is like Fig. 2.
3. the test of tunica fibrosa mechanical performance
Test condition and embodiment 1 are together.
The mechanical property that test shows has been introduced the nano fiber porous film of PUR formation half interpenetrating network structure obviously strengthens, and improves about 3 times.(seeing table 1).
Embodiment 5
1, the preparation of PET and PUR bicomponent fibers film
Polyester (PET) and PUR are dissolved in N by mass ratio=92: 8, in the mixed solvent of dinethylformamide (DMF) and toluene mass ratio=6: 4, are mixed with the solution that concentration is 20wt%, at room temperature stir 24h, to reach abundant dissolving.Solution is injected in the syringe pump that has the flat lancet head of 6#, and syringe needle connects high-voltage output end, is the metal roller electrode with high voltage source ground connection at the other end apart from syringe pump 10cm, as gathering-device.The injection speed of regulating syringe pump is 0.2ml/h, and slowly boosted voltage is to 15kv.Polymer Solution gushes out from the syringe needle of syringe pump under the effect of high pressure, is collected on the metal collection unit with the film of the form of nonwoven fabric; Gained nonwoven film is placed vacuum drying chamber, and normal temperature decompression operation 16h treats in the film behind the noresidue solvent; Take out, get PET and PUR bicomponent fibers film.Its SEM figure is like Fig. 1.
2.PET preparation with the PU composite cellulosic membrane
(1) the two component nano fiber porous films of the PET for preparing and PUR are placed in the baking oven 180 ℃ and handled 10 minutes, the constant temperature of putting into 110 ℃ of temperature, humidity again and be 50-75% adds wet tank and handles about 3h, makes PET and PUR composite membrane;
(2) PET and PUR composite membrane being placed air humidity is 50-75%, and temperature is under 20-45 ℃ the condition 1-3 days, finally prepares PET and PU composite nano fiber perforated membrane.Its SEM figure is like Fig. 2.
3. the test of tunica fibrosa mechanical performance
Test condition and embodiment 1 are together.
The mechanical property that test shows has been introduced the nano fiber porous film of PUR formation half interpenetrating network structure obviously strengthens, and improves about 2.8 times.(seeing table 1)
Table 1
Claims (6)
1. bicomponent fibers perforated membrane; It is characterized in that described bicomponent fibers perforated membrane is the bicomponent fibers perforated membrane that polyurethane and another kind of fluoropolymer resin are formed, it is the nano fiber non-woven fabric that the two component systems by enclosed polyurethane performed polymer and another kind of fluoropolymer resin are prepared into through electrostatic spinning technique; With this nonwoven fabric place earlier under the high temperature handle after; Add wet process through constant temperature again, placing air humidity at last is 50%-75%, and temperature is to leave standstill 1-3 days under 20-45 ℃ the condition; Make the end group deblocking of enclosed polyurethane performed polymer wherein obtain having the base polyurethane prepolymer for use as of isocyanate groups; In the base polyurethane prepolymer for use as-NCO key and water in air-react crosslinked, the auto polymerization of OH key generates polyurethane, thus prepare the bicomponent fibers perforated membrane of forming by polyurethane and another kind of fluoropolymer resin, and its film is a half interpenetrating network structure; Porosity is up to 60%-80%, and the TENSILE STRENGTH of film improves 2-3 doubly than fluoropolymer resin one-component fiber multihole film.
2. bicomponent fibers perforated membrane according to claim 1; It is characterized in that described fluoropolymer resin is meant polymethyl methacrylate, Kynoar, Kynoar-hexachloropropylene copolymer, PETG or polyacrylonitrile resin.
3. bicomponent fibers perforated membrane according to claim 1; It is characterized in that; Described enclosed polyurethane performed polymer be meant by the reaction of methyl diphenylene diisocyanate and crystallinity polyester diol obtain-NCO group containing ratio surpasses the polymer of 5wt%, again with caprolactam right-the NCO group carries out the base polyurethane prepolymer for use as that obtains after the termination process.
4. bicomponent fibers perforated membrane according to claim 3 is characterized in that, described crystallinity polyester diol is meant gathers adipic acid 1,6-hexylene glycol esterdiol, gathers adipic acid 1,4-butanediol ester glycol or polyethylene glycol adipate glycol.
5. prepare the method for the described bicomponent fibers perforated membrane of claim 1, it is characterized in that, comprise the following steps:
1), be that two component systems of 92:8 are dissolved in the solvent with a kind of fluoropolymer resin and enclosed polyurethane performed polymer mass ratio, form the solution system of stable homogeneous, solution concentration is 11 wt%-20wt%;
2), step 1) gained solution is packed in the syringe pump of electro-spinning equipment, the solution interface in the syringe pump extremely links to each other with one of high voltage source through lead; At the metal collection unit of placing a ground connection apart from the opposite side of syringe pump 10-25cm;
3), rising supply voltage; And the injection flow stream velocity of adjusting syringe pump, solution penetrates from the flat lancet head nozzle of syringe pump under the effect of high voltage electric field; It is moving and tangle that whip takes place in the motion process, and finally the film with the form of nonwoven fabric is collected on the metal collection unit; Gained nonwoven film is placed vacuum drying chamber, and normal temperature decompression operation 10-16h treats in the film behind the noresidue solvent, takes out;
4), the nanofiber nonwoven film of step 3) preparation be placed in the baking oven 110-180 ℃ handled 10-30 minute, the constant temperature of putting into temperature again and be 90-110 ℃, humidity and be 50%-75% adds wet tank and handles 1-3h, makes composite membrane;
5), the composite membrane of step 4) preparation is placed air humidity is 50%-75%, temperature is under 20-45 ℃ the condition 1-3 days, promptly makes fluoropolymer resin and polyurethane two-component nano fiber porous film;
Wherein, described fluoropolymer resin is meant polymethyl methacrylate, Kynoar, Kynoar-hexachloropropylene copolymer, PETG or polyacrylonitrile resin; Described enclosed polyurethane performed polymer be meant by the reaction of methyl diphenylene diisocyanate and crystallinity polyester diol obtain-NCO group containing ratio surpasses the polymer of 5wt%, again with caprolactam right-the NCO group carries out the base polyurethane prepolymer for use as that obtains after the termination process.
6. the preparation method of bicomponent fibers perforated membrane according to claim 5; It is characterized in that; The used solvent of bicomponent system of two kinds of fluoropolymer resin compositions is N; Dinethylformamide or N, the two component solvents or the N of dinethylformamide and acetone, two component solvents of dinethylformamide and toluene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100032136A CN102140734B (en) | 2011-01-10 | 2011-01-10 | Enhanced bi-component nanofiber porous membrane and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100032136A CN102140734B (en) | 2011-01-10 | 2011-01-10 | Enhanced bi-component nanofiber porous membrane and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102140734A CN102140734A (en) | 2011-08-03 |
| CN102140734B true CN102140734B (en) | 2012-12-19 |
Family
ID=44408514
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011100032136A Expired - Fee Related CN102140734B (en) | 2011-01-10 | 2011-01-10 | Enhanced bi-component nanofiber porous membrane and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102140734B (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102660794B (en) * | 2012-04-25 | 2014-01-29 | 东华大学 | Method for single-spinning poly-(vinyl caprolactam-co-methacrylic acid) nanometer fiber through static spinning technology |
| FI2781637T3 (en) * | 2012-11-30 | 2024-05-16 | Lg Energy Solution Ltd | Nonwoven fabric formed from fiber coated with organic binder polymer compound, electrochemical device comprising nonwoven fabric, and method for manufacturing nonwoven fabric |
| CN103015036B (en) * | 2012-12-27 | 2015-05-06 | 东南大学 | Mosaic-type nano film |
| CN103437067B (en) * | 2013-09-05 | 2015-08-05 | 天津工业大学 | A kind of manufacture method of oil suction fibre felt |
| KR101886190B1 (en) * | 2015-09-24 | 2018-08-08 | 주식회사 아모그린텍 | Separator for fuel cell, method for manufacturing the same and fuel cell electrode assembly |
| CN106087246A (en) * | 2016-07-30 | 2016-11-09 | 浙江理工大学 | A kind of superfine fibre strengthens hyaline membrane and preparation method thereof |
| CN106480710A (en) * | 2016-09-23 | 2017-03-08 | 安徽工程大学 | A kind of preparation method of feature PU AOPAN composite nano-fiber membrane |
| CN108017897B (en) * | 2017-11-30 | 2021-03-02 | 广西民族大学 | Polyacrylonitrile nanofiber membrane/thermoplastic polyurethane composite material and preparation method thereof |
| CN107904676B (en) * | 2017-12-05 | 2020-05-29 | 青岛大学 | Double-component reaction curing type solvent-free electrospinning device |
| CN108570767B (en) * | 2018-05-10 | 2021-08-13 | 苏州大学 | Preparation method of low-resistance high-filtration breathable fiber membrane |
| CN108411491B (en) * | 2018-05-14 | 2020-04-07 | 海信（山东）空调有限公司 | Preparation method of double-crosslinking electrostatic spinning fiber membrane |
| CN109346655A (en) * | 2018-09-21 | 2019-02-15 | 江苏微能电子科技有限公司 | Over capacity stablizes lithium battery and preparation method thereof |
| CN114583384A (en) * | 2022-02-24 | 2022-06-03 | 上海恩捷新材料科技有限公司 | Porous fiber composite diaphragm and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1189171A (en) * | 1995-06-07 | 1998-07-29 | H.B.福勒许可和财务有限公司 | Aqueous non-gelling anionic polyurethane dispersions and process for their manufacture |
| EP0740952B1 (en) * | 1994-01-17 | 2002-12-11 | Mitsubishi Rayon Co., Ltd. | Composite microporous polyolefin film and process for producing the same |
| CN1431253A (en) * | 2003-01-23 | 2003-07-23 | 上海交通大学 | Micro cross linking polyurethane/acrylate polymer electrolyte film and its preparing method |
| CN1856533A (en) * | 2003-09-25 | 2006-11-01 | 大赛璐化学工业株式会社 | Chemical-resistant porous film |
| CN101137422A (en) * | 2004-01-20 | 2008-03-05 | 多孔渗透电力技术公司 | Production of high porosity open-cell membranes |
| CN101270199A (en) * | 2008-05-15 | 2008-09-24 | 东华大学 | Method for improving hydrophilicity of polyacrylonitrile glycol cellulose nano-composite cellulosic membrane |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003041428A (en) * | 2001-07-26 | 2003-02-13 | Kuraray Co Ltd | Polyvinyl alcohol-based flame-resistant fiber and method for producing the same |
-
2011
- 2011-01-10 CN CN2011100032136A patent/CN102140734B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0740952B1 (en) * | 1994-01-17 | 2002-12-11 | Mitsubishi Rayon Co., Ltd. | Composite microporous polyolefin film and process for producing the same |
| CN1189171A (en) * | 1995-06-07 | 1998-07-29 | H.B.福勒许可和财务有限公司 | Aqueous non-gelling anionic polyurethane dispersions and process for their manufacture |
| CN1431253A (en) * | 2003-01-23 | 2003-07-23 | 上海交通大学 | Micro cross linking polyurethane/acrylate polymer electrolyte film and its preparing method |
| CN1856533A (en) * | 2003-09-25 | 2006-11-01 | 大赛璐化学工业株式会社 | Chemical-resistant porous film |
| CN101137422A (en) * | 2004-01-20 | 2008-03-05 | 多孔渗透电力技术公司 | Production of high porosity open-cell membranes |
| CN101270199A (en) * | 2008-05-15 | 2008-09-24 | 东华大学 | Method for improving hydrophilicity of polyacrylonitrile glycol cellulose nano-composite cellulosic membrane |
Non-Patent Citations (2)
| Title |
|---|
| JP特开2003-41428A 2003.02.13 |
| 胡晓宇，等.PU/PVDF共混物形貌及其中空纤维膜制备.《天津工业大学学报》.2008,第27卷(第3期),第9-11页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102140734A (en) | 2011-08-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102140734B (en) | Enhanced bi-component nanofiber porous membrane and preparation method thereof | |
| CN102140762B (en) | Reinforced nanofiber porous membrane and preparation method thereof | |
| Waqas et al. | Recent development in separators for high‐temperature lithium‐ion batteries | |
| CN101562243B (en) | Method for manufacturing electrospinning of high-performance polyarylether resin lithium battery diaphragm | |
| Li et al. | A review of electrospun nanofiber-based separators for rechargeable lithium-ion batteries | |
| Huang | Separator technologies for lithium-ion batteries | |
| CN104766938B (en) | A kind of compound lithium ion battery separator and preparation method thereof | |
| CN103469488A (en) | Preparation method of reinforced electrostatic spinning nano-fiber lithium-ion battery separator | |
| KR101301446B1 (en) | Secondary battery fibrous separation membrane and method thereof | |
| CN101326658B (en) | Organic/ inorganic composite separator having morphology gradient, manufacturing method thereof and electrochemical device containing the same | |
| CN102299287B (en) | Composite nanometer fiber lithium ion battery diaphragm and preparation method thereof | |
| Dai et al. | Research progress on high-temperature resistant polymer separators for lithium-ion batteries | |
| CN107819095B (en) | A kind of high security complex lithium electric separator and preparation method thereof | |
| CN103688387A (en) | Single-layer lithium ion battery separator | |
| CN107474270B (en) | Preparation method of polymer electrolyte membrane | |
| CN104466063B (en) | Poly-dopamine surface modification polyether sulfone nanofiber composite diaphragm, preparation method and application | |
| WO2008018657A1 (en) | Heat resisting separator having ultrafine fibrous layer and secondary battery having the same | |
| CN110983629B (en) | Preparation method of electrospun fiber diaphragm with excellent mechanical property | |
| CN103972452B (en) | A kind of preparation method of unidirectional enhancement mode Static Spinning lithium ion battery separator | |
| WO2012167728A1 (en) | Battery separator and method for preparing the same | |
| CN108807791B (en) | Composite diaphragm for lithium battery and preparation method thereof | |
| Tan et al. | Gel electrolytes based on polyacrylonitrile/thermoplastic polyurethane/polystyrene for lithium-ion batteries | |
| CN110233287A (en) | A kind of nylon base composite gel polymer electrolyte and preparation method thereof | |
| CN110854343B (en) | Preparation method of skin-core structure cellulose modified nanofiber lithium battery diaphragm | |
| CN103094513B (en) | Lithium ion battery film in situ preparation method, lithium ion battery film, and lithium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20121219 Termination date: 20150110 |
|
| EXPY | Termination of patent right or utility model |