CN103746130A - Preparation method of hollow fiber tube for fuel batteries - Google Patents
Preparation method of hollow fiber tube for fuel batteries Download PDFInfo
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- CN103746130A CN103746130A CN201410020917.8A CN201410020917A CN103746130A CN 103746130 A CN103746130 A CN 103746130A CN 201410020917 A CN201410020917 A CN 201410020917A CN 103746130 A CN103746130 A CN 103746130A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/08—Addition of substances to the spinning solution or to the melt for forming hollow filaments
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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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
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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
- 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 discloses a preparation method of a hollow fiber tube for fuel batteries, which comprises the following steps: 1) uniformly mixing 80-99.9 parts by mass of ion resin and 0.1-20 parts by mass of graphene to obtain a raw material; 2) melting the raw material, and extruding the molten raw material through a hollow spinning nozzle, cooling in air and coiling to obtain a nascent hollow fiber tube; and 3) treating the nascent hollow fiber tube in a 20-90 DEG C water bath under the condition of 1-5 times of stretching for 30-120 minutes to obtain the hollow fiber tube for fuel batteries. The graphene doped into the ion resin matrix can simultaneously enhance the ion-exchange property by 60% and the mechanical strength of the material by 30%; and by adopting the melt extrusion molding technology, the method has the advantages of simple technique and high production efficiency, and is beneficial to implementing industrialized production.
Description
Technical field
The invention belongs to proton exchange membrane preparation field, be specifically related to the preparation method of hollow fiber conduit for a kind of fuel cell.
Background technology
Proton Exchange Membrane Fuel Cells is the quiet electrochemical generating unit of a kind of high-efficiency cleaning, perfluorosulfonic acid proton exchange film fuel cell is low with its operating temperature, specific power is large, environmentally friendly, fuel handling convenient and at movable electrical appliances, automobile and other industries has good application.Perfluorosulfonic acid proton exchange film is as one of critical material of Proton Exchange Membrane Fuel Cells, plays exchange ion, separates the dual-use function of both positive and negative polarity active material.The amberplex using at present mainly comprises take the non-perfluor type sulfonate film that the perfluor type sulfonate film that the Nafion of du pont company series is representative and the sulfonated polyether-ether-ketone of take be representative.Nafion film has the features such as chemical property is good, stability is high, the life-span is long, but shortcoming be expensive, active material permeability is high, causes battery efficiency on the low side.Non-perfluor type sulfonate film has ion selectivity height and the low feature of cost, can obtain higher battery efficiency, but its mechanical property and less stable, thereby limited useful life.In addition, conventionally the method for preparing at present perfluorosulfonic acid proton exchange film is by perfluorinated sulfonic acid ion exchange resin is dissolved in corresponding solvent and makes perfluor sulfoacid resin solution, afterwards this solution is required to casting film-forming according to difference or deposit on matrix, after vaporing away solvent, obtain film, as US4731263, US5643968 and US3849243 etc.This film build method, dissolving perfluorinated sulfonic resin process need complete under HTHP, will pass through the complicated links such as concentrated afterwards, consumes energy higher; After casting film-forming, solvent will thoroughly volatilize, and the desolventizing time is longer, causes production efficiency low.
Graphene, due to its unique monoatomic layer two dimensional crystal structure, has excellent mechanics, electricity, proton conduction property.The people such as Mohammad Razaul Karim are at article (Journal of The American Chemical Society, 2013,135(22), 8097) in, research finds that graphene oxide has good proton conduction property equally, along with preparation in macroscopic quantity and the lower cost of graphene oxide, make graphene oxide as the ideal material that improves amberplex properties simultaneously.CN103219533 discloses a kind of method of Graphene cluster ion exchange membrane for flow battery, and this method is still utilized method preparation casting solution, the casting film-forming of solution blending.The more important thing is, with perfluor sulfoacid resin solution, can only be processed into film-form, can not be applied to the proton exchange device that some have special shape requirement, thereby greatly limited the range of application of perfluoro sulfonic acid membrane.And the course of dissolution of perfluorinated sulfonic resin need to complete under high-temperature and high-pressure conditions, very high to the requirement of process equipment.
Summary of the invention
The object of this invention is to provide the preparation method of hollow fiber conduit for the fuel cell of a kind of macroion switching performance and mechanics of materials intensity, the method is doped to Graphene in ion exchange resin matrix and can improves ion-exchange performance and mechanics of materials intensity simultaneously, and adopt and melt extrude forming technique, technique is simple, production efficiency is high, is beneficial to and realizes suitability for industrialized production.
For this reason, technical scheme of the present invention is as follows:
A preparation method for hollow fiber conduit for fuel cell, comprises the steps:
1) press mass fraction, the ion exchange resin of 80～99.9 parts is mixed with the Graphene of 0.1～20 part, obtain raw material;
2) described raw materials melt is extruded by hollow spinning head, then cooling through air, obtain nascent hollow fiber conduit after reeling;
3) described nascent hollow fiber conduit is processed to 30～120min under the condition of 1～5 times of stretching in 20～90 ℃ of water-baths, obtain described fuel cell hollow fiber conduit;
Described ion exchange resin be in perfluorinated sulfonic resin, sulfonated poly (phenylene oxide), sulfonated polyether-ether-ketone, sulfonated polyether-ether-ketone, sulfonated polyimide, sulfonated polyamide acid imide, sulfonated polyether acid imide, SPSF, sulfonated polyphenyl imidazoles, sulfonated polystyrene, sulfonation poly(p-benzamide), sulfonation poly, Sulfonated Polyphenylene Sulfide and sulfonation polyparaphenylene benzamide any one or any two kinds with arbitrarily than mixture;
Described Graphene be in sulfonated graphene, graphene oxide and carboxylic acid functionalized graphene any one or any two kinds with arbitrarily than mixture.
Wherein: the ion exchange resin in step 1) is 95～99.5 parts, Graphene is 0.5～5 part.
The external diameter of described hollow spinning head is 100～2000 μ m, and internal diameter is 80～1990 μ m.
Described hollow spinning head internal cavities passes into the compressed air that flow is 0～30L/min.Be used to form the internal cavities of hollow fiber conduit.
Described nascent hollow fiber conduit is processed to 30～120min under 2～3 times of conditions that stretch in 30～50 ℃ of water-baths.
Step 2) utilize double screw extruder to carry out melting to raw material.
The draw ratio of described double screw extruder is 30～50.
Utilizing double screw extruder to carry out melting Shi Ge district temperature to raw material is 150～400 ℃, and extruding rotating speed is 30～100rpm.
The external diameter of the hollow fiber conduit described in step 3) is: 50～2500 μ m, internal diameter is: 30～2490 μ m.
The external diameter of the hollow fiber conduit described in step 3) and internal diameter can be by regulating warp and outer warp in spinning nozzle, regulating compressed air require and stretch and recently control.
The fuel cell that the present invention makes is 0.5～3mmol/g with the ion exchange capacity IEC of hollow fiber conduit, preferred 0.7～1.5mmol/g, and mechanical strength is 50～110MPa.
Compared with prior art, the present invention has following beneficial effect:
(1), by Graphene and ion exchange resin blend, make fuel cell improve respectively 60% and 30% with mechanical strength and the ion-exchange performance of hollow fiber conduit, and can control by the addition of Graphene the ion-exchange performance of hollow fiber conduit.
(2) adopt and melt extrude the method for forming, avoided high temperature, the high pressure course of dissolution of solwution method, reduce energy consumption, enhance productivity, be convenient to suitability for industrialized production.
(3) can, by the adjustment of technological parameter being prepared to the hollow fiber conduit of different size, different exchange capacities, greatly expand its application aspect ion-exchange device.
Accompanying drawing explanation
Fig. 1 is that embodiment 1 makes the section field emission scanning electron microscope figure of hollow fiber conduit for fuel cell.
Fig. 2 is that embodiment 1 makes the surperficial field emission scanning electron microscope figure of hollow fiber conduit for fuel cell.
Embodiment
Below in conjunction with embodiment and accompanying drawing, technical scheme of the present invention is described in detail.
Embodiment 1
A preparation method for hollow fiber conduit for fuel cell, comprises the steps:
1) press mass fraction, the sulfonated graphene of the perfluorinated sulfonic resin of 99.9 parts and 0.1 part is joined and in high-speed mixer, stirs 20min, the raw material that obtains mixing;
2) described raw material is sent into double screw extruder through measuring pump, the draw ratio of extruder is 30, screw diameter is that 20mm, rotating speed are 40rpm, each district's Temperature Setting is 220～300 ℃, described raw materials melt is extruded by hollow spinning head, cooling in air, obtain nascent hollow fiber conduit after reeling, described hollow spinning head external diameter is that 1400 μ m, internal diameter are 1100 μ m, the compressed air require that passes into its internal cavities place is 3L/min; Incipient extension speed is 20m/min;
3) described nascent hollow fiber conduit is processed to 30min under the condition of 2 times of stretchings in 40 ℃ of water-baths, make sulfonated graphene for fuel cell/perfluorinated sulfonic acid hollow fiber conduit.
Sulfonated graphene/perfluorinated sulfonic acid hollow fiber conduit for fuel cell that the present embodiment makes, external diameter is that 1200 μ m, internal diameter are 1000 μ m; Smooth surface, tube wall is fine and close, zero defect; Hot strength is 40MPa, utilizes acid-base titration to test exchange capacity IEC=0.75mmol/g.
Sulfonated graphene/perfluorinated sulfonic acid hollow fiber conduit that step 3) is obtained is through chemistry after transition, and hot strength is 55MPa, and exchange capacity is IEC=0.75mmol/g.
Fig. 1,2 has provided respectively cross section, the surperficial field emission scanning electron microscope figure of sulfonated graphene/perfluorinated sulfonic acid hollow fiber conduit that the present embodiment makes.
As seen from the figure, the hollow fiber conduit smooth surface that adopts extrusion by melting to make, illustrates and under this proportioning, has good spinnability; From section, can draw doughnut bore and wall thickness homogeneous, be evenly distributed simultaneously.
Embodiment 2
The difference of the present embodiment and embodiment 1 is that the mass fraction of sulfonated graphene in step 1) is 0.5 part, and the mass fraction of perfluorinated sulfonic resin is 99.5 parts, and other step is identical with embodiment 1.
After testing, the hollow fiber conduit external diameter that the present embodiment obtains is 1200 μ m, and internal diameter is 1000 μ m; Smooth surface, tube wall is fine and close, zero defect; Hot strength is 65MPa, and exchange capacity is IEC=0.85mmol/g.
Embodiment 3
The present embodiment difference from Example 1 is that in step 1), sulfonated graphene mass fraction is 1 part, and perfluorinated sulfonic resin mass fraction is 99 parts, and other step is identical with embodiment 1.
After testing, the hollow fiber conduit external diameter that the present invention obtains is 1200 μ m, and internal diameter is 1000 μ m; Smooth surface, tube wall is fine and close, zero defect; Hot strength is 70MPa, and exchange capacity is IEC=0.89mmol/g.
Embodiment 4
The present embodiment difference from Example 1 is that in step 1), sulfonated graphene mass fraction is 3 parts, and perfluorinated sulfonic resin mass fraction is 97 parts, and other step is identical with embodiment 1.
After testing, the hollow fiber conduit external diameter that the present invention obtains is 1200 μ m, and internal diameter is 1000 μ m; Smooth surface, tube wall is fine and close, zero defect; Hot strength is 75MPa, and exchange capacity is IEC=0.94mmol/g.
Embodiment 5
The present embodiment difference from Example 1 is that in step 1), sulfonated graphene mass fraction is 5 parts, and perfluorinated sulfonic resin mass fraction is 95 parts, and other step is identical with embodiment 1.
After testing, the hollow fiber conduit external diameter that the present invention obtains is 1200 μ m, and internal diameter is 1000 μ m; Smooth surface, tube wall is fine and close, zero defect; Hot strength is 79MPa, and exchange capacity is IEC=1.06mmol/g.
Embodiment 6
The present embodiment difference from Example 1 is that in step 1), sulfonated graphene mass fraction is 8 parts, and perfluorinated sulfonic resin mass fraction is 92 parts, and other is identical with embodiment 1.
After testing, the hollow fiber conduit external diameter that the present invention obtains is 1200 μ m, and internal diameter is 1000 μ m; Smooth surface, tube wall is fine and close, zero defect; Hot strength is 65MPa, and exchange capacity is IEC=0.95mmol/g.
Comparative example 1
1. perfluorinated sulfonic resin thing is sent into double screw extruder through measuring pump, the draw ratio of extruder is 30, screw diameter is that 20mm, rotating speed are 40rpm, each district's Temperature Setting is 220～300 ℃, described perfluorinated sulfonic resin melting is extruded by the hollow spinning head of 285 ℃, cooling in air, obtain nascent hollow fiber conduit after reeling, described hollow spinning head external diameter is that 1400 μ m, internal diameter are 1100 μ m, the compressed air require that passes into its internal cavities place is 3L/min; Incipient extension speed is 20m/min;
2. described nascent hollow fiber conduit is processed to 30min under the condition of 2 times of stretchings in 40 ℃ of water-baths, make perfluorinated sulfonic acid hollow fiber conduit.
The external diameter of the perfluorinated sulfonic acid hollow fiber conduit making in this comparative example is 1200 μ m, and internal diameter is 1000 μ m; Smooth surface, tube wall is fine and close, zero defect; Hot strength is 38MPa.
The perfluorinated sulfonic acid fluorine type hollow fiber conduit that 2. step is obtained is after chemistry reason transition, and hot strength is 49MPa, and exchange capacity is IEC=0.74mmol/g.
Comparative example 1～6 and comparative example 1 test result are found, under the condition that fixedly spinning technique is constant, by changing the addition of sulfonated graphene, can obtain sulfonated graphene/perfluorinated sulfonic acid hollow fiber conduit of different ions exchange capacity and mechanical strength, and along with the increase of sulfonated graphene addition, ion exchange capacity and the mechanical strength of gained hollow fiber conduit all increase.
Total score is analysed ion exchange capacity and mechanical strength, and preferred sulfonated graphene mass fraction is 0.1～5 part, and perfluorinated sulfonic resin mass fraction is 95～99.9 parts.
Following examples object is to control the caliber of prepared hollow fiber conduit, wall thickness and mechanical strength.
Embodiment 7
A preparation method for hollow fiber conduit for fuel cell, comprises the steps:
1) press mass fraction, the perfluorinated sulfonic resin of the sulfonated graphene of 3 parts and 97 parts is joined and in high-speed mixer, stirs 20min, the raw material that obtains mixing;
2) described raw material is sent into double screw extruder through measuring pump, the draw ratio of extruder is 20, screw diameter is that 20mm, rotating speed are 40rpm, each district's Temperature Setting is 220～300 ℃, described raw materials melt is extruded by the hollow spinning head of 285 ℃, cooling in air, obtain nascent hollow fiber conduit after reeling, described hollow spinning head external diameter is that 1500 μ m, internal diameter are 1200 μ m, the compressed air require that passes into its internal cavities place is 3L/min; Incipient extension speed is 20m/min;
3) described nascent hollow fiber conduit is processed to 30min under the condition of 2 times of stretchings in 40 ℃ of water-baths, make sulfonated graphene for fuel cell/perfluorinated sulfonic acid hollow fiber conduit.
Sulfonated graphene/perfluorinated sulfonic acid hollow fiber conduit that the present embodiment makes, external diameter is that 1250 μ m, internal diameter are 980 μ m; Smooth surface, tube wall is fine and close, zero defect; Hot strength is 74MPa.
Sulfonated graphene/perfluorinated sulfonic acid hollow fiber conduit that step 3) is obtained is through chemistry after transition, and hot strength is 85MPa, and exchange capacity is IEC=0.94mmol/g.
The present embodiment is the proportioning adopting after optimizing above, and object is to control the diameter of prepared doughnut, and wall thickness etc., therefore the exchange capacity IEC in embodiment 7～9 does not change.
Embodiment 8
The difference of the present embodiment and embodiment 7 is: hollow spinning head external diameter is 1500 μ m, and internal diameter is 1100 μ m.
After testing, the hollow fiber conduit external diameter that the present embodiment obtains is 1250 μ m, and internal diameter is 880 μ m, smooth surface, and tube wall is fine and close, zero defect; Hot strength is 94MPa, and exchange capacity is IEC=0.94mmol/g.
Embodiment 9
The difference of the present embodiment and embodiment 7 is, hollow-fiber module spinning nozzle external diameter is 1500 μ m, and internal diameter is 1000 μ m.
After testing, the hollow fiber conduit external diameter that the present embodiment obtains is 1250 μ m, and internal diameter is 880 μ m, smooth surface, and tube wall is fine and close, zero defect; Hot strength is 96MPa, and exchange capacity is IEC=0.94mmol/g.
Embodiment 10
A preparation method for hollow fiber conduit for fuel cell, comprises the steps:
1) press mass fraction, the sulfonated graphene of the sulfonated polyether-ether-ketone of 99.9 parts and 0.1 part is joined and in high-speed mixer, stirs 20min, the raw material that obtains mixing;
2) described raw material is sent into double screw extruder through measuring pump, the draw ratio of extruder is 30, screw diameter is that 20mm, rotating speed are 40rpm, each district's Temperature Setting is 200～400 ℃, described raw materials melt is extruded by hollow spinning head, cooling in air, obtain nascent hollow fiber conduit after reeling, described hollow spinning head external diameter is that 1000 μ m, internal diameter are 900 μ m, the compressed air require that passes into its internal cavities place is 3L/min; Incipient extension speed is 20m/min;
3) described nascent hollow fiber conduit is processed to 30min under the condition of 2 times of stretching in 40 ℃ of water-baths, reel and obtain sulfonated graphene for fuel cell/perfluorinated sulfonic acid hollow fiber conduit.
Sulfonated graphene/perfluorinated sulfonic acid hollow fiber conduit for fuel cell that the present embodiment makes, external diameter is that 1200 μ m, internal diameter are 1000 μ m; Smooth surface, tube wall is fine and close, zero defect; Hot strength is 50MPa, exchange capacity IEC=0.37mmol/g.
Embodiment 11
The difference of the present embodiment and embodiment 10 is that the mass fraction of sulfonated graphene in step 1) is 0.5 part, and the mass fraction of sulfonated polyether-ether-ketone is 99.5 parts.
After testing, the hollow fiber conduit external diameter that the present embodiment obtains is 1200 μ m, and internal diameter is 1000 μ m; Smooth surface, tube wall is fine and close, zero defect; Hot strength is 73MPa, and exchange capacity is IEC=0.36mmol/g.
Embodiment 12
The difference of the present embodiment and embodiment 10 is that the mass fraction of sulfonated graphene in step 1) is 1 part, and the mass fraction of sulfonated polyether-ether-ketone is 99 parts.
After testing, the hollow fiber conduit external diameter that the present embodiment obtains is 1200 μ m, and internal diameter is 1000 μ m; Smooth surface, tube wall is fine and close, zero defect; Hot strength is 84MPa, and exchange capacity is IEC=1.32mmol/g.
Embodiment 13
The present embodiment difference from Example 10 is that in step 1), sulfonated graphene mass fraction is 3 parts, and sulfonated polyether-ether-ketone mass fraction is 97 parts, and other is identical with embodiment 10.
After testing, the hollow fiber conduit external diameter that the present invention obtains is 1200 μ m, and internal diameter is 1000 μ m; Smooth surface, tube wall is fine and close, zero defect; Hot strength is 93MPa, and exchange capacity is IEC=1.38mmol/g.
Embodiment 14
The difference of the present embodiment and embodiment 10 is that the mass fraction of sulfonated graphene in step 1) is 5 parts, and the mass fraction of sulfonated polyether-ether-ketone is 95 parts.
After testing, the hollow fiber conduit external diameter that the present embodiment obtains is 1200 μ m, and internal diameter is 1000 μ m; Smooth surface, tube wall is fine and close, zero defect; Hot strength is 89MPa, and exchange capacity is IEC=1.27mmol/g.
Embodiment 15
The difference of the present embodiment and embodiment 10 is that the mass fraction of sulfonated graphene in step 1) is 8 parts, and the mass fraction of sulfonated polyether-ether-ketone is 92 parts.
After testing, the hollow fiber conduit external diameter that the present embodiment obtains is 1200 μ m, and internal diameter is 1000 μ m; Smooth surface, tube wall is fine and close, zero defect; Hot strength is 77MPa, and exchange capacity is IEC=1.14mmol/g.
Comparative example 2
1. sulfonated polyether-ether-ketone is sent into double screw extruder through measuring pump, the draw ratio of extruder is 30, screw diameter is that 20mm, rotating speed are 40rpm, each district's Temperature Setting is 200～400 ℃, described perfluorinated sulfonic resin melting is extruded by the hollow spinning head of 285 ℃, cooling in air, obtain nascent hollow fiber conduit after reeling, described hollow spinning head external diameter is that 1000 μ m, internal diameter are 900 μ m, the compressed air require that passes into its internal cavities place is 3L/min; Incipient extension speed is 20m/min;
2. described nascent hollow fiber conduit is processed to 30min under the condition of 2 times of stretchings in 40 ℃ of water-baths, make perfluorinated sulfonic acid hollow fiber conduit.
The external diameter of the sulfonated polyether-ether-ketone hollow fiber conduit making in this comparative example is 1200 μ m, and internal diameter is 1000 μ m; Smooth surface, tube wall is fine and close, zero defect; Hot strength is 43MPa, exchange capacity IEC=1.35mmol/g.
Comparative example 11～15 and comparative example 2 test results are found, under the condition that fixedly spinning technique is constant, by changing the addition of sulfonated graphene, can obtain Graphene/sulfonated polyether-ether-ketone hollow fiber conduit of different ions exchange capacity and mechanical strength, and the increase along with sulfonated graphene addition, the mechanical strength of hollow fiber conduit increases, little on exchange capacity impact.Total score is analysed ion exchange capacity and mechanical strength, and preferred sulfonated graphene mass fraction is 0.1～3 part, and perfluorinated sulfonic resin mass fraction is 97～99.9 parts.
Embodiment 16
A preparation method for hollow fiber conduit for fuel cell, comprises the steps:
1) press mass fraction, the sulfonated graphene of the sulfonated polyether-ether-ketone of 97 parts and 3 parts is joined and in high-speed mixer, stirs 20min, the raw material that obtains mixing;
2) described raw material is sent into double screw extruder through measuring pump, the draw ratio of extruder is 30, screw diameter is that 20mm, rotating speed are 40rpm, each district's Temperature Setting is 200～400 ℃, described raw materials melt is extruded by hollow spinning head, cooling in air, obtain nascent hollow fiber conduit after reeling, described hollow spinning head external diameter is that 1500 μ m, internal diameter are 1200 μ m, the compressed air require that passes into its internal cavities place is 3L/min; Incipient extension speed is 20m/min;
3) described nascent hollow fiber conduit is processed to 30min under the condition of 2 times of stretching in 40 ℃ of water-baths, reel and obtain sulfonated graphene for fuel cell/sulfonated polyether-ether-ketone hollow fiber conduit.
Sulfonated graphene/perfluorinated sulfonic acid hollow fiber conduit for fuel cell that the present embodiment makes, external diameter is that 1250 μ m, internal diameter are 980 μ m; Smooth surface, tube wall is fine and close, zero defect; Hot strength is 90MPa, exchange capacity IEC=1.38mmol/g.
Embodiment 17
The difference of the present embodiment and embodiment 16 is: hollow spinning head external diameter is 1500 μ m, and internal diameter is 1100 μ m.
After testing, the hollow fiber conduit external diameter that the present embodiment obtains is 1350 μ m, and internal diameter is 900 μ m, smooth surface, and tube wall is fine and close, zero defect; Hot strength is 100MPa, and exchange capacity is IEC=1.38mmol/g.
Embodiment 18
The difference of the present embodiment and embodiment 16 is: hollow spinning head external diameter is 1500 μ m, and internal diameter is 1000 μ m.
After testing, the hollow fiber conduit external diameter that the present embodiment obtains is 1350 μ m, and internal diameter is 960 μ m, smooth surface, and tube wall is fine and close, zero defect; Hot strength is 108MPa, and exchange capacity is IEC=1.38mmol/g.
Embodiment 19
The present embodiment and embodiment 16 differences are, hollow-fiber module spinning nozzle external diameter is 1500 μ m, and internal diameter is 900 μ m; Other is identical with embodiment 16.
After testing, the hollow fiber conduit external diameter that the present invention obtains is 1350 μ m, and internal diameter is 870 μ m, smooth surface, and tube wall is fine and close, zero defect; Hot strength is 117MPa, and exchange capacity is IEC=1.38mmol/g.
Embodiment 20
A preparation method for hollow fiber conduit for fuel cell, comprises the steps:
1) press mass fraction, the sulfonated graphene of the perfluorinated sulfonic resin of 50 parts, the sulfonated polyether-ether-ketone of 47 parts and 3 parts is joined and in high-speed mixer, stirs 20min, the raw material that obtains mixing;
2) described raw material is sent into double screw extruder through measuring pump, the draw ratio of extruder is 30, screw diameter is that 20mm, rotating speed are 40rpm, each district's Temperature Setting is 200～400 ℃, described raw materials melt is extruded by hollow spinning head, cooling in air, obtain nascent hollow fiber conduit after reeling, described hollow spinning head external diameter is that 1000 μ m, internal diameter are 900 μ m, the compressed air require that passes into its internal cavities place is 3L/min; Incipient extension speed is 20m/min;
3) described nascent hollow fiber conduit is processed to 30min under the condition of 2 times of stretching in 40 ℃ of water-baths, reel and obtain fuel cell hollow fiber conduit.
The fuel cell hollow fiber conduit that the present embodiment makes, external diameter is that 1150 μ m, internal diameter are 960 μ m; Smooth surface, tube wall is fine and close, zero defect; Hot strength is 95MPa, exchange capacity IEC=0.54mmol/g.
The hollow fiber conduit that step 3) is obtained is through chemistry after transition, and hot strength is 75MPa, and exchange capacity is IEC=0.93mmol/g.
Embodiment 21
The difference of the present embodiment and embodiment 20 is that the mass fraction of sulfonated graphene in step 1) is 3 parts, and perfluorinated sulfonic resin is 40 parts, and sulfonated polyether-ether-ketone is 57 parts.
After testing, the hollow fiber conduit external diameter that the present embodiment obtains is 1150 μ m, and internal diameter is 980 μ m; Smooth surface, tube wall is fine and close, zero defect; Hot strength is 103MPa, and exchange capacity is IEC=1.04mmol/g.
Embodiment 22
The difference of the present embodiment and embodiment 20 is that the mass fraction of sulfonated graphene in step 1) is 3 parts, and perfluorinated sulfonic resin is 30 parts, and sulfonated polyether-ether-ketone is 67 parts.
After testing, the hollow fiber conduit external diameter that the present embodiment obtains is 1200 μ m, and internal diameter is 980 μ m; Smooth surface, tube wall is fine and close, zero defect; Hot strength is 112MPa, and exchange capacity is IEC=1.16mmol/g.
Embodiment 23
The difference of the present embodiment and embodiment 20 is that the mass fraction of sulfonated graphene in step 1) is 3 parts, and perfluorinated sulfonic resin is 20 parts, and sulfonated polyether-ether-ketone is 77 parts.
After testing, the hollow fiber conduit external diameter that the present embodiment obtains is 1200 μ m, and internal diameter is 980 μ m; Smooth surface, tube wall is fine and close, zero defect; Hot strength is 116MPa, and exchange capacity is IEC=1.24mmol/g.
Embodiment 24
The difference of the present embodiment and embodiment 20 is that the mass fraction of sulfonated graphene in step 1) is 3 parts, and perfluorinated sulfonic resin is 10 parts, and sulfonated polyether-ether-ketone is 87 parts.
After testing, the hollow fiber conduit external diameter that the present embodiment obtains is 1200 μ m, and internal diameter is 980 μ m; Smooth surface, tube wall is fine and close, zero defect; Hot strength is 113MPa, and exchange capacity is IEC=1.30mmol/g.
Embodiment 25
A preparation method for hollow fiber conduit for fuel cell, comprises the steps:
1) press mass fraction, the perfluorinated sulfonic resin of the carboxylic acid functionalized graphene of 0.5 part, the sulfonated graphene of 4.5 parts and 95 parts is joined and in high-speed mixer, stirs 20min, the raw material that obtains mixing;
2) described raw material is sent into double screw extruder through measuring pump, the draw ratio of extruder is 30, screw diameter is that 20mm, rotating speed are 40rpm, each district's Temperature Setting is 220～300 ℃, described raw materials melt is extruded by hollow spinning head, cooling in air, obtain nascent hollow fiber conduit after reeling, described hollow spinning head external diameter is that 1400 μ m, internal diameter are 1100 μ m, the compressed air require that passes into its internal cavities place is 3L/min; Incipient extension speed is 20m/min;
3) described nascent hollow fiber conduit is processed to 30min under the condition of 2 times of stretching in 40 ℃ of water-baths, reel and obtain fuel cell hollow fiber conduit.
The fuel cell hollow fiber conduit that the present embodiment makes, external diameter is that 1200 μ m, internal diameter are 1000 μ m; Smooth surface, tube wall is fine and close, zero defect; Hot strength is 78MPa, exchange capacity IEC=0.06mmol/g.Owing to carrying out chemistry in the present embodiment, do not make the transition, so exchange capacity is less.
The hollow fiber conduit that step 3) is obtained is through chemistry after transition, and its hot strength is 85MPa, and exchange capacity is IEC=1.15mmol/g.
Embodiment 26
The difference of the present embodiment and embodiment 25 is that the mass fraction of sulfonated graphene in step 1) is 4 parts, and carboxylic acid functionalized graphene mass fraction is 1 part, and perfluorinated sulfonic resin is 95 parts.
After testing, the hollow fiber conduit external diameter that the present embodiment obtains is 1200 μ m, and internal diameter is 1000 μ m; Smooth surface, tube wall is fine and close, zero defect; Hot strength is 93MPa, and exchange capacity is IEC=1.26mmol/g.
Embodiment 27
The present embodiment and embodiment 25 differences are that in step 1), sulfonated graphene mass fraction is 3.5 parts, and carboxylic acid functionalized graphene mass fraction is 1.5 parts, and perfluorinated sulfonic resin mass fraction is 95 parts, and other is identical with embodiment 25.
After testing, the hollow fiber conduit external diameter that the present invention obtains is 1200 μ m, and internal diameter is 1000 μ m; Smooth surface, tube wall is fine and close, zero defect; Hot strength is 96MPa, and exchange capacity is IEC=1.55mmol/g.
Embodiment 28
The present embodiment and embodiment 25 differences are that in step 1), sulfonated graphene mass fraction is 3 parts, and carboxylic acid functionalized graphene mass fraction is 2 parts, and perfluorinated sulfonic resin mass fraction is 95 parts, and other is identical with embodiment 25.
After testing, the hollow fiber conduit external diameter that the present invention obtains is 1200 μ m, and internal diameter is 1000 μ m; Smooth surface, tube wall is fine and close, zero defect; Hot strength is 90MPa, and exchange capacity is IEC=1.75mmol/g.
Embodiment 29
The present embodiment and embodiment 25 differences are that in step 1), sulfonated graphene mass fraction is 2 parts, and carboxylic acid functionalized graphene mass fraction is 3 parts, and perfluorinated sulfonic resin mass fraction is 95 parts, and other is identical with embodiment 25.
After testing, the hollow fiber conduit external diameter that the present invention obtains is 1200 μ m, and internal diameter is 1000 μ m; Smooth surface, tube wall is fine and close, zero defect; Hot strength is 95MPa, and exchange capacity is IEC=2.03mmol/g.
Embodiment 30
The present embodiment and embodiment 25 differences are that in step 1), sulfonated graphene mass fraction is 1 part, and carboxylic acid functionalized graphene mass fraction is 4 parts, and perfluorinated sulfonic resin mass fraction is 95 parts, and other is identical with embodiment 25.
After testing, the hollow fiber conduit external diameter that the present invention obtains is 1200 μ m, and internal diameter is 1000 μ m; Smooth surface, tube wall is fine and close, zero defect; Hot strength is 97MPa, and exchange capacity is IEC=2.21mmol/g.
Preferably, sulfonated Graphene mass fraction is: 3～4 parts, carboxylic acid functionalized graphene mass fraction is: 1～2 part, perfluorinated sulfonic resin mass fraction is 95 parts.
Embodiment 31
The present embodiment and embodiment 25 differences are that in step 1), sulfonated graphene mass fraction is 4 parts, and carboxylic acid functionalized graphene mass fraction is 1 part, and sulfonated polystyrene mass fraction is 95 parts, and other is identical with embodiment 25.
After testing, the hollow fiber conduit external diameter that the present invention obtains is 1200 μ m, and internal diameter is 1000 μ m; Smooth surface, tube wall is fine and close, zero defect; Hot strength is 68MPa, and exchange capacity is IEC=0.92mmol/g.
Embodiment 32
The present embodiment and embodiment 25 differences are that in step 1), sulfonated graphene mass fraction is 4 parts, and carboxylic acid functionalized graphene mass fraction is 1 part, and sulfonation poly(p-benzamide) mass fraction is 95 parts, and other is identical with embodiment 25.
After testing, the hollow fiber conduit external diameter that the present invention obtains is 1200 μ m, and internal diameter is 1000 μ m; Smooth surface, tube wall is fine and close, zero defect; Hot strength is 70MPa, and exchange capacity is IEC=0.8mmol/g.
Embodiment 33
The present embodiment and embodiment 25 differences are that in step 1), sulfonated graphene mass fraction is 4 parts, and carboxylic acid functionalized graphene mass fraction is 1 part, and SPSF mass fraction is 95 parts, and other is identical with embodiment 25.
After testing, the hollow fiber conduit external diameter that the present invention obtains is 1200 μ m, and internal diameter is 1000 μ m; Smooth surface, tube wall is fine and close, zero defect; Hot strength is 90MPa, and exchange capacity is IEC=1.02mmol/g.
Described in each embodiment, chemical transformation process is: the NaOH aqueous solution that is 6mol/L by the effective concentration of the doughnut obtaining soaks 24h under 80 ℃ of conditions, then removes the aqueous slkali of hollow fiber conduit surface attachment, then the H that is 4mol/L by concentration
2sO
4the aqueous solution soaks 4h under 80 ℃ of conditions.
Claims (8)
1. a preparation method for hollow fiber conduit for fuel cell, is characterized in that comprising the steps:
1) press mass fraction, the ion exchange resin of 80～99.9 parts is mixed with the Graphene of 0.1～20 part, obtain raw material;
2) described raw materials melt is extruded by hollow spinning head, then cooling through air, obtain nascent hollow fiber conduit after reeling;
3) by described nascent hollow fiber conduit under the condition of 1～5 times of stretching, in 20～90 ℃ of water-baths, process 30～120min, obtain described fuel cell hollow fiber conduit;
Described ion exchange resin be in perfluorinated sulfonic resin, sulfonated poly (phenylene oxide), sulfonated polyether-ether-ketone, sulfonated polyether-ether-ketone, sulfonated polyimide, sulfonated polyamide acid imide, sulfonated polyether acid imide, SPSF, sulfonated polyphenyl imidazoles, sulfonated polystyrene, sulfonation poly(p-benzamide), sulfonation poly, Sulfonated Polyphenylene Sulfide and sulfonation polyparaphenylene benzamide any one or any two kinds with arbitrarily than mixture;
Described Graphene be in sulfonated graphene, graphene oxide and carboxylic acid functionalized graphene any one or any two kinds with arbitrarily than mixture.
2. preparation method as claimed in claim 1, is characterized in that: the ion exchange resin in step 1) is 95～99.5 parts, and Graphene is 0.5～5 part.
3. preparation method as claimed in claim 1, is characterized in that: the external diameter of described hollow spinning head is 100～2000 μ m, and internal diameter is 80～1990 μ m.
4. preparation method as claimed in claim 1, is characterized in that: described hollow spinning head internal cavities passes into the compressed air that flow is 0～30L/min.
5. preparation method as claimed in claim 1, is characterized in that: described nascent hollow fiber conduit, under 2～3 times of conditions that stretch, is processed to 30～120min in 30～50 ℃ of water-baths.
6. preparation method as claimed in claim 1, is characterized in that: step 2) utilize double screw extruder to carry out melting to raw material.
7. preparation method as claimed in claim 6, is characterized in that: the draw ratio of described double screw extruder is 30～50.
8. preparation method as claimed in claim 6, is characterized in that: utilizing double screw extruder to carry out melting Shi Ge district temperature to raw material is 150～400 ℃, and extruding rotating speed is 30～100rpm.
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| CN104894680A (en) * | 2015-06-15 | 2015-09-09 | 东华大学 | PPS (polyphenylene sulfide)/graphene hybrid composite fiber and preparation method thereof |
| CN105603568A (en) * | 2016-01-21 | 2016-05-25 | 济南圣泉集团股份有限公司 | Modified hollow cotton and preparation method thereof |
| TWI568781B (en) * | 2013-09-25 | 2017-02-01 | 宸鴻光電科技股份有限公司 | Sulfonated polymer/graphene nano-composite material and its preparation method and application |
| CN109589802A (en) * | 2018-11-06 | 2019-04-09 | 国电南瑞科技股份有限公司 | A kind of porous diffusion barrier and its preparation method utilize the made battery of the porous diffusion barrier |
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| TWI568781B (en) * | 2013-09-25 | 2017-02-01 | 宸鴻光電科技股份有限公司 | Sulfonated polymer/graphene nano-composite material and its preparation method and application |
| CN104894680A (en) * | 2015-06-15 | 2015-09-09 | 东华大学 | PPS (polyphenylene sulfide)/graphene hybrid composite fiber and preparation method thereof |
| CN105603568A (en) * | 2016-01-21 | 2016-05-25 | 济南圣泉集团股份有限公司 | Modified hollow cotton and preparation method thereof |
| CN105603568B (en) * | 2016-01-21 | 2018-05-01 | 济南圣泉集团股份有限公司 | A kind of modified hollow cotton and preparation method thereof |
| CN109589802A (en) * | 2018-11-06 | 2019-04-09 | 国电南瑞科技股份有限公司 | A kind of porous diffusion barrier and its preparation method utilize the made battery of the porous diffusion barrier |
| CN109589802B (en) * | 2018-11-06 | 2021-08-24 | 国电南瑞科技股份有限公司 | Porous separation membrane for zinc-bromine flow battery and preparation method thereof |
| CN111921567A (en) * | 2020-06-22 | 2020-11-13 | 山东东岳高分子材料有限公司 | Enhanced perfluorinated sulfonic acid ion exchange membrane and preparation method thereof |
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