CN105280939A - Device and method for preparing multi-layer composite nanofiber proton exchange membrane - Google Patents

Device and method for preparing multi-layer composite nanofiber proton exchange membrane Download PDF

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Publication number
CN105280939A
CN105280939A CN201410322908.4A CN201410322908A CN105280939A CN 105280939 A CN105280939 A CN 105280939A CN 201410322908 A CN201410322908 A CN 201410322908A CN 105280939 A CN105280939 A CN 105280939A
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spinning
proton exchange
electrostatic spinning
exchange membrane
receiving system
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陈慧明
姜涛
王丹
张克金
安宇鹏
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FAW Group Corp
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FAW Group Corp
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention relates to a device and a method for preparing a multi-layer composite nanofiber proton exchange membrane. The device is characterized in that each set of electrostatic spinning system comprises an electrostatic spinning machine with an efficient multi-needle spinning nozzle, a high-voltage direct current power supply, a metering infusion pump, a receiving device, a temperature control device and a gas recovering device, wherein a pyrrole polymerization system comprises two parts, namely a papermaking groove and a polymerization groove; the polymerization groove comprises a temperature control system; a rolling system comprises a cleaning device, a drying device and a rolling device; the rolling device comprises the temperature control system to control the rolling temperature; and all devices are in integrated uniform control through a mechanical control. A composite filament film of heteropolyacid and nanoparticles is formed on the surface of a non-fluorinated proton exchange membrane material in an electrostatic spinning manner, so that the proton exchange capacity and the mechanical strength of the material are increased.

Description

A kind of device and method preparing MULTILAYER COMPOSITE nanofiber proton exchange membrane
Technical field
The present invention relates to a kind of device and method preparing MULTILAYER COMPOSITE nanofiber proton exchange membrane, belong to battery material technical field.
Background technology
Fuel cell is the development trend of following secondary cell, the bottleneck of present fuel cell is proton exchange membrane (PEMFC), the perfluor sulfuric acid proton exchange membrane (Nafion film) that present proton exchange membrane generally adopts du pont company to develop, although this film has a lot of advantage in many-side, but still there is a lot of defects, one is the water content that the conductivity of this film depends on barrier film, and amberplex can only be used in humidified gas; Two is because perfluor acid resin sparkling temperature is lower, is 130 DEG C, and this point causes the thermal stability of barrier film poor; Three is that the mechanical strength of this barrier film and dimensional stability are not good; The price of Nafion film costliness also drastically influence the industrialization process of full vanadium cell in addition.At present like a raging fire to the research of fuel cell, therefore the demand of the proton exchange membrane of cheap, good combination property is also increased gradually, also more and more higher to the technical requirement of proton exchange membrane.In recent years, people constantly study the new material with excellent chemical performance and mechanical performance, such as non-fluorine proton exchange membrane material, such as sulfonated polyether-ether-ketone, sulfonated polyether-ether-ketone, and sulfonation gathers (ether) sulfone.But the non-fluorine proton exchange membrane of research at present generally has two problems: one is the contradiction between proton conductivity and barrier film mechanical stability; The non-oxidizability of this barrier film is poor in addition, can not meet the requirement of fuel battery service life.
This patent adopts non-fluorine proton exchange membrane as base material, at the silk union film of its surface electrostatic spinning one deck heteropoly acid and nano particle.Heteropoly acid has higher proton conducting ability, unique structure and chemical property, and the frequent electrolyte as normal temperature fuel cell and surperficial cocatalyst, can increase the ability of the proton conduction of barrier film to membrane surface by its spinning over the years.In spinning film, add mechanical strength and the mechanical stability that nano particle can improve material simultaneously, have some nano particle of bibliographical information can increase the water absorption rate of composite membrane when high temperature, such as SiO simultaneously 2, TiO 2deng.Also the coated of polypyrrole has been carried out after spinning receives, one deck polypyrrole coating layer is synthesized on the surface of barrier film, containing a large amount of NH base in polypyrrole main chain, he can produce electrostatic interaction and the score hydrogen bond action in prostatitis with heteropolyacid anions, heteropoly acid molecule firmly can be adsorbed on around polypyrrole cation, play fixing heteropoly acid, prevent it from coming off.
" a kind of preparation method of modified polyetheretherketonefiber fiber " that the patent No. is " CN101387017A " adds inorganic nano material and high-molecular organic material in polyether-ether-ketone, obtains modified polyetheretherketonefiber fiber after being shaped by hot-stretch.Similarity is not had with this patent.
" multilayer of used in proton exchange membrane fuel cell is from humidification composite membrane and preparation method thereof " that the patent No. is " CN101079487A " what deliver is porous is strengthened film upper or be coated with proton exchange film resin, form the composite membrane strengthened, pour into a mould what be made up of catalyst and proton exchange film resin from humidification composite bed or be sprayed on the composite membrane both sides of enhancing.Final formation has good stability, higher sub-conductivity and preferably from the proton exchange membrane of moisturization.Similarity is not had with this patent.
Show through the retrieval of patent and analysis, the preparation method of proton exchange membrane described in this patent does not appear in the newspapers.
Summary of the invention
The object of this invention is to provide a kind of device and method preparing MULTILAYER COMPOSITE nanofiber proton exchange membrane, at the silk union film of non-fluorine proton exchange membrane material surface electrostatic spinning one deck heteropoly acid and nano particle, increase proton exchange ability and the mechanical strength of material.
Technical scheme of the present invention is achieved in that the device of preparation MULTILAYER COMPOSITE nanofiber proton exchange membrane, comprises transmission wrap-up, two cover electrostatic spinning systems, a set of pyrroles's paradigmatic system and roll extrusion system; It is characterized in that: often cover electrostatic spinning system comprises electrostatic spinning machine, high-voltage DC power supply, metering infusion pump, the receiving system with efficient spininess spinning head, attemperating unit, gas concentration unit; Pyrroles's paradigmatic system comprises copy paper groove and polymerization tank two parts, and polymerization tank is with temperature control system; Containing cleaning device, drying unit and rolling device in roll extrusion system, rolling device contains temperature control system and controls its rolling temperatures; All devices are by the integrated unified control of Mechanical course; Non-fluorine proton exchange film base material and the transmission unwinding device of rolling are fixed; By non-fluorine proton exchange film base material by first receiving system, device for spinning is positioned on receiving system, and spinning solution is injected device for spinning, high voltage between device for spinning and receiving system, under high-tension effect, electrostatic spinning is carried out to the one side of base material.Second receiving system is positioned at directly over first receiving system, and the non-fluorine proton exchange film base material completing one side spinning is turned on second receiving system by roller, and the same device for spinning that uses carries out spinning to base material another side; Attemperating unit controls the temperature of whole spinning cabin body, and retracting device is arranged in the solvent being used for reclaiming spinning process directly over the body of spinning cabin and evaporating; The base material that spinning completes, through copy paper groove, makes substrate surface form one deck pyrroles liquid film, carries out the polymerization of pyrroles afterwards through polymerization tank; Then enter in drying unit and dry, cleaning device will be had before entering drying unit to wash barrier film, wash unnecessary liquid off; Composite diaphragm after oven dry is collected by transmission wrap-up after rolling device roll extrusion, just obtains composite diaphragm.
Described electrostatic spinning system mesohigh DC power supply of often overlapping is added between spinning syringe needle and receiving system, receiving system ground connection, and receiving system is aluminium foil; High efficiency electrostatic spinning syringe needle is single or array arrangement; The aperture of syringe needle is 0.3 ~ 1mm, and needle length is at 3 ~ 5cm.
Prepare a method for MULTILAYER COMPOSITE nanofiber proton exchange membrane, it is characterized in that concrete preparation process is as follows:
(1) configuration of electrostatic spinning solution:
The polymeric binder of certain mass and heteropoly acid are added in a certain amount of solvent, under certain condition through fully stirring, being uniformly dissolved, add nano particle afterwards wherein and continue to stir, form final electrostatic spinning solution;
(2) electrostatic spinning step:
Use syringe pump by spinning solution syringe needle under certain speed, syringe needle applies high-tension electricity, and on base material, electrostatic is weaved one deck nanofibers film; Substrate another side in the same way electrostatic to weave one deck nano fibrous membrane.Control environment in spinning process temperature;
(3) polypyrrole load:
Pyrrole is soluble in water, form certain density pyrroles's aqueous solution; Configure certain density FeCl again 3the aqueous solution.First the composite diaphragm completed by electrostatic spinning immerses in pyrroles's aqueous solution and soaks a period of time, immerses FeCl after taking out cleaning 3soak a period of time in solution, after cleaning, drying, obtain polypyrrole tack coat;
(4) heat-press step:
Obtained composite diaphragm is carried out roll extrusion by the twin rollers being heated to uniform temperature, increases the binding ability between each layer.
Described heteropoly acid comprises phosphotungstic acid (H 3pW 12o 4 .nH 2o), silico-tungstic acid (H 4siW 12o 4 .h 2o), phosphomolybdic acid (H 3pMo 12o 4 .nH 2o) etc.; Binding agent comprises polyvinyl alcohol (PVA), polypropylene fine (PAN), Kynoar-hexafluoropropylene (PVDF-HFP) etc.; Solvent comprises water, DMF (DMF), acetone etc.; Nano particle comprises Al 2o 3, SiO 2, TiO 2.
The concentration that described polymeric binder accounts for solvent is 8% ~ 15%; The quality of heteropoly acid is 0.3 ~ 1.5 times that adds polymeric binder quality; The quality of inorganic nano-particle and the mass ratio of binding agent are between 1:8 ~ 1:1; The thickness of spinning is between 30 ~ 200 μm.
Described stirring condition can be add thermal agitation, cooling for reflux stirring, ultrasonic vibration stirring etc.
Described syringe pump fltting speed is between 0.5 ~ 2ml/min; Spinning voltage is 8 ~ 25kV; Base material selects polyether-ether-ketone, sulfonated polyether-ether-ketone or sulfonated poly aryl ether ketone porous membrane; Spinning temperature controls, between 25 ~ 40 DEG C, to reclaim organic solvent simultaneously.
In described polypyrrole loading process, the concentration of the monomer polypyrrole aqueous solution is at 0.04 ~ 0.1mol/L, and the soak time of proton exchange membrane in the pyrrole aqueous solution is between 50 ~ 300s; FeCl 3concentration of aqueous solution is at 0.4 ~ 0.7mol/L, and the proton exchange membrane of dipped polypyrrole is at FeCl 3middle immersion 50 ~ 300s; Control polymerization tank temperature between 0 ~ 15 DEG C; Repeatedly can pass through these two steps, ensure the complete of polymerization, but not want long soaking time, in order to avoid pyrroles infiltrates among proton exchange membrane cause barrier film internal short-circuit at every turn; The bake out temperature of proton exchange membrane is 30 ~ 80 DEG C.
In described heat-press step, the heating-up temperature of twin rollers is 25 ~ 80 DEG C, and after roll extrusion, thickness is 50 ~ 90% before roll extrusion.
Good effect of the present invention is the silk union film at non-fluorine proton exchange membrane material surface electrostatic spinning one deck heteropoly acid and nano particle, increases proton exchange ability and the mechanical strength of material.
Accompanying drawing explanation
Fig. 1 preparation facilities schematic diagram of the present invention.
Fig. 2 is electrostatic spinning layer scanning electron microscope diagram spectrum in example 1 of the present invention.
Fig. 3 is electrostatic spinning layer scanning electron microscope diagram spectrum in example 2 of the present invention.
Fig. 4 is electrostatic spinning layer scanning electron microscope diagram spectrum in example 3 of the present invention.
Wherein 1. transmission anti-curling device 2. non-fluorine proton exchange film base material 3. receiving system 4. device for spinning 5. copy paper groove 6. polymerization tank 7. cleaning device 8. drying unit 9. rolling device 10. transmission wrap-up 11. composite diaphragms.
Embodiment
Below in conjunction with drawings and Examples, the present invention is further described: a kind of device preparing MULTILAYER COMPOSITE nanofiber proton exchange membrane, comprise transmission wrap-up 1, two and overlap electrostatic spinning system, a set of pyrroles's paradigmatic system and roll extrusion system; It is characterized in that: often cover electrostatic spinning system comprises electrostatic spinning machine, high-voltage DC power supply, metering infusion pump, the receiving system 3 with efficient spininess spinning head, attemperating unit, gas concentration unit; Pyrroles's paradigmatic system comprises copy paper groove 5 and polymerization tank 6 two parts, and polymerization tank 6 is with temperature control system; Containing cleaning device 7, drying unit 8 and rolling device 9 in roll extrusion system, rolling device 9 controls its rolling temperatures containing temperature control system; All devices are by the integrated unified control of Mechanical course; The non-fluorine proton exchange film base material 2 of rolling is fixed with transmission unwinding device 1; By non-fluorine proton exchange film base material 2 by first receiving system 3, device for spinning 4 is positioned on receiving system 3, spinning solution is injected device for spinning 4, high voltage between device for spinning 4 and receiving system 3, under high-tension effect, electrostatic spinning is carried out to the one side of base material.Second receiving system 3 is positioned at directly over first receiving system 3, and the non-fluorine proton exchange film base material 2 completing one side spinning is turned on second receiving system 3 by roller, and the same device for spinning 4 pairs of base material another sides that use carry out spinning; Attemperating unit controls the temperature of whole spinning cabin body, and retracting device is arranged in the solvent being used for reclaiming spinning process directly over the body of spinning cabin and evaporating; The base material that spinning completes, through copy paper groove 5, makes substrate surface form one deck pyrroles liquid film, carries out the polymerization of pyrroles afterwards through polymerization tank 6; Then enter in drying unit 8 and dry, cleaning device 7 pairs of barrier films will be had before entering drying unit 8 to wash, wash unnecessary liquid off; Composite diaphragm 11 after oven dry is collected by transmission wrap-up 10 after rolling device 9 roll extrusion, just obtains composite diaphragm 11.
embodiment 1
As shown in Figure 1-2, by organic polymer binding agent polyvinyl alcohol (PVA) soluble in water, configuration concentration is the PVA aqueous solution of 8%, and dissolving method is that at 100 DEG C, cooling for reflux stirs.Add phosphotungstic acid afterwards, after dissolving, add Nano-meter SiO_2 again 2powder, wherein phosphotungstic acid quality and PVA mass ratio are 1.5:1, SiO 2quality and the mass ratio of PVA be 1:3.Through the stirring of 12 hours, suspension-turbid liquid is stirred and obtains spinning solution.Use composite membrane preparation facilities, select polyether-ether-ketone Porous proton exchange as base material, transmission winding system runs with the speed of 50cm/min, spinning solution is injected array spinning syringe needle, needle aperture is 0.3mm, needle length is 3cm, and syringe pump fltting speed is every root syringe needle 0.5ml/min; Between syringe needle and receiving system, apply 25kV voltage, controlling spinning environment temperature is 40 DEG C, at the electrospinning layer that base material tow sides electrostatic spinning one deck 30 μm is thick.Afterwards in the pyrrole aqueous solution of 0.04mol/L, soak time is 300s; Immerse the FeCl of 0.4mol/L afterwards again 3in solution, 300s carries out polymerization reaction, controls polymerization temperature at 15 DEG C.The barrier film be polymerized washes through cleaning device water the solvent that surface is reaction, and hot pressing after 50 DEG C dry, hot pressing temperature is 80 DEG C, and after roll extrusion, thickness is 50% of thickness before roll extrusion.Finally form finished product composite diaphragm by wrap-up rolling.The method raw material are cheap, and solvent is aqueous solvent, pollution-free, nontoxic, and the barrier film intensity of final synthesis is high, and proton conductivity is strong.
embodiment 2
As shown in Figure 3, be dissolved in acetone by organic polymer binding agent Kynoar-hexafluoropropylene (PVDF-HFP), configuration concentration is the PVDF-HFP acetone soln of 15%, and dissolving method is that at 25 DEG C, cooling for reflux stirs.Add phosphomolybdic acid afterwards, after dissolving, add nano-TiO again 2powder, adopt ultrasonic vibration to stir and coordinate cooling for reflux to mix, wherein phosphomolybdic acid quality and PVDF-HFP mass ratio are 1:1, TiO 2quality and the mass ratio of PVDF-HFP be 1:1.Through the stirring of 12 hours, suspension-turbid liquid is stirred and obtains spinning solution.Use composite membrane preparation facilities, select sulfonated polyether-ether-ketone Porous proton exchange as base material, transmission winding system runs with the speed of 50cm/min, spinning solution is injected single row type spinning syringe needle, needle aperture is 1mm, needle length is 4cm, and syringe pump fltting speed is every root syringe needle 1ml/min; Between syringe needle and receiving system, apply 8kV voltage, controlling spinning environment temperature is 25 DEG C, at the electrospinning layer that base material tow sides electrostatic spinning one deck 100 μm is thick.Afterwards in the pyrrole aqueous solution of 0.06mol/L, soak time is 250s; Immerse the FeCl of 0.5mol/L afterwards again 3in solution, 200s carries out polymerization reaction, controls polymerization temperature at 5 DEG C.The barrier film be polymerized washes through cleaning device water the solvent that surface is reaction, and hot pressing after 80 DEG C dry, hot pressing temperature is 70 DEG C, and the thickness after roll extrusion is 60% of thickness before roll extrusion.Finally form finished product composite diaphragm by wrap-up rolling.
embodiment 3
As shown in Figure 4, be dissolved in DMF (DMF) by fine for organic polymer binding agent polypropylene (PAN), configuration concentration is the DMF solution of 10%PAN, and dissolving method is that at 40 DEG C, heating water bath stirs.Add silico-tungstic acid afterwards, after dissolving, add nanometer Al again 2o 3powder, adopt ultrasonic vibration to be uniformly mixed, wherein silico-tungstic acid quality and PAN mass ratio are 0.3:1, Al 2o 3quality and the mass ratio of PAN be 1:8.Through the stirring of 12 hours, suspension-turbid liquid is stirred and obtains spinning solution.Use composite membrane preparation facilities, select sulfonated poly aryl ether ketone Porous proton exchange as base material, transmission winding system runs with the speed of 50cm/min, spinning solution is injected array spinning syringe needle, needle aperture is 0.8mm, needle length is 5cm, and syringe pump fltting speed is every root syringe needle 2ml/min; Between syringe needle and receiving system, apply 15kV voltage, controlling spinning environment temperature is 30 DEG C, at the electrospinning layer that base material tow sides electrostatic spinning one deck 200 μm is thick.Afterwards in the pyrrole aqueous solution of 0.1mol/L, soak time is 50s; Immerse the FeCl of 0.7mol/L afterwards again 3in solution, 50s carries out polymerization reaction, controls polymerization temperature at 0 DEG C.The barrier film be polymerized washes through cleaning device water the solvent that surface is reaction, and cold pressing after 60 DEG C dry, roll extrusion at normal temperature 25 DEG C, the thickness after roll extrusion is 90% of thickness before roll extrusion.Finally form finished product composite diaphragm by wrap-up rolling.

Claims (10)

1. prepare the device of MULTILAYER COMPOSITE nanofiber proton exchange membrane, comprise transmission wrap-up, two cover electrostatic spinning systems, a set of pyrroles's paradigmatic system and roll extrusion system; It is characterized in that: often cover electrostatic spinning system comprises electrostatic spinning machine, high-voltage DC power supply, metering infusion pump, the receiving system with efficient spininess spinning head, attemperating unit, gas concentration unit; Pyrroles's paradigmatic system comprises copy paper groove and polymerization tank two parts, and polymerization tank is with temperature control system; Containing cleaning device, drying unit and rolling device in roll extrusion system, rolling device contains temperature control system and controls its rolling temperatures; All devices are by the integrated unified control of Mechanical course; Non-fluorine proton exchange film base material and the transmission unwinding device of rolling are fixed; By non-fluorine proton exchange film base material by first receiving system, device for spinning is positioned on receiving system, and spinning solution is injected device for spinning, high voltage between device for spinning and receiving system, under high-tension effect, electrostatic spinning is carried out to the one side of base material.
2. second receiving system is positioned at directly over first receiving system, and the non-fluorine proton exchange film base material completing one side spinning is turned on second receiving system by roller, and the same device for spinning that uses carries out spinning to base material another side; Attemperating unit controls the temperature of whole spinning cabin body, and retracting device is arranged in the solvent being used for reclaiming spinning process directly over the body of spinning cabin and evaporating; The base material that spinning completes, through copy paper groove, makes substrate surface form one deck pyrroles liquid film, carries out the polymerization of pyrroles afterwards through polymerization tank; Then enter in drying unit and dry, cleaning device will be had before entering drying unit to wash barrier film, wash unnecessary liquid off; Composite diaphragm after oven dry is collected by transmission wrap-up after rolling device roll extrusion, just obtains composite diaphragm.
3. the device of preparation MULTILAYER COMPOSITE nanofiber proton exchange membrane according to claim 1, it is characterized in that described often cover electrostatic spinning system mesohigh DC power supply is added between spinning syringe needle and receiving system, receiving system ground connection, receiving system is aluminium foil; High efficiency electrostatic spinning syringe needle is single or array arrangement; The aperture of syringe needle is 0.3 ~ 11mm, and needle length is at 3 ~ 5cm.
4. prepare a method for MULTILAYER COMPOSITE nanofiber proton exchange membrane, it is characterized in that concrete preparation process is as follows:
(1) configuration of electrostatic spinning solution:
The polymeric binder of certain mass and heteropoly acid are added in a certain amount of solvent, under certain condition through fully stirring, being uniformly dissolved, add nano particle afterwards wherein and continue to stir, form final electrostatic spinning solution;
(2) electrostatic spinning step:
Use syringe pump by spinning solution syringe needle under certain speed, syringe needle applies high-tension electricity, and on base material, electrostatic is weaved one deck nanofibers film; Substrate another side in the same way electrostatic to weave one deck nano fibrous membrane;
Control environment in spinning process temperature;
(3) polypyrrole load:
Pyrrole is soluble in water, form certain density pyrroles's aqueous solution; Configure certain density FeCl again 3the aqueous solution;
First the composite diaphragm completed by electrostatic spinning immerses in pyrroles's aqueous solution and soaks a period of time, immerses FeCl after taking out cleaning 3soak a period of time in solution, after cleaning, drying, obtain polypyrrole tack coat;
(4) heat-press step:
Obtained composite diaphragm is carried out roll extrusion by the twin rollers being heated to uniform temperature, increases the binding ability between each layer.
5. according to claim 3, it is characterized in that, described in the configuration of (1) electrostatic spinning solution, heteropoly acid comprises phosphotungstic acid (H 3pW 12o 4.nH 2o), silico-tungstic acid (H 4siW 12o 4.H 2o), phosphomolybdic acid (H 3pMo 12o 4.nH 2o) etc.; Binding agent comprises polyvinyl alcohol (PVA), polypropylene fine (PAN), Kynoar-hexafluoropropylene (PVDF-HFP) etc.; Solvent comprises water, DMF (DMF), acetone etc.; Nano particle comprises Al 2o 3, SiO 2, TiO 2.
6. according to claim 3, it is characterized in that, it is 8% ~ 15% that polymeric binder described in the configuration of (1) electrostatic spinning solution accounts for the concentration of solvent; The quality of heteropoly acid is 0.3 ~ 1.5 times that adds polymeric binder quality; The quality of inorganic nano-particle and the mass ratio of binding agent are between 1:8 ~ 1:1; The thickness of spinning is between 30 ~ 200 μm.
7. according to claim 3, it is characterized in that, the stirring condition described in configuration of (1) electrostatic spinning solution can be add thermal agitation, cooling for reflux stirring, ultrasonic vibration stirring etc.
8. according to claim 3, it is characterized in that, in (2) electrostatic spinning step, syringe pump fltting speed is between 0.5 ~ 2ml/min; Spinning voltage is 8 ~ 25kV; Base material selects polyether-ether-ketone, sulfonated polyether-ether-ketone or sulfonated poly aryl ether ketone porous membrane; Spinning temperature controls, between 25 ~ 40 DEG C, to reclaim organic solvent simultaneously.
9. according to claim 3, it is characterized in that in (3) polypyrrole loading process, the concentration of the monomer polypyrrole aqueous solution is at 0.04 ~ 0.1mol/L, and the soak time of proton exchange membrane in the pyrrole aqueous solution is between 50 ~ 300s; FeCl 3concentration of aqueous solution is at 0.4 ~ 0.7mol/L, and the proton exchange membrane of dipped polypyrrole is at FeCl 3middle immersion 50 ~ 300s; Control polymerization tank temperature between 0 ~ 15 DEG C; Repeatedly can pass through these two steps, ensure the complete of polymerization, but not want long soaking time, in order to avoid pyrroles infiltrates among proton exchange membrane cause barrier film internal short-circuit at every turn; The bake out temperature of proton exchange membrane is 30 ~ 80 DEG C.
10. according to claim 3, it is characterized in that the heating-up temperature of twin rollers in (4) heat-press step is 25 ~ 80 DEG C, after roll extrusion, thickness is 50 ~ 90% before roll extrusion.
CN201410322908.4A 2014-07-09 2014-07-09 Device and method for preparing multi-layer composite nanofiber proton exchange membrane Pending CN105280939A (en)

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CN110652886A (en) * 2018-06-29 2020-01-07 杭州帝凡过滤技术有限公司 Production device and production method of multilayer composite nanofiber filtering membrane
CN111403785A (en) * 2020-03-27 2020-07-10 长春工业大学 Sulfonated polyaryletherketone sulfone composite membrane and preparation method thereof
CN112659421A (en) * 2020-11-27 2021-04-16 南京肯特复合材料股份有限公司 Polytetrafluoroethylene film surface treatment equipment
CN114447382A (en) * 2020-10-31 2022-05-06 中国石油化工股份有限公司 Proton exchange membrane containing concentric axis microstructure and preparation method thereof

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