CN103159973A - New process for preparing porous high polymer reinforced perfluorinated sulfonic acid resin composite membrane - Google Patents
New process for preparing porous high polymer reinforced perfluorinated sulfonic acid resin composite membrane Download PDFInfo
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- CN103159973A CN103159973A CN2013101095856A CN201310109585A CN103159973A CN 103159973 A CN103159973 A CN 103159973A CN 2013101095856 A CN2013101095856 A CN 2013101095856A CN 201310109585 A CN201310109585 A CN 201310109585A CN 103159973 A CN103159973 A CN 103159973A
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- pfsa
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- perfluorinated sulfonic
- solution
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- 239000012528 membrane Substances 0.000 title claims abstract description 68
- 229920000642 polymer Polymers 0.000 title claims abstract description 27
- 239000000805 composite resin Substances 0.000 title claims abstract description 15
- 150000003460 sulfonic acids Chemical class 0.000 title abstract description 3
- 238000004519 manufacturing process Methods 0.000 title description 3
- 239000002131 composite material Substances 0.000 claims abstract description 37
- 238000002360 preparation method Methods 0.000 claims abstract description 31
- 239000011347 resin Substances 0.000 claims abstract description 30
- 229920005989 resin Polymers 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 21
- 239000000446 fuel Substances 0.000 claims abstract description 12
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 65
- 238000001035 drying Methods 0.000 claims description 21
- 230000007704 transition Effects 0.000 claims description 19
- 238000007669 thermal treatment Methods 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 10
- -1 perfluoro Chemical group 0.000 claims description 10
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 9
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 8
- 239000012670 alkaline solution Substances 0.000 claims description 7
- 238000007598 dipping method Methods 0.000 claims description 7
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 6
- 230000002708 enhancing effect Effects 0.000 claims description 5
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 229940058401 polytetrafluoroethylene Drugs 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- 239000013638 trimer Substances 0.000 claims description 4
- XBNGYFFABRKICK-UHFFFAOYSA-N 2,3,4,5,6-pentafluorophenol Chemical compound OC1=C(F)C(F)=C(F)C(F)=C1F XBNGYFFABRKICK-UHFFFAOYSA-N 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachloro-phenol Natural products OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 claims description 3
- RVZRBWKZFJCCIB-UHFFFAOYSA-N perfluorotributylamine Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)N(C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F RVZRBWKZFJCCIB-UHFFFAOYSA-N 0.000 claims description 3
- 239000002033 PVDF binder Substances 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 2
- 239000012779 reinforcing material Substances 0.000 abstract 2
- 229920000557 Nafion® Polymers 0.000 abstract 1
- 229920005597 polymer membrane Polymers 0.000 abstract 1
- 230000009466 transformation Effects 0.000 abstract 1
- 229920000295 expanded polytetrafluoroethylene Polymers 0.000 description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 20
- 239000008367 deionised water Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 7
- 229910017604 nitric acid Inorganic materials 0.000 description 7
- 239000012467 final product Substances 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 230000004913 activation Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000004587 chromatography analysis Methods 0.000 description 5
- 229960004756 ethanol Drugs 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000012046 mixed solvent Substances 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- 229940126680 traditional chinese medicines Drugs 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000005357 flat glass Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000002203 pretreatment Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical group OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- PRPAGESBURMWTI-UHFFFAOYSA-N [C].[F] Chemical compound [C].[F] PRPAGESBURMWTI-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002433 hydrophilic molecules Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- URXNVXOMQQCBHS-UHFFFAOYSA-N naphthalene;sodium Chemical compound [Na].C1=CC=CC2=CC=CC=C21 URXNVXOMQQCBHS-UHFFFAOYSA-N 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- WGRULTCAYDOGQK-UHFFFAOYSA-M sodium;sodium;hydroxide Chemical compound [OH-].[Na].[Na+] WGRULTCAYDOGQK-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Fuel Cell (AREA)
Abstract
The invention relates to the field of high polymer composite membrane materials, and in particular relates to a new method for preparing a high polymer membrane for a proton exchange membrane fuel cell. According to the method, the characteristic of hydrophobic property of a perfluorinated sulfonic acid (PFSA) resin precursor solution is used, the problem that in a conventional process, a hydrophilic PFSA solution and a hydrophobic reinforcing material directly generate compatibility in the compounding process is solved, and a high-performance porous high polymer reinforced PFSA composite membrane is successfully prepared. The preparation method of the porous high polymer reinforced PFSA resin composite membrane comprises the following steps of: (1) preparing a PFSA precursor solution; (2) compounding the precursor solution with a reinforcing material; (3) performing heat treatment on a load membrane; and (4) performing transformation and purification treatment to obtain the high polymer reinforced PFSA composite membrane. Compared with the prior art, the method has the characteristics of simplicity and effectiveness and is particularly suitable for industrial large-scale application, the prepared composite membrane is strong in capacity of conducting protons and capacity of resisting gas permeation, and the performance of the cell reaches a commercial Nafion.NRE211 level.
Description
Technical field
The present invention relates to the polymer compound film Material Field, be specifically related to a kind of preparation method of used in proton exchange membrane fuel cell macromolecule member material.
Background technology
Proton Exchange Membrane Fuel Cells is a kind ofly directly fuel chemical energy to be converted into the power generation assembly of electric energy by electrochemical means, is considered to the cleaning of 21 century first-selection, generation technology efficiently.Proton exchange membrane (proton exchange membrane, PEM) is the critical material of Proton Exchange Membrane Fuel Cells (proton exchange membrane fuel cell, PEMFC).
The PFSA proton exchange membrane of using now has good proton-conducting and chemical stability under (80 ℃) and higher humidity at a lower temperature.But they also have a lot of defectives: such as poor dimensional stability, physical strength are not high, and the working medium infiltration problem still need improve.Film water-intake rate and size of causing because of suction under different humidity expand also different, and when film is under the different operating environment, different variations also will occur the size of film.So repeatedly, finally make proton exchange membrane generation mechanical damage.In addition, existing PFSA resin price is expensive, blocked up film can increase production cost, and can increase greatly the ohm voltage drop of battery in fuel cells applications, yet excessively thin PFSA film can reduce physical strength again, increase the problems such as working medium infiltration, therefore, how to improve intensity, the dimensional stability of perfluorosulfonic acid proton exchange film, the perviousness of reduction working medium and reduction PFSA resin demand etc. becomes the key subjects that fuel cell industries faces.
people have proposed certain methods and have solved these problems at present, wherein tool prospect is to utilize expanded microporous polytetra fluoroethylene-EPTEE (Porous Expanded Polytetrafluoroethylene, ePTFE) the ePTFE/PFSA composite membrane that strengthens, this technique can utilize the over-all properties of tetrafluoroethylene excellence to prepare thinner composite membrane, thereby reduce the PFSA resin demand, but the problem of this scheme maximum is hydrophobicity and PFSA solution system wetting ability that tetrafluoroethylene is strong and causes material easily to be separated at recombination process, resin solution is difficult for abundant inlet hole footpath to be only had in the base material of 1 micron left and right.
The case that this scheme early sees enforcement is the Gore-Select series composite membrane (US5547551, US5635041, US5599614) of W.L.Gore company exploitation.This film has higher proton conductive and larger dimensional stability.
Sang-Yeoul Ahn(Electrochimica Acta50 (2004) 571-575) etc. utilize consistency good between PFSA precursor and ePTFE, employing is with the first hot pressing of PFSF and ePTFE compound rear transition of way, PFSA and ePTFE is compound, preparation ePTFE/PFSA composite membrane, but the PFSF melt viscosity is large, be unfavorable for that it infiltrates among the base material micropore, answer this, the same pore that easily produces in the middle of film.
Chinese patent (CN1706540A) is announced a kind of scheme, utilizes gaseous tension that the PFSA resin solution is fully entered in porous matrix, solves preferably the pore problem, but, it is dry that this technique need to vacuumize dipping/venting repeatedly, and equipment requirements and complicated operation are unfavorable for large-scale practical application.
The people (Electrochimica Acta52 (2007) 5304-5311) such as Haolin Tang adopt naphthalene sodium system to process the ePTFE surface, and hydrophilic molecule in grafting, to improve the wetting ability of base material, this scheme complex process, and the base material after processing is introduced and hydrocarbon etc. is suffered easily that under electrochemical environment free radical etc. attacks and the group of degraded, and composite membrane stability is in use stayed hidden danger.
Summary of the invention
The object of the invention is to overcome the defective of prior art, a kind of novel process for preparing the perfluorinated sulfonic resin composite membrane of expanded microporous polytetra fluoroethylene-EPTEE enhancing is provided.Adopt the composite membrane of novel process of the present invention preparation to have that the resin filling degree is high, surface resistance is low, the low and low characteristics of cost of hydrogen transmitance are specially adapted to Proton Exchange Membrane Fuel Cells.
At first the present invention discloses a kind of novel preparation method of perfluorinated sulfonic resin composite membrane of porous polymer enhancing, comprises the following steps:
1) preparation of precursor solution: the heating of PFSA presoma perfluor sulfonyl fluorine (Perfluorinated Sulfonyl Fluoride, PFSF) resin is dissolved in fluorocarbon solvent, obtains hydrophobic precursor solution;
2) film is compound: the hydrophobic precursor solution of previous step preparation is undertaken by the methods such as dipping, spraying, blade coating and porous polymer base material compound, drying, acquisition loaded film;
3) thermal treatment: with loaded film naturally cooling after 110～200 ℃ of thermal treatment for some time of previous step acquisition;
4) process transition: the loaded film after thermal treatment first is hydrolyzed transition by alkaline solution, then carries out acidifying, can obtain the perfluorinated sulfonic resin composite membrane that porous polymer strengthens.
More excellent, in the described hydrophobic precursor solution of step 1), the content of perfluor sulfonyl fluoro-resin is 1～20wt%.When namely preparing, the mass ratio of PFSF resin and fluorocarbon solvent is 1～20:80～99.
More excellent, in the described hydrophobicity precursor solution of step 1), the content of perfluor sulfonyl fluoro-resin is 2～15wt%.
PFSA presoma of the present invention is the perfluor sulfonyl fluoro-resin.
Fluorocarbon solvent of the present invention can dissolve the PFSF resin, has simultaneously very strong hydrophobicity.More excellent, described fluorocarbon solvent comprises perfluoro solvent, partially fluorinated organic solvent and other halogen-containing organic solvents.
More excellent, described fluorocarbon solvent is selected from hexafluoropropylene trimer, perfluorotributylamine, Pentafluorophenol or perfluor (methyl naphthane).
The temperature of step 1) heating for dissolving is different different with the proton exchange capacity (IEC) of PFSA, and the higher dissolving of IEC is temperature required lower, at last gained hydrophobicity precursor solution is removed by filter insolubles stand-by.This area routine techniques means that are defined as of this solvent temperature.
More excellent, step 2) in, with hydrophobic precursor solution and the porous polymer base material compound before, also need hydrophobic porous polymer base material is carried out pre-treatment.The purpose of pre-treatment is to obtain cleaning surfaces, the base material that inclusion-free adheres to.
More excellent, described pre-treatment is specially: the film of hydrophobic porous polymer base material is put into the dehydrated alcohol ultrasonic cleaning, impurity except the striping surface adsorption, then film is shakeout on sheet glass or be fixed on and carry out drying on stainless steel frame, dried film carries out Combined Processing with precursor solution again.
Step 2 of the present invention) in, precursor solution and the compound method of porous polymer base material are not limited to dipping, spraying, the techniques such as blade coating.Adopt the inventive method not only can make the hydrophobicity precursor solution be compound in the surface of polymeric membrane, can also enter in the hole in polymeric membrane.
More excellent, step 2) described drying temperature is room temperature to 380 ℃.Described room temperature is generally 24 ℃.
More excellent, 2) described drying temperature is 120 ℃.
The present invention is for improving resin-carried amount, step 2) in can repeatedly carry out load and the drying of film.Preferably, load and drying process triplicate.
More excellent, in step 3), the heat treated time is 0.5～4h.Heat treatment time can suitably shorten with the temperature increase.
More excellent, step 3) is: with step 2) loaded film naturally cooling after 160～180 ℃ of thermal treatment 2h of obtaining.This step can make the proton conductive resin internal structure effectively reform in removing film in residual solvent, improve the performance of composite membrane.
Process step 4) transition alkaline solution hydrolysis transition and the acidifying adopted and be this area routine techniques means, its purpose is after composite membrane basic hydrolysis and acidifying, acquisition Hydrogen composite membrane.Described alkaline solution is the MOH (M of 2～8M
+Be Na
+, K
+Deng) solution; The condition of described alkaline solution hydrolysis transition is: the loaded film after thermal treatment is placed in the alkaline solution 24～48 hours of 60～100 ℃.Described acidifying is: carry out ion exchange treatment in strong acid (as nitric acid, the sulfuric acid etc.) solution with the fresh configuration of the immersion of the loaded film after the alkaline solution hydrolysis treatment, the Hydrogen composite membrane of acquisition is final product of the present invention after purifying.
For example, step 4) can for: 80 ℃ of NaOH solution that the loaded film after thermal treatment are placed in 8M were processed 24 hours transition, obtained sodium type composite membrane; Carry out ion exchange treatment at the salpeter solution that sodium type composite membrane is placed in 3M, the ion exchange process triplicate obtains composite membrane after purification.
Porous polymer base material film of the present invention should have chemical stability and mechanical stability preferably, as tetrafluoroethylene, and polyvinylidene difluoride (PVDF) etc.
More excellent, the film thickness of described porous polymer base material is 4～50 microns (preferred 5～20 microns); 0.05～4 micron, aperture, porosity 70%～95%.
More excellent, described porous polymer base material is selected from microporous poly tetrafluoroethylene, polyvinylidene fluoride porous film or tetrafluoroethylene screen cloth.
More excellent, described porous polymer base material is microporous poly tetrafluoroethylene.When adopting microporous poly tetrafluoroethylene as base material, the product that the present invention makes is that tetrafluoroethylene strengthens PFSA composite membrane (ePTFE/PFSA composite membrane).
The present invention has adopted the PFSA presoma (PFSF) that has an excellent compatibility with ePTFE directly to be dissolved in the fluorine carbon solution.Wherein, PFSA presoma PFSF comprise long side chain (as
Presoma), short-side chain is (as Aquiviom
TMPresoma) and perfluor sulfonyl fluoro-resin of obtaining of copolymerization both.
Second aspect present invention discloses the perfluorinated sulfonic resin composite membrane of the porous polymer enhancing of adopting the preceding method preparation.
Preferably, described composite membrane is that tetrafluoroethylene strengthens perfluorinated sulfonic resin composite membrane (ePTFE/PFSA composite membrane).
The present invention disclose at last aforementioned preparation method with and the perfluorinated sulfonic resin composite membrane that strengthens of the porous polymer of preparation in the application in Proton Exchange Membrane Fuel Cells field.
The present invention utilizes the hydrophobic characteristics of perfluorinated sulfonic acid (Perfluorosulfonic Acid, PFSA) resin precursor solution, has overcome in traditional technology wetting ability PFSA solution and hydrophobicity strongthener recombination process to be difficult to compatible problem.Beneficial effect of the present invention is: the present invention compared with prior art has simple and effective characteristics, being particularly suitable for large-scale industrialization uses, it is residual that the composite membrane of its preparation has lower pore, strengthening matrix in film is combined with proton conductive resin closely, make its proton conductivity strengthen, the gas-permeable ability reduces, and its battery performance performance has reached business
The NRE211 level.
Description of drawings
Fig. 1 is the present invention's PFSA precursor solution used and ePTFE film contact angle photo.
Fig. 2 is in prior art, adopts PFSA solution and the ePTFE film contact angle photo of isopropanol/water (4:1w/w) mixed solvent preparation.
Fig. 3 is the prepared ePTFE/PFSA composite membrane profile scanning Electronic Speculum figure of the present invention.
Fig. 4 is in prior art, adopts the PFSA solution of isopropanol/water (4:1w/w) mixed solvent preparation and the composite membrane profile scanning Electronic Speculum picture of ePTFE preparation.
Fig. 5 is composite membrane and the commercial film of the made PFSA/ePTFE composite membrane of the present invention and prior art
211 polarization curve and power densities on proton membrane fuel battery are relatively schemed.
Embodiment
Further set forth the present invention below in conjunction with specific embodiment, should be understood that embodiment only is used for explanation the present invention and is not used in restriction protection scope of the present invention.
Those skilled in the art can understand other advantages of the present invention and effect easily by the disclosed content of this specification sheets.The present invention can also be implemented or be used by other different embodiment, and the every details in this specification sheets also can be based on different viewpoints and application, carries out various modifications or change under spirit of the present invention not deviating from.
With reference to following nonrestrictive embodiment, can more fully understand the present invention.Extensive stock title and abbreviation used in embodiment are defined as follows:
The g gram
M mole every liter
Ω cm
2Ohm square centimeter
MA/cm
2Every square centimeter of milliampere
The every gram of meq/g milliequivalent
μ m micron
EPTFE expanded microporous polytetra fluoroethylene-EPTEE (Teflon) film, Shanghai Da Gong produces
PFSA perfluorinated sulfonic acid proton exchange resins, Eastern Mountain, Shandong group produces
NaOH sodium hydroxide is available from traditional Chinese medicines group company
Nitric acid 65-68% is available from Pinghu chemical reagent factory
H
2O
230% hydrogen peroxide is available from traditional Chinese medicines group
H
2SO
4Sulfuric acid is available from traditional Chinese medicines group
Fluorocarbon solvent Shandong Eastern Mountain group produces
The ethanol dehydrated alcohol is available from traditional Chinese medicines group company
IEC Ion Exchange Capacity loading capacity
Virahol reagent is pure, available from traditional Chinese medicines group company
Embodiment 1
The PFSA presoma resin of 20g IEC=1.12 mole/kilogram is dissolved in 180g perfluor (methyl naphthane), will gets supernatant liquid after solution centrifugal, then by the aluminium sesquioxide chromatography column after activation, obtain purified solution after filtering at last.The ePTFE film is fixed with stainless steel frame, and clean up rear drying with ethanol, then will immerse in PFSA presoma resin solution with clean ePTFE, shift out after 5 minutes, be placed in baking oven 120 degree dry 5 minutes, for improving resin-carried amount, dipping and the general triplicate of drying process are at last with the lower thermal treatment of film 160 degree 2 hours.The composite membrane that makes is put into the NaOH solution 80 degree reactions of 8M and was processed 48 hours transition, and transition, caudacoria was cleaned with deionized water, immersed immediately 3M nitric acid 3 hours, changed one time salpeter solution every one hour.Use afterwards 5% H
2O
2Solution boiled 1 hour, immersed deionized water 30 minutes, then used 1M H
2SO
4Boiled washed with de-ionized water one hour.Obtain pure final product after drying.
Embodiment 2
This embodiment is dissolved in the PFSA presoma resin of 10g IEC=1.12 mole/kilogram in the 190g hexafluoropropylene trimer, will get supernatant liquid after solution centrifugal, then by the aluminium sesquioxide chromatography column after activation, obtains purified solution after filtering at last.The ePTFE film cleans up rear drying with ethanol, divide with clean sheet glass on, then will spray its surface with PFSA presoma resin solution, be placed in baking oven 120 degree dry 5 minutes, for improving resin-carried amount, spraying and the general triplicate of drying process are at last with the lower thermal treatment of film 160 degree 2 hours.The composite membrane that makes is put into the NaOH solution 80 degree reactions of 8M and was processed 48 hours transition, and transition, caudacoria was cleaned with deionized water, immersed immediately 3M nitric acid 3 hours, changed one time salpeter solution every one hour.Use afterwards 5% H
2O
2Solution boiled 1 hour, immersed deionized water 30 minutes, then used 1M H
2SO
4Boiled washed with de-ionized water one hour.Obtain pure final product after drying.
Embodiment 3
This embodiment is dissolved in the PFSA presoma resin of 5g IEC=1.12 mole/kilogram in the 195g hexafluoropropylene trimer, will get supernatant liquid after solution centrifugal, then by the aluminium sesquioxide chromatography column after activation, obtains purified solution after filtering at last.The ePTFE film is fixed with stainless steel frame, and clean up rear drying with ethanol, then will immerse in PFSA presoma resin solution with clean ePTFE, shift out after 5 minutes, be placed in baking oven 120 degree dry 5 minutes, for improving resin-carried amount, dipping and the general triplicate of drying process are at last with the lower thermal treatment of film 160 degree 2 hours.The composite membrane that makes is put into the NaOH solution 80 degree reactions of 8M and was processed 48 hours transition, and transition, caudacoria was cleaned with deionized water, immersed immediately 3M nitric acid 3 hours, changed one time salpeter solution every one hour.Use afterwards 5% H
2O
2Solution boiled 1 hour, immersed deionized water 30 minutes, then used 1M H
2SO
4Boiled washed with de-ionized water one hour.Obtain pure final product after drying.
Embodiment 4
This embodiment is dissolved in the PFSA presoma resin of 4g IEC=1.01 mole/kilogram in the 196g Pentafluorophenol, will get supernatant liquid after solution centrifugal, then by the aluminium sesquioxide chromatography column after activation, obtains purified solution after filtering at last.The ePTFE film is fixed with stainless steel frame, and clean up rear drying with ethanol, then will immerse in PFSA presoma resin solution with clean ePTFE, shift out after 5 minutes, be placed in baking oven 120 degree dry 5 minutes, for improving resin-carried amount, dipping and the general triplicate of drying process are at last with the lower thermal treatment of film 160 degree 2 hours.The composite membrane that makes is put into the NaOH solution 80 degree reactions of 8M and was processed 48 hours transition, and transition, caudacoria was cleaned with deionized water, immersed immediately 3M nitric acid 3 hours, changed one time salpeter solution every one hour.Use afterwards 5% H
2O
2Solution boiled 1 hour, immersed deionized water 30 minutes, then used 1M H
2SO
4Boiled washed with de-ionized water one hour.Obtain pure final product after drying.
Embodiment 5
This embodiment is dissolved in the PFSA presoma resin of 30g IEC=1.34 mole/kilogram in the 170g perfluorotributylamine, will get supernatant liquid after solution centrifugal, then by the aluminium sesquioxide chromatography column after activation, obtains purified solution after filtering at last.The ePTFE film of cleaning is divided be fixed on clean sheet glass, then a certain amount of PFSA presoma resin solution is poured on the ePTFE film, hang back with scraper and be coated with for several times, be placed in baking oven 120 degree dry 5 minutes, for improving resin-carried amount, apply and the general triplicate of drying process, at last with the lower thermal treatment of film 160 degree 2 hours.The composite membrane that makes is put into the NaOH solution 80 degree reactions of 8M and was processed 48 hours transition, and transition, caudacoria was cleaned with deionized water, immersed immediately 3M nitric acid 3 hours, changed one time salpeter solution every one hour.Use afterwards 5% H
2O
2Solution boiled 1 hour, immersed deionized water 30 minutes, then used 1M H
2SO
4Boiled washed with de-ionized water one hour.Obtain pure final product after drying.
Embodiment 6
Film and commercial film with the composite membrane of novel process preparation of the present invention and the PFSA solution direct combination method of prior art (adopting the PFSA solution of isopropanol/water=4:1w/w mixed solvent preparation) preparation
The salient features of NRE211 compares, and the salient features comparative result of mould material is as shown in table 1.
In embodiment 4 contact angle of hydrophobicity precursor solution and ePTFE as shown in Figure 1, the composite membrane section is as shown in Figure 3; As a comparison, the contact angle of the PFSA solution under the same concentrations that art methods obtains (adopting the PFSA solution of isopropanol/water=4:1w/w mixed solvent preparation) and ePTFE as shown in Figure 2, its composite membrane section is as shown in Figure 4.
The film of the composite membrane (the solution combined film of PFSF) of the embodiment of the present invention 4 preparations and the PFSA solution direct combination method of prior art (adopting the PFSA solution of isopropanol/water=4:1w/w mixed solvent preparation) preparation, and commercial film
The battery performance performance of NRE211 as shown in Figure 5.
The Specifeca tion speeification of table 1 composite membrane
Claims (9)
1. the preparation method of the perfluorinated sulfonic resin composite membrane that strengthens of a porous polymer comprises the following steps:
1) preparation of precursor solution: the heating of PFSA presoma perfluor sulfonyl fluoro-resin is dissolved in fluorocarbon solvent, obtains hydrophobic precursor solution;
2) film is compound: the method with the hydrophobic precursor solution of previous step preparation by dipping, spraying or blade coating and porous polymer base material carry out compound, drying, acquisition loaded film;
3) thermal treatment: with loaded film naturally cooling after 110～200 ℃ of thermal treatment for some time of previous step acquisition;
4) process transition: the loaded film after thermal treatment first is hydrolyzed transition by alkaline solution, then carries out acidifying, can obtain the perfluorinated sulfonic resin composite membrane that porous polymer strengthens.
2. preparation method as claimed in claim 1, is characterized in that, in the described hydrophobic precursor solution of step 1), the content of perfluor sulfonyl fluoro-resin is 1～20wt%.
3. preparation method as claimed in claim 1, is characterized in that, described fluorocarbon solvent comprises perfluoro solvent and partially fluorinated organic solvent.
4. the described preparation method of claim as arbitrary in claim 1 or 3, is characterized in that, described fluorocarbon solvent is selected from hexafluoropropylene trimer, perfluorotributylamine, Pentafluorophenol or perfluor (methyl naphthane).
5. preparation method as claimed in claim 1, is characterized in that, in step 3), the heat treated time is 0.5～4h.
6. preparation method as claimed in claim 1, is characterized in that, described porous polymer base material is selected from microporous poly tetrafluoroethylene, polyvinylidene fluoride porous film or tetrafluoroethylene screen cloth.
7. the perfluorinated sulfonic resin composite membrane that porous polymer strengthens, prepare for adopting the described method of the arbitrary claim of claim 1-6.
8. the perfluorinated sulfonic resin composite membrane of porous polymer enhancing as claimed in claim 7, is characterized in that, described composite membrane is that tetrafluoroethylene strengthens the perfluorinated sulfonic resin composite membrane.
9. the perfluorinated sulfonic resin composite membrane of the described preparation method of the arbitrary claim of claim 1-6, the described porous polymer enhancing of the arbitrary claim of claim 7 or 8 is in the application in Proton Exchange Membrane Fuel Cells field.
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| CN105037604A (en) * | 2015-05-25 | 2015-11-11 | 上海交通大学 | Short chain perfluorosulfonamide anion ionomer for fuel cells, preparation and applications thereof |
| CN106925347A (en) * | 2015-12-29 | 2017-07-07 | 山东华夏神舟新材料有限公司 | The preparation method of porous perfluorinated sulfonic resin catalyst |
| CN107283704A (en) * | 2016-04-13 | 2017-10-24 | 北京化工大学 | Novel multi-layer solution casting method prepares perfluorosulfonic acid ion film |
| CN108604688A (en) * | 2016-02-15 | 2018-09-28 | 东丽株式会社 | The manufacturing method and manufacturing device of ion-conductive membranes |
| CN112436168A (en) * | 2020-11-30 | 2021-03-02 | 山东东岳未来氢能材料股份有限公司 | Long-life enhanced perfluorinated proton membrane and preparation method thereof |
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| CN112757731A (en) * | 2020-12-25 | 2021-05-07 | 南京大学 | High-durability enhanced proton exchange membrane and preparation method and application thereof |
| 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 |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105037604A (en) * | 2015-05-25 | 2015-11-11 | 上海交通大学 | Short chain perfluorosulfonamide anion ionomer for fuel cells, preparation and applications thereof |
| CN106925347A (en) * | 2015-12-29 | 2017-07-07 | 山东华夏神舟新材料有限公司 | The preparation method of porous perfluorinated sulfonic resin catalyst |
| CN106925347B (en) * | 2015-12-29 | 2019-10-29 | 山东东岳未来氢能材料有限公司 | The preparation method of porous perfluorinated sulfonic resin catalyst |
| CN108604688A (en) * | 2016-02-15 | 2018-09-28 | 东丽株式会社 | The manufacturing method and manufacturing device of ion-conductive membranes |
| CN107283704A (en) * | 2016-04-13 | 2017-10-24 | 北京化工大学 | Novel multi-layer solution casting method prepares perfluorosulfonic acid ion film |
| CN112745445A (en) * | 2019-10-31 | 2021-05-04 | 中国石油化工股份有限公司 | Perfluoro sulfonyl fluororesin, preparation method thereof and perfluoro sulfonic acid resin prepared from perfluoro sulfonyl fluororesin |
| CN112745445B (en) * | 2019-10-31 | 2022-06-07 | 中国石油化工股份有限公司 | Perfluoro sulfonyl fluororesin, preparation method thereof and perfluoro sulfonic acid resin prepared from perfluoro sulfonyl fluororesin |
| CN112467184A (en) * | 2020-11-25 | 2021-03-09 | 上海汽车集团股份有限公司 | Enhanced proton exchange membrane and preparation method thereof |
| CN112436168A (en) * | 2020-11-30 | 2021-03-02 | 山东东岳未来氢能材料股份有限公司 | Long-life enhanced perfluorinated proton membrane and preparation method thereof |
| CN112757731A (en) * | 2020-12-25 | 2021-05-07 | 南京大学 | High-durability enhanced proton exchange membrane and preparation method and application thereof |
| CN112757731B (en) * | 2020-12-25 | 2022-04-05 | 南京大学 | High-durability enhanced proton exchange membrane and preparation method and application thereof |
| 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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