CN103551058A - Flat plate type moisture permeable membrane as well as preparation method thereof - Google Patents
Flat plate type moisture permeable membrane as well as preparation method thereof Download PDFInfo
- Publication number
- CN103551058A CN103551058A CN201310517322.9A CN201310517322A CN103551058A CN 103551058 A CN103551058 A CN 103551058A CN 201310517322 A CN201310517322 A CN 201310517322A CN 103551058 A CN103551058 A CN 103551058A
- Authority
- CN
- China
- Prior art keywords
- permeable membrane
- moisture permeable
- short fibers
- plastic short
- flat
- 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.)
- Granted
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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Fuel Cell (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a flat plate type moisture permeable membrane as well as a preparation method thereof. The flat plate type moisture permeable membrane is prepared by compounding perfluorinated sulfonic acid ion exchange resin and super absorbent plastic short fiber, wherein the resin is in continuous phase and the fiber is in dispersion phase. The end part of 20-90% of the super absorbent plastic short fiber is exposed out of one side close to moisture or water, of the flat plate type moisture permeable membrane. The flat plate type moisture permeable membrane provided by the invention is high in mechanical strength and applicable to humidifying or drying gases under a condition of a high differential pressure. The flat plate type moisture permeable membrane has high moisture transmittance and good gas barrier property and is particularly applicable to gas humidifying systems of fuel cells.
Description
Technical field
The present invention relates to a kind of flat moisture permeable membrane and preparation method thereof, specifically a kind of flat moisture permeable membrane of applying in fuel cell humidifying system and preparation method thereof, belongs to functional membrane technical field.
Background technology
Moisture permeable membrane is the critical material of space flight and aviation, Medical Devices and new-energy automobile vitals.Moisture permeable membrane belongs to hydrophilic film, and the kind of film can be organic film or inoranic membrane, and the form of film can be flat, can be also to have the very doughnut formula of high loading density.Its application is mainly to have utilized this function film to have strong hydrophilicity group, conducts, thereby have wet function by moisture absorption.
Proton Exchange Membrane Fuel Cells has the advantages such as environmental protection, efficient, toggle speed is fast, power density is large, is considered to one of main competitor of future transportation dynamical system.PEM only under suitable wet condition fuel cell could obtain good service behaviour.Fuel battery air and hydrogen gas all need to be humidified to prevent that PEM dehydration from reducing battery performance and working life, make fuel cell be able to efficient operation.
Permeable membrane humidifier is high-power humidifier the most frequently used in current fuel cell, and this humidifier film used has a variety of: microfiltration membranes, milipore filter, reverse osmosis membrane, TESLIN@film, NAFION@film and GORE-TEX@film.Wherein common with traditional NAFION@film.At present, this material is all almost Nafion115 film, Nafion117 film or the Nafion212 film that adopts DuPont company to produce.Therefore Nafion film is perfluoro sulfonic acid membrane, and its expensive main development obstacle that becomes such moistened membrane, reduces costs or product that development efficiency is higher is a development trend of perfluorinated sulfonic acid class moisture permeable membrane.
Chinese patent literature CN1621136A(application number 200310119265.5) a kind of cellulose hollow fiber gas moistened membrane is disclosed, but such film is wet method spinning, there is numerous and diverse techniques such as solvent recovery, and thoroughly wet effect and service life aspect and perfluorinated sulfonic acid class film also there is larger gap.
Also there is document to attempt the permeable membrane of hydrocarbon class to be applied to fuel cell humidifying system, but because the diffusion flux of water in film is subject to the restriction of diffusion coefficient and film both sides concentration difference, once select certain membrane humidifier, wherein the diffusion flux of water will be limited within limits, for vehicle-mounted high power fuel cell, the general volume of needed membrane humidifier is larger, and the system dynamic response of membrane humidifier is slow, is difficult to realize the accurate control of amount of humidification; After long-time use, film is easily damaged, causes and collaborates.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, a kind of under High Pressure Difference condition, have higher water flux, low gas permeation, high-intensity flat moisture permeable membrane are provided, be more suitable for the gas humidification system of fuel cell.Meanwhile, provide the preparation method of this moisture permeable membrane, the method technique is simple, easy to operate, pollution-free.
Term explanation:
Perfluorinated sulfonic acid ion exchange resin, has the general structure shown in following formula I:
In formula I: M is functional group-SO
2f, x=2～10, y=1, n=0 or 1, m=1～5; When n=0, being short chain resin, is long-chain resin during n=1.
High-hydroscopicity plastic short fibers, refers to strong water suction groups such as containing hydroxyl in molecule and has the functional high molecule material short fiber of certain degree of cross linking, has that water imbibition is high, the characteristic of good water-retaining property.
Above-described perfluorinated sulfonic acid ion exchange resin and high-hydroscopicity plastic short fibers, be prior art, can buy in market, also can prepare by prior art.
Technical scheme of the present invention is as follows:
A kind of flat moisture permeable membrane, it is characterized in that, the moisture permeable membrane of the writing board shape being prepared from by perfluorinated sulfonic acid ion exchange resin and high-hydroscopicity plastic short fibers composite, moisture permeable membrane thickness is 20～500 microns, moisture permeable membrane is two-phase open structure, wherein perfluorinated sulfonic acid ion exchange resin is continuous phase, high-hydroscopicity plastic short fibers is decentralized photo, the mass percent that described decentralized photo accounts for flat moisture permeable membrane gross mass is that flat moisture permeable membrane is exposed near a side of moisture or water in the end of 2～40%, 20～90% high-hydroscopicity plastic short fibers.
Described moisture permeable membrane, owing to being the composite of resin and fiber, so overall structure is comparatively loose with respect to homogeneous membrane, and loose structure is more conducive to the transmission of steam.
Flat moisture permeable membrane is exposed near a side of moisture or water in the end of 20～90% described high-hydroscopicity plastic short fibers, object is the short fiber end of the exposing moisture content in absorbing moisture rapidly, and be introduced into film body inside, strengthen the water saturation of perfluorinated sulfonic acid ion exchange resin continuous phase, when the water content of film is higher, wet efficiency will be higher thoroughly; And not allowing short fiber end to expose near a side of dry gas, reason is to prevent that short fiber from causing the surfaces externally and internally of flat moisture permeable membrane to be communicated with, thereby causes dry gas one side to occur water droplet.
The mass percent that accounts for flat moisture permeable membrane gross mass when decentralized photo is lower than 2% time, the humidification of high-hydroscopicity plastic short fibers is just not obvious, and the mass percent that accounts for flat moisture permeable membrane gross mass when decentralized photo is higher than 40% time, short fiber is easy to be agglomerated into coma, dispersed variation, the seeing through effect and can weaken of steam, and can form that stress is concentrated and the intensity that affects flat moisture permeable membrane.
The film body thickness of described moisture permeable membrane is crossed when thin, can cause insufficient strength; When thickness is blocked up, causes masking cost significantly to increase, and can increase the moist insulating value of film.
Preferred according to the present invention, the ion exchange capacity of described perfluorinated sulfonic acid ion exchange resin is 0.8～1.8mmol/g.
Preferred according to the present invention, described high-hydroscopicity plastic short fibers is selected from one of natural macromolecule modification water suction plastic short fibers, polyacrylic acid series high-hydroscopicity plastic short fibers, polypropylene fat series high-hydroscopicity plastic short fibers, polyvinyl alcohol series high-hydroscopicity plastic short fibers or Pluronic F-127, isobutene cis-butenedioic anhydride class high-hydroscopicity plastic short fibers or both above mixtures.
Further preferred according to the present invention, described high-hydroscopicity plastic short fibers is selected from one of polyacrylic acid series high-hydroscopicity plastic short fibers, polypropylene fat series high-hydroscopicity plastic short fibers, polyvinyl alcohol series high-hydroscopicity plastic short fibers or Pluronic F-127, isobutene cis-butenedioic anhydride class high-hydroscopicity plastic short fibers or both above mixtures.
Described high-hydroscopicity plastic short fibers is material known in this field, as: the short fiber that natural macromolecule modification water suction plastic short fibers can adopt the Starch with Acrylic Acid copolymer (SDL-A-700, SDL-B-1000) of Shanghai University's development to prepare.
Polyacrylic acid series high-hydroscopicity plastic short fibers: the short fiber that can adopt Polyacrylic Acid Sodium Salt High Water Absorbent Resin BOFENG-001 to prepare, Polyacrylic Acid Sodium Salt High Water Absorbent Resin BOFENG-001 Guangzhou Bo Feng Chemical Industry Science Co., Ltd is on sale;
Polypropylene fat series high-hydroscopicity plastic short fibers: can adopt the standby short fiber of SAP GR-28 type resin, SAP GR-28 type resin Lanzhou Li Xin Science and Technology Development Co., Ltd. is on sale;
Polyvinyl alcohol series high-hydroscopicity plastic short fibers, Pluronic F-127 class high-hydroscopicity plastic short fibers, isobutene cis-butenedioic anhydride class high-hydroscopicity plastic short fibers, all can adopt the high hydroscopic resin of Stockhausen company, U.S. Chemdal company or the BASF AG of Japanese catalyst chemical company, Deggusa/Huels group to prepare short fiber as raw material.
The preparation method of short fiber can be with reference to conventional process technology-solwution method (as the content of recording with reference to Chinese patent literature CN102433599A) or fusion method (content of recording with reference to Chinese patent literature CA101285218).
The heat resistance of natural macromolecule modification water suction plastic short fibers is bad, is not suitable for the higher situation of application places temperature of moisture permeable membrane.
Preferred according to the present invention, the length of described high-hydroscopicity plastic short fibers is 5～100mm, and thickness was 10～100 dawn.
Further preferred according to the present invention, the length of described high-hydroscopicity plastic short fibers is 10～50mm.When high-hydroscopicity plastic short fibers length too in short-term, in preparation process, be difficult to fiber end to expose, when high-hydroscopicity plastic short fibers length is long, easily produces and reunite, affect water permeability.
Above-mentioned flat moisture permeable membrane, is applicable to the humidification of gas under High Pressure Difference 0～400Kpa condition or is dried, and possessing high moisture vapor permeability and good barrier properties for gases, is particularly useful for the gas humidification system of fuel cell.
A preparation method for flat moisture permeable membrane, step is as follows:
1) take in proportion perfluorinated sulfonic acid ion exchange resin and high-hydroscopicity plastic short fibers, adopt double screw extruder to carry out blend granulation under 180～280 ℃ of conditions, make blend pellet;
2) blend pellet step 1) being made joins in single screw extrusion machine, under 180～280 ℃ of conditions, carries out fusion plastification, and melt is extruded by T-shaped mould curtain coating, through drawing-off, cooling aftershaping, makes flat sheet membrane;
The flat moisture permeable membrane of the molding runners of described T-shaped mould is Ra 3.2,6.3 or 12.5 μ m near the roughness of the forming surface of a side of moisture or water, and the roughness of the forming surface of opposite side is Ra0.005 μ m;
3) by step 2) flat sheet membrane that makes is converted into Hydrogen functional membrane, makes flat moisture permeable membrane.
Preferred according to the present invention, the conversion in described step 3), step is as follows:
By step 2) flat sheet membrane that makes soaks 100～200 hours in 85～95 ℃, the sodium hydroxide solution of mass percentage concentration 10～20%, adopt afterwards the sulfuric acid solution of mass percentage concentration 3～8% to clean 2～3 times, then in 85～95 ℃, the sulfuric acid solution of mass percentage concentration 4～9%, soak 2～3 times, each 10～15 hours, finally with pure water, clean in the pure water that is immersed in again 85～95 ℃ after 2～4 times, every 2～3 hours, change one time water, until pure water is neutral, make flat moisture permeable membrane.
Above-mentioned T-shaped mould curtain coating is extruded, drawing-off, cooling aftershaping step are this area conventional steps, can be referring to document: Wang Fengxia, Yuan Huilin, Cao Huilin, the preparation that melt extrudes processing characteristics and amberplex thereof of perfluorinated sulfonic resin, < < membrane science and technology > >, 27(5) 2007.
Above-mentioned double screw extruder, single screw extrusion machine are the conventional membrane equipment in this area.
The application of above-mentioned flat moisture permeable membrane in preparing fuel cell unit humidification system.
The present invention compared with prior art has following excellent results:
1, adding of the flat moisture permeable membrane middle short fiber of the present invention, played obvious humidification, film bend-resistance, stretch-proof, not embrittlement, long service life.
2, feature is exposed in the short fiber end in the flat moisture permeable membrane of the present invention, reduced membrane body water suction equilibration time, increased saturated water adsorptive value, improved water permeability and permeable efficiency.
3, the high strength of the flat moisture permeable membrane of the present invention allows its long-term work under High Pressure Difference condition, can not break.
4, the two-phase open structure of the flat moisture permeable membrane of the present invention, not only increases steam and sees through effect, and the volume of resin and high-hydroscopicity plastic short fibers expands rapidly after film water suction, and the densification of structure change has excellent barriering effect for the infiltration of gas.
Accompanying drawing explanation
Fig. 1 is the cross section structure schematic diagram of flat moisture permeable membrane;
Wherein: 1, perfluorinated sulfonic acid ion exchange resin (continuous phase), 2, high-hydroscopicity plastic short fibers (decentralized photo), 3, flat moisture permeable membrane is near a side of moisture or water, and 4, flat moisture permeable membrane is near the one side of dry gas, 5, expose the high-hydroscopicity plastic short fibers end on film surface;
Fig. 2 is the gas humidification system experimental provision structure chart that adopts the flat moisture permeable membrane assembling of the present invention;
Wherein: 1, cleaner, 2, air compressor machine, 3, pressure maintaining valve, 4, gas flowmeter, 5, temperature and pressure sensor, 6, membrane humidifier, 7, thermometer, 8, counterbalance valve, 9, water ga(u)ge, 10, constant temperature water bath apparatus, 11, valve.
The specific embodiment
Below in conjunction with the specific embodiment, technical scheme of the present invention is described further, but institute of the present invention protection domain is not limited to this.
Raw material explanation
Perfluorinated sulfonic resin Shandong Huaxia Shenzhou New Material Co., Ltd. described in embodiment 1～4 is on sale;
Polyacrylic acid series high-hydroscopicity plastic short fibers described in embodiment, polyvinyl alcohol series high-hydroscopicity plastic short fibers, polyvinyl alcohol series high-hydroscopicity plastic short fibers, isobutene cis-butenedioic anhydride class high-hydroscopicity plastic short fibers are that prepare by this area conventional method common commercially available prod.
Employing IEC(ion exchange capacity) perfluorinated sulfonic resin of=1.3mmol/g, structural formula is as follows
In formula, M is-SO
2f, x=3.4, n=1, m=3;
Polyacrylic acid series high-hydroscopicity plastic short fibers, length is 30mm, thickness was 35 dawn;
By above-mentioned perfluorinated sulfonic resin and polyacrylic acid series high-hydroscopicity plastic short fibers, according to mass ratio, be after 65:35 mixes, by double screw extruder, at 210 ℃, carry out blend granulation, make blend pellet;
The blend pellet making is joined and in single screw extrusion machine, at 210 ℃, carries out fusion plastification, melt is extruded by T-shaped mould curtain coating, wherein the flat moisture permeable membrane of molding runners is Ra=6.3 μ m near the forming surface roughness of a side of moisture or water, flat moisture permeable membrane is Ra=0.005 μ m near the forming surface roughness of dry gas one side, then pass through drawing-off, cooling aftershaping, make flat sheet membrane;
In the flat sheet membrane obtaining, perfluorinated sulfonic acid ion exchange resin is continuous phase, the high water suction of polyacrylic acid series plastic short fibers is decentralized photo, 110 microns of dull and stereotyped thickness, external diameter 1.02mm, wherein flat moisture permeable membrane is exposed near a side of moisture or water in the end of 55% polyacrylic acid series high-hydroscopicity plastic short fibers;
The flat sheet membrane making is soaked 150 hours in 90 ℃, the sodium hydroxide solution of mass percentage concentration 15%, adopt afterwards the sulfuric acid solution of mass percentage concentration 5% to clean three times, then in 90 ℃, the sulfuric acid solution of mass percentage concentration 5%, soak 2 times, each 10 hours, finally with pure water, clean in the pure water that is immersed in again 90 ℃ after three times, every 2 hours, change one time water, until pure water is neutral, make flat moisture permeable membrane.
Above-mentioned make flat moisture permeable membrane be by perfluorinated sulfonic acid ion exchange resin and polyacrylic acid series high-hydroscopicity plastic short fibers in mass ratio 65:35 composite be prepared from, this film is two-phase open structure, wherein perfluorinated sulfonic acid ion exchange resin is continuous phase, polyacrylic acid series high-hydroscopicity plastic short fibers is decentralized photo, described decentralized photo accounts for the end of the polyacrylic acid series high-hydroscopicity plastic short fibers that the mass percent of flat moisture permeable membrane gross mass is 35%, 55% and exposes flat moisture permeable membrane near a side of moisture.
Above-mentioned flat moisture permeable membrane is assembled into the assembly that is applicable to 5KW fuel cell unit humidification system, and the film gross area is 6200cm
2.At gas flow, be 10m
3/ h, water temperature are that 83 ℃, dry gas temperature are 75 ℃, pressure reduction while being 100KPa, and the rate of perviousness of this assembly reaches 89470g/m
224h, can be by unstripped gas, and the humidity of dry gas is increased to 91%RH, meets the humidification requirement of fuel cell unstripped gas completely, and result is as shown in table 1.
Gas humidification system experimental provision as shown in Figure 2, comprise cleaner 1, air compressor machine 2, pressure maintaining valve 3, gas flowmeter 4, temperature and pressure sensor 5, membrane humidifier 6, thermometer 7, counterbalance valve 8, water ga(u)ge 9, constant temperature water bath apparatus 10 and valve 11, dry gas is successively by cleaner 1, air compressor machine 2, pressure maintaining valve 3, gas flowmeter 4, after temperature and pressure sensor 5, enter membrane humidifier 6 humidifications, then through thermometer 7 and counterbalance valve 8, discharge, the moisture of membrane humidifier 6 derives from constant temperature water bath apparatus 10, water in constant temperature water bath apparatus 10 enters membrane humidifier 6 through valve 11 and temperature and pressure sensor 5, after exchange of moisture, residual moisture is back to constant temperature water bath apparatus 10 through water ga(u)ge 9.
The membrane humidifier of above-mentioned employing, is comprised of 15 flat moisture permeable membranes, and there are 18 runners every flat moisture permeable membrane both sides, adopts rectangle channel; The dry air for the treatment of humidification is provided by air compressor machine, and the aqueous water that humidification is used is provided by water bath with thermostatic control, and air and hydromining counter-current operation utilize hygronom to measure the humidity of gas after humidification.
Adopting the patent No. is the detection method of the gas permeability of the moisture permeable membrane that in CN 1621136A, embodiment partly sets forth, and records in the present embodiment the H of moisture permeable membrane after saturated humidification
2infiltration rate is 1.06 * 10
-8cm
3(STP)/(cm
2* s*cmHg), meet the application in fuel cell Wetting System For Feed Gas completely.The resistance to tearing that records film according to the method in GB GB/T 16578.2 is 62N, and the folding strength that records film according to the method in GB GB/T 457 is 4.3, and the bursting strength that records film according to the method in GB GB/T 454 is 2.3MPa.
Comparative example 1
Adopt Nafion117 film according to the method for embodiment 1, to be assembled into the assembly of 5KW fuel cell unit humidification system, and under identical condition, carry out Performance Detection, comparing result is as shown in table 1.
Employing IEC(ion exchange capacity) perfluorinated sulfonic resin of=1.20mmol/g, structural formula is as follows
In formula, M is-SO
2f, x=5.5, n=0, m=4;
Polyvinyl alcohol series high-hydroscopicity plastic short fibers, length is 15mm, thickness was 60 dawn;
By above-mentioned perfluorinated sulfonic resin and polyvinyl alcohol series high-hydroscopicity plastic short fibers, according to mass ratio, be after 4:1 mixes, by double screw extruder, at 230 ℃, carry out blend granulation, make blend pellet;
The blend pellet making is joined and in single screw extrusion machine, at 220 ℃, carries out fusion plastification, melt is extruded by T-shaped mould curtain coating, wherein the flat moisture permeable membrane of molding runners is Ra=12.5 μ m near the forming surface roughness of a side of moisture or water, flat moisture permeable membrane is Ra=0.005 μ m near the forming surface roughness of dry gas one side, then pass through drawing-off, cooling aftershaping, make flat sheet membrane;
In the flat sheet membrane obtaining, perfluorinated sulfonic acid ion exchange resin is continuous phase, polyvinyl alcohol series high-hydroscopicity plastic short fibers is decentralized photo, 65 microns of dull and stereotyped thickness, wherein flat moisture permeable membrane is exposed near a side of moisture or water in the end of 65% polyvinyl alcohol series high-hydroscopicity plastic short fibers;
The flat sheet membrane making is processed according to the method for embodiment 1, obtained flat moisture permeable membrane.
Above-mentioned flat moisture permeable membrane is assembled into the assembly of 5KW fuel cell unit humidification system according to the method for embodiment 1, and under identical condition, carries out Performance Detection, wherein pressure reduction is 200KPa, and result is as shown in table 1.
Employing IEC(ion exchange capacity) perfluorinated sulfonic resin of=1.80mmol/g, structural formula is as follows
In formula, M is-SO
2f, x=2.0, n=1, m=3;
Isobutene cis-butenedioic anhydride class high-hydroscopicity plastic short fibers, length is 70mm, thickness was 25 dawn;
By above-mentioned perfluorinated sulfonic resin and isobutene cis-butenedioic anhydride class high-hydroscopicity plastic short fibers, according to mass ratio, be after 92:8 mixes, by double screw extruder, at 190 ℃, carry out blend granulation, make blend pellet;
The blend pellet making is joined and in single screw extrusion machine, at 185 ℃, carries out fusion plastification, melt is extruded by T-shaped mould curtain coating, wherein the flat moisture permeable membrane of molding runners is Ra=3.2 μ m near the forming surface roughness of a side of moisture or water, flat moisture permeable membrane is Ra=0.005 μ m near the forming surface roughness of dry gas one side, then pass through drawing-off, cooling aftershaping, make flat sheet membrane;
In the flat sheet membrane obtaining, perfluorinated sulfonic acid ion exchange resin is continuous phase, isobutene cis-butenedioic anhydride class high-hydroscopicity plastic short fibers is decentralized photo, 230 microns of dull and stereotyped thickness, wherein flat moisture permeable membrane is exposed near a side of moisture or water in the end of 45% isobutene cis-butenedioic anhydride class high-hydroscopicity plastic short fibers; The flat sheet membrane making is processed according to the method for embodiment 1, obtained flat moisture permeable membrane.
Above-mentioned flat moisture permeable membrane is assembled into the assembly of 5KW fuel cell unit humidification system according to the method for embodiment 1, and under identical condition, carries out Performance Detection, wherein pressure reduction is 300KPa, and result is as shown in table 1.
Employing IEC(ion exchange capacity) perfluorinated sulfonic resin of=0.90mmol/g, structural formula is as follows
In formula, M is-SO
2f, x=6.8, n=1, m=5;
Isobutene cis-butenedioic anhydride class high-hydroscopicity plastic short fibers, length is 15mm, thickness was 20 dawn;
By above-mentioned perfluorinated sulfonic resin and isobutene cis-butenedioic anhydride class high-hydroscopicity plastic short fibers, according to mass ratio, be after 3:2 mixes, by double screw extruder, at 270 ℃, carry out blend granulation, make blend pellet;
The blend pellet making is joined and in single screw extrusion machine, at 260 ℃, carries out fusion plastification, melt is extruded by T-shaped mould curtain coating, wherein the flat moisture permeable membrane of molding runners is Ra=6.3 μ m near the forming surface roughness of a side of moisture or water, flat moisture permeable membrane is Ra=0.005 μ m near the forming surface roughness of dry gas one side, then pass through drawing-off, cooling aftershaping, make flat sheet membrane;
In the flat sheet membrane obtaining, perfluorinated sulfonic acid ion exchange resin is continuous phase, isobutene cis-butenedioic anhydride class high-hydroscopicity plastic short fibers is decentralized photo, 50 microns of dull and stereotyped thickness, wherein flat moisture permeable membrane is exposed near a side of moisture or water in the end of 75% isobutene cis-butenedioic anhydride class high-hydroscopicity plastic short fibers; The flat sheet membrane making is processed according to the method for embodiment 1, obtained flat moisture permeable membrane.
Above-mentioned flat moisture permeable membrane is assembled into the assembly of 5KW fuel cell unit humidification system according to the method for embodiment 1, and under identical condition, carries out Performance Detection, wherein pressure reduction is 400KPa, and result is as shown in table 1.
Table 1
Interpretation of result
As can be seen from Table 1, with respect to the existing Nafion117 film of comparative example 1, moisture permeable membrane of the present invention has higher vapor transfer rate, lower H
2infiltration rate, and under same service condition, the humidification successful of dry gas is better than to comparative example 1, possess higher mechanical strength simultaneously.
Claims (9)
1. a flat moisture permeable membrane, it is characterized in that, the moisture permeable membrane of the writing board shape being prepared from by perfluorinated sulfonic acid ion exchange resin and high-hydroscopicity plastic short fibers composite, moisture permeable membrane thickness is 20～500 microns, moisture permeable membrane is two-phase open structure, wherein perfluorinated sulfonic acid ion exchange resin is continuous phase, high-hydroscopicity plastic short fibers is decentralized photo, the mass percent that described decentralized photo accounts for flat moisture permeable membrane gross mass is that flat moisture permeable membrane is exposed near a side of moisture or water in the end of 2～40%, 20～90% high-hydroscopicity plastic short fibers.
2. flat moisture permeable membrane as claimed in claim 1, is characterized in that, the ion exchange capacity of described perfluorinated sulfonic acid ion exchange resin is 0.8～1.8mmol/g.
3. flat moisture permeable membrane as claimed in claim 1, it is characterized in that, described high-hydroscopicity plastic short fibers is selected from one of natural macromolecule modification water suction plastic short fibers, polyacrylic acid series high-hydroscopicity plastic short fibers, polypropylene fat series high-hydroscopicity plastic short fibers, polyvinyl alcohol series high-hydroscopicity plastic short fibers or Pluronic F-127, isobutene cis-butenedioic anhydride class high-hydroscopicity plastic short fibers or both above mixtures.
4. flat moisture permeable membrane as claimed in claim 3, it is characterized in that, described high-hydroscopicity plastic short fibers is selected from one of polyacrylic acid series high-hydroscopicity plastic short fibers, polypropylene fat series high-hydroscopicity plastic short fibers, polyvinyl alcohol series high-hydroscopicity plastic short fibers or Pluronic F-127, isobutene cis-butenedioic anhydride class high-hydroscopicity plastic short fibers or both above mixtures.
5. flat moisture permeable membrane as claimed in claim 1, is characterized in that, the length of described high-hydroscopicity plastic short fibers is 5～100mm, and thickness was 10～100 dawn.
6. flat moisture permeable membrane as claimed in claim 5, is characterized in that, the length of described high-hydroscopicity plastic short fibers is 10～50mm.
7. a preparation method for flat moisture permeable membrane described in claim 1, is characterized in that, step is as follows:
1) take in proportion perfluorinated sulfonic acid ion exchange resin and high-hydroscopicity plastic short fibers, adopt double screw extruder to carry out blend granulation under 180～280 ℃ of conditions, make blend pellet;
2) blend pellet step 1) being made joins in single screw extrusion machine, under 180～280 ℃ of conditions, carries out fusion plastification, and melt is extruded by T-shaped mould curtain coating, through drawing-off, cooling aftershaping, makes flat sheet membrane;
The flat moisture permeable membrane of the molding runners of described T-shaped mould is Ra 3.2,6.3 or 12.5 μ m near the roughness of the forming surface of a side of moisture or water, and the roughness of the forming surface of opposite side is Ra 0.005 μ m;
3) by step 2) flat sheet membrane that makes is converted into Hydrogen functional membrane, makes flat moisture permeable membrane.
8. preparation method as claimed in claim 7, is characterized in that, the conversion in described step 3), and step is as follows:
By step 2) flat sheet membrane that makes soaks 100～200 hours in 85～95 ℃, the sodium hydroxide solution of mass percentage concentration 10～20%, adopt afterwards the sulfuric acid solution of mass percentage concentration 3～8% to clean 2～3 times, then in 85～95 ℃, the sulfuric acid solution of mass percentage concentration 4～9%, soak 2～3 times, each 10～15 hours, finally with pure water, clean in the pure water that is immersed in again 85～95 ℃ after 2～4 times, every 2～3 hours, change one time water, until pure water is neutral, make flat moisture permeable membrane.
9. the application of flat moisture permeable membrane in preparing fuel cell unit humidification system described in claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310517322.9A CN103551058B (en) | 2013-10-28 | 2013-10-28 | Flat plate type moisture permeable membrane as well as preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310517322.9A CN103551058B (en) | 2013-10-28 | 2013-10-28 | Flat plate type moisture permeable membrane as well as preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103551058A true CN103551058A (en) | 2014-02-05 |
| CN103551058B CN103551058B (en) | 2015-07-15 |
Family
ID=50005520
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310517322.9A Active CN103551058B (en) | 2013-10-28 | 2013-10-28 | Flat plate type moisture permeable membrane as well as preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103551058B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107008166A (en) * | 2017-03-22 | 2017-08-04 | 同济大学 | A kind of nano combined moisture permeable membrane and preparation method and application |
| CN110406257A (en) * | 2018-04-30 | 2019-11-05 | 精工爱普生株式会社 | Precision equipment and its manufacturing method and its used hygroscopic agent and its preparation method |
| CN111804348A (en) * | 2020-05-30 | 2020-10-23 | 山东东岳高分子材料有限公司 | Reinforcing net for fluorine-containing cation exchange membrane and application thereof |
| CN112993352A (en) * | 2019-12-14 | 2021-06-18 | 中国科学院大连化学物理研究所 | High-water-retention resin composite film and preparation method thereof |
| CN113150333A (en) * | 2021-02-07 | 2021-07-23 | 浙江汉丞科技有限公司 | Preparation method of fluorine-containing super-oleophobic microporous membrane with high moisture permeability |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101071873A (en) * | 2007-06-06 | 2007-11-14 | 武汉理工大学 | Polymer supershort fiber reinforced fuel cell proton exchange membrane and its preparing method |
-
2013
- 2013-10-28 CN CN201310517322.9A patent/CN103551058B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101071873A (en) * | 2007-06-06 | 2007-11-14 | 武汉理工大学 | Polymer supershort fiber reinforced fuel cell proton exchange membrane and its preparing method |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107008166A (en) * | 2017-03-22 | 2017-08-04 | 同济大学 | A kind of nano combined moisture permeable membrane and preparation method and application |
| CN107008166B (en) * | 2017-03-22 | 2020-07-07 | 同济大学 | Nano composite moisture permeable film and preparation method and application thereof |
| CN110406257A (en) * | 2018-04-30 | 2019-11-05 | 精工爱普生株式会社 | Precision equipment and its manufacturing method and its used hygroscopic agent and its preparation method |
| US10828895B2 (en) | 2018-04-30 | 2020-11-10 | Seiko Epson Corporation | Precision instrument, moisture absorbent used therefor, manufacturing method of moisture absorbent, and manufacturing method of precision instrument |
| CN112993352A (en) * | 2019-12-14 | 2021-06-18 | 中国科学院大连化学物理研究所 | High-water-retention resin composite film and preparation method thereof |
| CN111804348A (en) * | 2020-05-30 | 2020-10-23 | 山东东岳高分子材料有限公司 | Reinforcing net for fluorine-containing cation exchange membrane and application thereof |
| CN113150333A (en) * | 2021-02-07 | 2021-07-23 | 浙江汉丞科技有限公司 | Preparation method of fluorine-containing super-oleophobic microporous membrane with high moisture permeability |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103551058B (en) | 2015-07-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103551058B (en) | Flat plate type moisture permeable membrane as well as preparation method thereof | |
| CN104362277A (en) | Composite separator with multilayered structure and preparation method of separator | |
| CN112292198B (en) | Composite hollow fiber membrane, method for producing same, hollow fiber membrane cartridge comprising same, and fuel cell membrane humidifier | |
| EP3640014B1 (en) | Reinforced membrane for separation in battery and preparation method therefor | |
| CN111916807B (en) | Ultrathin enhanced composite proton exchange membrane, preparation method and application | |
| CA2717354C (en) | Hybrid membrane comprising chitosan, hydroxy ethyl cellulose, and montmorillonite | |
| CN101728549B (en) | High-temperature proton exchange compound film | |
| CN109608794B (en) | PTFE microporous membrane and preparation method thereof and composite proton exchange membrane | |
| CN104157815A (en) | Bacterial cellulose porous thin film and preparation method thereof | |
| CN107732273B (en) | Preparation method of graphene quantum dot modified proton exchange membrane | |
| CN108285643A (en) | Cellulose nano-fibrous/the Sulfonated Polyethersulfone Proton Exchange Membrane of one kind and preparation method | |
| TWI577078B (en) | Bilayer complex proton exchange membrane and membrane electrode assembly | |
| CN113926316B (en) | Leakage-proof humidifying composite hollow fiber membrane, preparation method and application thereof | |
| CN103515640B (en) | A kind of carbon nanofiber-reinforcedproton proton exchange membrane and preparation method thereof | |
| CN104716353A (en) | Porous membrane used for liquid flow cell and preparation and application thereof | |
| CN110247090A (en) | A kind of preparation method of the fuel cell modified Nafion proton exchange membrane of zeolite imidazole ester skeleton nanofiber | |
| WO2011156933A1 (en) | Composite having ion exchange function and preparation method and use thereof | |
| CN108630972B (en) | Preparation method of antioxidant graphene quantum dot modified proton exchange membrane | |
| CN102489174A (en) | Composite gel type gas separation membrane and preparation method thereof | |
| CN103474680A (en) | Super absorbent proton exchange membrane and preparation method thereof | |
| CN102569855A (en) | Electrolyte membrane and fuel cell employing it | |
| CN103551059B (en) | Fiber tube type moisture permeable film and preparation method thereof | |
| CN110556558B (en) | Multilayer composite proton exchange membrane and preparation method thereof | |
| CN105355939A (en) | Proton exchange membrane for fuel cell and preparation method of proton exchange membrane | |
| CN112717731A (en) | Ion conductive film and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20180409 Address after: 256401 Zibo Huantai County, Shandong Province, Tangshan town Dongyue Fluorosilicic Industrial Park Patentee after: Shandong Dongyue future hydrogen energy materials Co., Ltd. Address before: 256401 Tangshan, Shandong, Huantai Town, Zibo Patentee before: Shandong Dongyue Polymer Material Co., Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200429 Address after: 256401 Tangshan Town, Huantai County, Zibo, Shandong Patentee after: SHANDONG DONGYUE POLYMER MATERIAL Co.,Ltd. Address before: 256401 Zibo Huantai County, Shandong Province, Tangshan town Dongyue Fluorosilicic Industrial Park Patentee before: Shandong Dongyue future hydrogen energy materials Co.,Ltd. |