CN101752574A - Preparation method of ultra-thin enhanced proton exchange membrane - Google Patents
Preparation method of ultra-thin enhanced proton exchange membrane Download PDFInfo
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- CN101752574A CN101752574A CN200810203545A CN200810203545A CN101752574A CN 101752574 A CN101752574 A CN 101752574A CN 200810203545 A CN200810203545 A CN 200810203545A CN 200810203545 A CN200810203545 A CN 200810203545A CN 101752574 A CN101752574 A CN 101752574A
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- 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
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- 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
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Abstract
The invention relates to a preparation method of an ultra-thin enhanced proton exchange membrane, which is characterized by comprising the following steps of: (1) pretreatment: firstly, immersing a PTFE millipore membrane in a low carbon alcohol solution for 2-10 hours, and then, irradiating the millipore membrane with ultraviolet rays for 1-4 hours; (2) compounding: compounding under a vacuum condition and in a heating state, spraying a sulfoacid resin solution to the PTFE millipore membrane, seeping into millipores, and forming a proton exchange membrane by the PTFE milipores and sulfoacid resin membrane layers on both sides of the PTFE millipore membrane; (3) rolling: hot rolling the primarily formed proton exchange membrane in double rollers, and finally, forming the compact proton exchange membrane. The thickness of the proton exchange membrane is from 4 to 12 mum, the deviation value of non-uniform thickness is from +/-0.2 to +/-0.5 mum, the electrical conductivity is from 0.1 to 0.15 s/cm, and the tensile strength is from 40 to 50 MPa.
Description
Technical field:
The present invention relates to a kind of proton exchange membrane, particularly relate to a kind of preparation method of ultra-thin enhanced proton exchange membrane.
Background technology:
Proton exchange membrane is one of critical component of Proton Exchange Membrane Fuel Cells, and its quality is directly connected to this fuel battery performance and useful life.
Ultrathin perfluorinated sulfonic resin proton exchange membrane is used for proton conducting, and operation principle is based on electrochemistry.In anode-side, hydrogen dissociates on the anode catalyst surface and generates proton and electronics, and this proton is by the sulfonic group (SO on the proton exchange membrane
3H) be delivered to negative electrode, and this electronics arrives anode by the external circuit load, thereby form the work done of powering to external world of a complete electric loop.The proton exchange membrane made from sulfonate resin is the important focus of researching and developing both at home and abroad.
The perfluorinated sulfonic resin proton exchange membrane is succeeded in developing and large-scale production by offshore company the earliest.But its intensity is not high, and costs an arm and a leg.For improving its intensity, thereby reduce the sulfonate resin consumption and reduce cost, the back adopts polytetrafluoroethylene film to make pedestal, the composite sulfoacid resin is made enhanced proton exchange membrane and large-scale production on this film, but price is still expensive, and also have the bigger shortcoming of thickness, its thickness is generally more than 20 μ m.Domestic also have unit research and development perfluorinated sulfonic resin proton exchange membrane, yet the problem that domestic proton exchange membrane exists is that conductivity is little, is generally below the 0.12s/cm; Hot strength is lower, generally at 26Mpa.
Summary of the invention:
The objective of the invention is to provide a kind of preparation method of ultra-thin enhanced proton exchange membrane, not only technology is reasonable, perfect for it, easy to operate, and, can improve penetrating power, speed that sulfonate resin solution penetrates into the polytetrafluoroethylene film micropore, and significantly strengthened the strong bonded of sulfonate resin solution and polytetrafluoroethylmicroporous microporous membrane, thickness is even, and makes the proton exchange membrane stable performance.Utilize the preparation method of ultra-thin enhanced proton exchange membrane of the present invention, resulting proton exchange thin film thickness, conductivity is big, and hot strength height, and the also reduction greatly of sulfonate resin consumption are not only enhanced productivity but also reduce production costs.
The present invention is achieved in that to achieve the above object
The preparation method of ultra-thin enhanced proton exchange membrane of the present invention comprises the following steps:
(1) preliminary treatment is placed on polytetrafluoroethylmicroporous microporous membrane in the low-carbon alcohol solution earlier and floods, and dip time is 2-10 hour, uses ultraviolet irradiation then, and the ultraviolet illumination time is 1-4 hour;
(2) compound, compound is to carry out under vacuum condition and heating status, sulfonate resin solution is ejected into polytetrafluoroethylmicroporous microporous membrane and infiltration into microporous, forms continuous proton exchange membrane at this polytetrafluoroethylene film micropore and polytetrafluoroethylmicroporous microporous membrane two side sulfonate resin retes;
(3) roll-in is heated roll-in with the proton exchange membrane that just forms in two running rollers, obtain forming fine and close proton exchange membrane at last.
The thickness of described polytetrafluoroethylmicroporous microporous membrane is 2-10 μ m, and the aperture is 0.2-1.5 μ m, and porosity is 65-95%.
Described low-carbon alcohols is methyl alcohol, ethanol, propyl alcohol or isopropyl alcohol.
The wavelength of described ultraviolet irradiation is 100-200nm, and makes the polytetrafluoroethylmicroporous microporous membrane surface temperature reach 40-80 ℃.
Sulfonate resin concentration is at 2.5-50g/L in the described sulfonate resin solution, and the consumption of described sulfonate resin solution is 100-450mL/m
2
The vacuum degree of described vacuum condition is-6--600mmHg that described heating status is that temperature is 40-90 ℃.
The described pair of running roller made by stainless steel and had endogenous pyrogen, and diameter is 20-50cm, and the running roller gap is 4-20 μ m, and adjustable gaps, and the running roller surface temperature is 50-230 ℃.
Described endogenous pyrogen is that electric heating is held in both hands electric heater, conduction oil electric heater or superheated vapor.
The thickness of described ultra-thin enhanced proton exchange membrane is 4-12 μ m, and deviate in uneven thickness is ± 0.2-± 0.5 μ m, and conductivity is 0.1-0.15s/cm, and hot strength is 40-50MPa.
The preparation method of ultra-thin enhanced proton exchange membrane of the present invention has following characteristics:
1, the preparation method of ultra-thin enhanced proton exchange membrane of the present invention is when preliminary treatment, the dipping and the ultraviolet irradiation combination simultaneously of low-carbon alcohols are used, adopting the advantage of low-carbon alcohols dipping polytetrafluoroethylmicroporous microporous membrane is the surface modification that makes polytetrafluoroethylmicroporous microporous membrane, adjust the contact angle of p-sulfonic acid resin solution, improve solution and penetrate into the interior speed of micropore.Adopt UV-irradiation can change the interior C-F key bond energy of certain limit, thereby improve the ability that sulfonate resin solution infiltrates through polytetrafluoroethylmicroporous microporous membrane.
2, the preparation method of ultra-thin enhanced proton exchange membrane of the present invention is at compound tense, be chosen under vacuum condition and the heating status and carry out, vacuum condition can increase the pressure reduction of polytetrafluoroethylmicroporous microporous membrane both sides, even solution increases by the motive force of polytetrafluoroethylmicroporous microporous membrane, this can improve penetrating power can improve productive rate, and this pressure reduction has also strengthened the stress effect at sulfonate resin and polytetrafluoroethylmicroporous microporous membrane interface.Described heating temperature can increase the interior energy of solution molecule warm-up movement, strengthened the Contact Effect of sulfonate resin molecule and polytetrafluoroethylmicroporous microporous membrane, and making proton exchange membrane stable performance, sulfonate resin be unlikely to separate with polytetrafluoroethylmicroporous microporous membrane, conjugation significantly improves.
3, also utilize two running rollers to heat roll-in among the preparation method of ultra-thin enhanced proton exchange membrane of the present invention, adopt roll-in can make sulfonate resin solution film of undercompounding moulding also on polytetrafluoroethylmicroporous microporous membrane, the sulfonic acid system forms the continuous medium of a densification, and can also make the proton exchange film thickness that is become even.
The thickness of the prepared described ultra-thin enhanced proton exchange membrane of preparation method of ultra-thin enhanced proton exchange membrane of the present invention is 4-12 μ m, deviate in uneven thickness is ± 0.2-± 0.5 μ m, conductivity is 0.1-0.15s/cm, hot strength is 40-50MPa, and all is better than existing other proton exchange membrane.
Description of drawings:
The present invention is provided by following embodiment and accompanying drawing thereof.
Fig. 1 is the schematic diagram of Enhanced proton exchange membrane integrated apparatus used in the present invention.
Fig. 2 is a kind of schematic diagram that sprays the sprayer unit that sulfonate resin solution uses used in the present invention.
Embodiment:
Following example further specifies the present invention.
Embodiment
The preparation method's of ultra-thin enhanced proton exchange membrane of the present invention step is as follows:
At first polytetrafluoroethylmicroporous microporous membrane is carried out preliminary treatment, with thickness is 4 μ m, the aperture is 0.9 μ m, porosity is that the polytetrafluoroethylmicroporous microporous membrane of 70-80% is placed in the low-carbon alcohol solution and floods, dip time is 3-4 hour, after use ultraviolet irradiation again, the ultraviolet illumination time is 1.5-2.5 hour, the wavelength of described ultraviolet irradiation is 140-160nm, and makes the polytetrafluoroethylmicroporous microporous membrane surface temperature reach 55-65 ℃.
Carry out compoundly then, the employed equipment of compound tense is Enhanced proton exchange membrane integrated apparatus and a kind ofly sprays the sprayer unit that sulfonate resin solution is used.
Its that Enhanced proton exchange membrane integrated apparatus comprises set successively stainless steel supporting network compartment 14 in the compound dish 11, compound dish 11 from bottom to top, have infrared heater 18 on the left side wall of the end, upper end of thick film lamella 15, the thin clathrum 16 of polytetrafluoroethylene, compound dish 11 in the high performance polymer of micropore and an end, lower end in the compound dish 11 gone up porose 12 the right-hand member end of distributing and stretched out equal uniform flow exhaust tube 13 outside described compound dish 11 right side walls.
Be compounded under vacuum condition and the heating status and implement, concrete operations, to be placed on the thin clathrum 16 of polytetrafluoroethylene of described Enhanced proton exchange membrane integrated apparatus through pretreated polytetrafluoroethylmicroporous microporous membrane 17, then its that makes vacuum pump and described Enhanced proton exchange membrane integrated apparatus by conduit gone up the end formation that right side wall that porose 12 the equal uniform flow exhaust tube 13 of distributing stretches out described compound dish 11 locates outward and is communicated with, and startup vacuum pump, simultaneously, with described a kind of opening by the high-pressure air source 21 that tube connector 28 is connected of sprayer unit that sulfonate resin solution uses of spraying with described airtight pressure-vessel 22, described high-pressure air source 21 is an inert gas, pressurized inert gases in the epicoele 25 of described airtight pressure-vessel 22 force the described one-way pressure valve 27 at described interlayer 24 middle parts to be opened, utilize inert gas in the described airtight pressure-vessel 22 as working media immediately, sulfonate resin solution in the cavity of resorption 26 of described airtight pressure-vessel 22 are ejected into sulfonate resin solution on the described polytetrafluoroethylmicroporous microporous membrane 17 equably by the described shower nozzle 23 that pipeline 29 connects, the pressure energy that the dynamic pressure of droplet is changed into, in the micropore on the sulfonate resin solution infiltration polytetrafluoroethylmicroporous microporous membrane 17, meanwhile, promptly form a size at the place, end, compound dish 11 lower end of described Enhanced proton exchange membrane integrated apparatus and be 5-20mmH
2The negative pressure of o, also impel sulfonate resin solution can comparatively fast be filled to the interior and evenly distribution of realization of micropore of described polytetrafluoroethylmicroporous microporous membrane 17, then, combine securely with it, and it is covered, micropore and polytetrafluoroethylmicroporous microporous membrane 17 2 side sulfonate resin retes at this polytetrafluoroethylmicroporous microporous membrane 17 form continuous proton exchange membrane, again by infrared heater 18 heating, heating-up temperature is 50-60 ℃, after the heating, can form well-balanced proton exchange membrane, sulfonate resin concentration is at 2.5-50g/L in the described sulfonate resin solution, and the consumption of described sulfonate resin solution is 150-250mL/m
2, the vacuum degree of described vacuum condition is-150--250mmHg.
Implement roll-in at last, the proton exchange membrane that just forms is heated roll-in in two running rollers, obtain forming fine and close proton exchange membrane at last, the thickness of described proton exchange membrane is 6-9 μ m, deviate in uneven thickness is ± 0.2-± 0.5 μ m, conductivity is 0.1-0.15s/cm, and hot strength is 40-50MPa.Described pair of running roller made by stainless steel, and diameter is 20-50cm, and the running roller gap is 4-20 μ m, and adjustable gaps, described pair of running roller and have endogenous pyrogen, and described endogenous pyrogen is the conduction oil electric heater, the running roller surface temperature is 150-180 ℃.
Described Enhanced proton exchange membrane integrated apparatus and a kind of to spray the sprayer unit that sulfonate resin solution uses be home-built equipment, this equipment patent No. is respectively ZL200720077053.9, ZL200720067134.0.
Claims (9)
1. the preparation method of a ultra-thin enhanced proton exchange membrane is characterized in that this method comprises the following steps:
(1) preliminary treatment is placed on polytetrafluoroethylmicroporous microporous membrane in the low-carbon alcohol solution earlier and floods, and dip time is 2-10 hour, uses ultraviolet irradiation then, and the ultraviolet illumination time is 1-4 hour;
(2) compound, compound is to carry out under vacuum condition and heating status, sulfonate resin solution is ejected into polytetrafluoroethylmicroporous microporous membrane and infiltration into microporous, forms continuous proton exchange membrane at this polytetrafluoroethylene film micropore and polytetrafluoroethylmicroporous microporous membrane two side sulfonate resin retes;
(3) roll-in is heated roll-in with the proton exchange membrane that just forms in two running rollers, obtain forming fine and close proton exchange membrane at last.
2. the preparation method of ultra-thin enhanced proton exchange membrane according to claim 1, the thickness that it is characterized in that described polytetrafluoroethylmicroporous microporous membrane is 2-10 μ m, and the aperture is 0.2-1.5 μ m, and porosity is 65-95%.
3. the preparation method of ultra-thin enhanced proton exchange membrane according to claim 1 is characterized in that described low-carbon alcohols is methyl alcohol, ethanol, propyl alcohol or isopropyl alcohol.
4. the preparation method of ultra-thin enhanced type proton exchange membrane according to claim 1 is characterized in that the wavelength of described ultraviolet irradiation is 100-200nm, and makes the polytetrafluoroethylmicroporous microporous membrane surface temperature reach 40-80 ℃.
5. the preparation method of ultra-thin enhanced proton exchange membrane according to claim 1 is characterized in that sulfonate resin concentration is at 2.5-50g/L in the described sulfonate resin solution, and the consumption of described sulfonate resin solution is 100-450mL/m
2
6. the preparation method of ultra-thin enhanced proton exchange membrane according to claim 1 is characterized in that the vacuum degree of described vacuum condition is-6--600mmHg, and described heating status is that temperature is 40-90 ℃.
7. the preparation method of ultra-thin enhanced proton exchange membrane according to claim 1, it is characterized in that described pair of running roller made by stainless steel and have endogenous pyrogen, diameter is 20-50cm, and the running roller gap is 4-20 μ m, and adjustable gaps, running roller surface temperature are 50-230 ℃.
8. the preparation method of ultra-thin enhanced proton exchange membrane according to claim 7 is characterized in that described endogenous pyrogen is that electric heating is held in both hands electric heater, conduction oil electric heater or superheated vapor.
9. the preparation method of ultra-thin enhanced proton exchange membrane according to claim 1, the thickness that it is characterized in that described ultra-thin enhanced proton exchange membrane is 4-12 μ m, deviate in uneven thickness is ± 0.2-± 0.5 μ m, and conductivity is 0.1-0.15s/cm, and hot strength is 40-50MPa.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111916807A (en) * | 2020-07-16 | 2020-11-10 | 苏州科润新材料股份有限公司 | Ultrathin enhanced composite proton exchange membrane, preparation method and application |
| CN112599824A (en) * | 2020-12-14 | 2021-04-02 | 中国科学院大连化学物理研究所 | Preparation process of composite membrane for fuel cell |
| CN114288855A (en) * | 2021-11-25 | 2022-04-08 | 国家电投集团氢能科技发展有限公司 | Water electrolysis membrane and preparation method thereof |
| WO2022127563A1 (en) * | 2020-12-14 | 2022-06-23 | 中国科学院大连化学物理研究所 | Preparation method for ultrathin composite proton exchange membrane having high proton conductivity |
-
2008
- 2008-11-28 CN CN200810203545A patent/CN101752574A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111916807A (en) * | 2020-07-16 | 2020-11-10 | 苏州科润新材料股份有限公司 | Ultrathin enhanced composite proton exchange membrane, preparation method and application |
| CN111916807B (en) * | 2020-07-16 | 2022-04-26 | 苏州科润新材料股份有限公司 | Ultrathin enhanced composite proton exchange membrane, preparation method and application |
| CN112599824A (en) * | 2020-12-14 | 2021-04-02 | 中国科学院大连化学物理研究所 | Preparation process of composite membrane for fuel cell |
| CN112599824B (en) * | 2020-12-14 | 2022-01-28 | 中国科学院大连化学物理研究所 | Preparation process of composite membrane for fuel cell |
| WO2022127563A1 (en) * | 2020-12-14 | 2022-06-23 | 中国科学院大连化学物理研究所 | Preparation method for ultrathin composite proton exchange membrane having high proton conductivity |
| CN114288855A (en) * | 2021-11-25 | 2022-04-08 | 国家电投集团氢能科技发展有限公司 | Water electrolysis membrane and preparation method thereof |
| CN114288855B (en) * | 2021-11-25 | 2023-03-10 | 国家电投集团氢能科技发展有限公司 | Water electrolysis membrane and preparation method thereof |
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Open date: 20100623 |