CN101728549B - High-temperature proton exchange compound film - Google Patents
High-temperature proton exchange compound film Download PDFInfo
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- CN101728549B CN101728549B CN2009102311216A CN200910231121A CN101728549B CN 101728549 B CN101728549 B CN 101728549B CN 2009102311216 A CN2009102311216 A CN 2009102311216A CN 200910231121 A CN200910231121 A CN 200910231121A CN 101728549 B CN101728549 B CN 101728549B
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- ion exchange
- acid resin
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- 150000001875 compounds Chemical class 0.000 title abstract 4
- 229920005989 resin Polymers 0.000 claims abstract description 59
- 239000011347 resin Substances 0.000 claims abstract description 59
- -1 polytrifluorochloroethylene Polymers 0.000 claims abstract description 25
- 238000005342 ion exchange Methods 0.000 claims abstract description 24
- 239000011148 porous material Substances 0.000 claims abstract description 20
- 239000002033 PVDF binder Substances 0.000 claims abstract description 14
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 14
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 11
- 239000011737 fluorine Substances 0.000 claims abstract description 11
- 229920006254 polymer film Polymers 0.000 claims abstract description 6
- 239000012528 membrane Substances 0.000 claims description 94
- 239000002131 composite material Substances 0.000 claims description 39
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 21
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 21
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- ABDBNWQRPYOPDF-UHFFFAOYSA-N carbonofluoridic acid Chemical compound OC(F)=O ABDBNWQRPYOPDF-UHFFFAOYSA-N 0.000 claims description 9
- 229920002313 fluoropolymer Polymers 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- 239000004811 fluoropolymer Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000007650 screen-printing Methods 0.000 claims description 7
- 238000005507 spraying Methods 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 238000005266 casting Methods 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 238000007731 hot pressing Methods 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- 238000010345 tape casting Methods 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000012982 microporous membrane Substances 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- 230000002457 bidirectional effect Effects 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical compound FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 claims 1
- 239000000446 fuel Substances 0.000 abstract description 11
- 238000011049 filling Methods 0.000 abstract description 3
- 210000004027 cell Anatomy 0.000 abstract 2
- 210000003850 cellular structure Anatomy 0.000 abstract 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract 1
- 239000005977 Ethylene Substances 0.000 abstract 1
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 21
- 238000000576 coating method Methods 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229920000557 Nafion® Polymers 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229920000831 ionic polymer Polymers 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- WQXFWRCHCCQMBY-UHFFFAOYSA-N propan-1-ol;propan-2-ol;hydrate Chemical compound O.CCCO.CC(C)O WQXFWRCHCCQMBY-UHFFFAOYSA-N 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000011712 cell development Effects 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 1
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- KIDBBTHHMJOMAU-UHFFFAOYSA-N propan-1-ol;hydrate Chemical compound O.CCCO KIDBBTHHMJOMAU-UHFFFAOYSA-N 0.000 description 1
- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical compound FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
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)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention relates to a high-temperature proton exchange compound film. The film is formed by using a fluorine-containing thin polymer film having a cellular structure as a carrier, filling a perfluor resin having a function of ion exchange into the micro-pores of a micro-porous film and covering the surface of the micro-porous film, wherein the compound film is 5 to 15 microns thick. The fluorine-containing thin polymer film having a cellular structure is a polyfluortetraethylene porous film, a polyvinylidene fluoride porous film, a polytrifluorochloroethylene porous film or a polyfluortetraethylene ethylene porous film. The perfluor resin having a function of ion exchange is a perfluor sulfo resin, a perfluor carboxylic resin or a perfluor phosphoric resin. The compound film of the invention is thin and can be applied to a fuel cell having a decreased internal resistance in order to promote the output power of the cell.
Description
Technical Field
The invention relates to a high-temperature proton exchange membrane, in particular to a composite membrane consisting of a fluorine-containing ionic polymer and a porous membrane.
Background
The proton exchange membrane fuel cell is a power generation device which directly converts chemical energy into electric energy in an electrochemical mode, and is considered as a first choice clean and efficient power generation technology in the 21 st century. Proton Exchange Membranes (PEM) are key materials for Proton Exchange Membrane Fuel Cells (PEMFCs).
The proton exchange membrane of the perfluorosulfonic acid used at present has good proton conductivity and chemical stability at lower temperature (80 ℃) and higher humidity. However, they also have many disadvantages such as poor dimensional stability, low mechanical strength, poor chemical stability, and the like. The water absorption rate and the size expansion caused by water absorption of the membrane are different under different humidity, and when the membrane is changed under different working conditions, the size of the membrane is changed accordingly. Such repetition eventually leads to mechanical breakage of the proton exchange membrane. In addition, the positive electrode reaction of the fuel cell often generates a large amount of strongly oxidizing substances such as hydroxyl radicals and hydrogen peroxide, which attack non-fluorine groups on the film-forming resin molecules, resulting in chemical degradation and breakage of the film, resulting in foaming. Finally, when the operating temperature of the perfluorosulfonic acid exchange membrane is higher than 90 ℃, the proton conductivity of the membrane is drastically reduced due to rapid water loss of the membrane, thereby greatly reducing the efficiency of the fuel cell. But the high operating temperature can greatly improve the carbon monoxide resistance of the fuel cell catalyst. In addition, the existing perfluorosulfonic acid membranes have certain hydrogen or methanol permeability, and particularly in direct methanol fuel cells, the methanol permeability is very high, which is a fatal problem. Therefore, it is a major problem in the fuel cell industry to improve the strength, dimensional stability, and proton conduction efficiency at high temperature of the perfluorosulfonic acid proton exchange membrane and to reduce the permeability of the working medium.
Several approaches have been proposed to address these problems. For example, JP-B-5-75835 uses perfluorosulfonic acid resin to impregnate a porous medium made of Polytetrafluoroethylene (PTFE) to reinforce the strength of the membrane. However, such porous media of PTFE have not been able to solve the above problems because the PTFE material is relatively soft and the reinforcing effect is insufficient. The Gore-Select series composite membrane liquid developed by Gore company adopts a method of filling Nafion ion conductive liquid with porous Teflon (US5547551, US 56565041, US5599614), and the membrane has high proton conductivity and larger dimensional stability, but the Teflon creeps greatly at high temperature, so that the performance is reduced. JP-B-7-68377 also proposes a method of filling a porous medium made of polyolefin with a proton exchange resin, but has insufficient chemical durability and thus has a problem in long-term stability. And because of the addition of the porous medium without proton conductivity, the proton conduction path is reduced, and the proton exchange capacity of the membrane is reduced.
Further, Japanese patent JP-A-6-231779 proposes another reinforcing method using fluororesin fibers. Which employs an ion exchange membrane reinforced with a fibril form of fluorocarbon polymer reinforcement. However, this method necessitates the addition of a relatively large amount of reinforcing material, and in this case, the processing of the film tends to be difficult, and an increase in the film resistance is likely to occur.
While european patent EP0875524B1 discloses a technique for reinforcing nafion membranes with glass fiber membranes prepared by a glass fiber nonwoven technique, in which oxides such as silica are also mentioned. However, the non-woven glass fiber cloth in the patent is a necessary substrate, which greatly limits the range of applications of the reinforcement.
U.S. Pat. No. 6,6692858 discloses the art of polytetrafluoroethylene fiber reinforced perfluorosulfonic acid resins. In this technique, a perfluorosulfonyl fluoride resin and a polytetrafluoroethylene fiber are mixed, extruded, and transformed to prepare a fiber-reinforced perfluorosulfonic acid resin. This method does not allow continuous production due to the time consuming transformation process.
The US RE37701 describes the invention of compounding ionic polymers with expanded tetrafluoroethylene membranes into composite membranes, but the expanded tetrafluoroethylene membranes used by them have a thickness greater than 20 μm and cannot be adapted to the trend of modern fuel cell development and to thinner and stronger membranes. Therefore, the method can not adapt to the use condition of the high-temperature proton exchange membrane fuel cell.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a high-temperature proton exchange composite membrane and a preparation method thereof.
The technical scheme of the invention is as follows:
a proton exchange composite membrane uses a fluorine-containing polymer film with a microporous structure as a carrier, and full fluororesin with an ion exchange function is filled in micropores of a microporous membrane and covers the surface of the microporous membrane, and the thickness of the composite membrane is 5-15 microns.
The fluoropolymer membrane with the microporous structure is a Polytetrafluoroethylene (PTFE) porous membrane, a polyvinylidene fluoride porous membrane (PVDF), a polychlorotrifluoroethylene porous membrane and a polytetrafluoroethylene-ethylene (ETFE) porous membrane.
The thickness of the fluoropolymer film with the microporous structure is 1-20 micrometers, the porosity is 60-97%, and the pore diameter is 0.2-5 micrometers.
The preferable thickness of the fluoropolymer film carrier with the microporous structure is 5-20 micrometers, the more preferable thickness is 5-15 micrometers, and the most preferable thickness is 8-12 micrometers; the preferable porosity is 80-95%; the preferred pore size is 0.5 to 4 microns, and the more preferred pore size is 1 to 3 microns.
Preferably, the thickness of the fluoropolymer film carrier with the microporous structure is 5-15 micrometers, the void ratio is 80-95%, and the pore diameter is 1-3 micrometers.
The fluoropolymer film with the microporous structure can be a unidirectional stretching film or a bidirectional stretching film.
The perfluoro resin with ion exchange function is selected from one or the combination of the following: perfluorosulfonic acid resin, perfluorocarboxylic acid resin, or perfluorophosphoric acid resin. Wherein,
the perfluorosulfonic acid resin has the following general formula:
wherein x is 3 to 15, n is 0 to 2, p is 2 to 5, and the ion exchange capacity is 0.90 to 1.60 mmol/g. The molecular weight is 10-60 ten thousand, preferably 15-30 ten thousand.
The perfluorocarboxylic acid resin has the following structural unit:
in the formula (II), c is 0 or 1, d is 1-5, a is 3-11, b is 1-3, and the ion exchange capacity is 0.85-1.50 mmol/g. The molecular weight is 10-60 ten thousand, preferably 15-30 ten thousand.
The perfluoro phosphoric acid resin has the following structural units:
in the formula (III), e is 3-20, f is 1, and the ion exchange capacity is 0.80-2.5 mmol/g. The molecular weight is 10-60 ten thousand, preferably 15-30 ten thousand.
The perfluorosulfonic acid resin, the perfluorocarboxylic acid resin or the perfluorophosphoric acid resin is prepared by a known method.
The preparation method of the proton exchange composite membrane comprises the following steps:
(1) the full fluorine resin with ion exchange function or the precursor thereof is compounded with the fluorine-containing polymer film with a microporous structure into a film by extrusion, hot pressing, solution casting, tape casting, screen printing, spraying or dipping processes;
(2) and (2) carrying out heat treatment on the membrane prepared in the step (1) at 30-250 ℃ to obtain the high-temperature proton exchange composite membrane.
The extrusion, hot pressing, solution casting, screen printing, spraying or dipping processes in step (1) above can be according to the state of the art. Wherein,
when the process of solution casting, tape casting, screen printing, spraying or dipping is used, the perfluorinated resin is dissolved in a solvent to prepare a perfluorinated resin solution, and the used solvent is selected from one or the combination of the following solvents: one or more of dimethylformamide, dimethylacetamide, methylformamide, dimethyl sulfoxide, N-methylpyrrolidone, hexamethyl ammonium phosphate, acetone, water, ethanol, methanol, propanol, isopropanol, ethylene glycol or glycerol. The solvent used is preferably an alcohol-water solution, the ratio of alcohol to water being chosen as is conventional in the art, and the preferred ratio of alcohol to water in the present invention is 1: 1 by volume.
The solid content of the perfluorinated resin solution is 1-80%, the weight ratio and the viscosity are 1-4000 cP, and 20-2000 cP is preferred.
Preferably, the heat treatment time of the film in the step (2) is 10-600 minutes, and preferably 20-120 min.
The proton exchange composite membrane after heat treatment needs post treatment according to the form of the membrane forming substance and the kind of solvent of the membrane forming solution, and the post treatment method is the prior art in the field, for example, boiling in 5% sulfuric acid for 30-60 minutes, boiling in distilled water for 30 minutes to swell the membrane, hydrolyzing in 10% KOH solution for 6-8 hours, and then placing in 5% H solution2SO4And (5) neutralizing for 1 h.
The more important detailed preparation is illustrated in the examples, which are not intended to limit the invention in any way according to the prior art.
The invention has the following excellent effects:
according to the invention, the film thickness of the composite membrane is less than 20 microns by compounding the fluorine-containing polymer porous membrane of 1-20 microns with the perfluorinated ionic polymer, the conductivity of the composite membrane is superior to that of the composite membrane with large thickness due to the small thickness of the ionic membrane, the influence on the performance of the fuel cell is unexpected, and the internal resistance of the cell is greatly reduced due to the reduction of the thickness, so that the output power of the cell is improved. It is particularly surprising that such thin composite membranes are comparable membranes that perform well above 20 microns at high temperatures > 95 ℃ and low humidity (30% RH) cells. The possible reason is that when the membrane becomes very thin, water generated at the positive electrode of the cell, i.e., the oxygen and hydrogen ion reaction electrode, can easily migrate backwards to another stage, and thus the membrane is humidified during the reverse migration, thereby improving the conductivity of the membrane and the output performance of the cell virtually.
Drawings
Fig. 1 is a plot of the output performance (95 degrees, 30% RH) of the single cells of example 3 and comparative example, with voltage on the ordinate, hydrogen permeation current on the abscissa, 10 micron composite membrane on the top line, and 25 micron composite membrane on the bottom line.
Detailed Description
The present invention will be further described with reference to examples and comparative examples. The concentration of all the perfluoro resin solutions in the examples is mass percent.
Example 1
Soaking a 5-micron polytetrafluoroethylene membrane (with the porosity of 80 percent and the pore diameter of 0.5-3 microns) in 5 percent perfluorosulfonic acid resin propanol-water solution, wherein the structural formula of the perfluorosulfonic acid resin is shown in the specification
n is 1, p is 2, ion exchange capacity is 0.97mmol/g, molecular weight is 19 ten thousand.
The wet film samples were then dried in an oven at 140 ℃ for 30 seconds. This process step can be repeated more than 2 times in order to completely occlude the pores in the membrane. And finally, treating the composite membrane for 30 minutes at 190 ℃ to obtain a composite membrane with the thickness of 8 microns, and then boiling the composite membrane in 5% sulfuric acid for 30 minutes at normal pressure to obtain the 5 micron composite membrane.
Example 2
A biaxially oriented polytetrafluoroethylene film (porosity 89%, pore diameter 0.2-2 microns) 10 microns thick was fixed on a flat plate. And (3) coating a 15% perfluorosulfonic acid resin isopropanol-water solution on one side of the polytetrafluoroethylene membrane to completely fill the pore volume in the membrane with the perfluorosulfonic acid resin solution so as to completely block all pores. Wherein the structural formula of the perfluorinated sulfonic acid resin is shown in the specification
n is 1, p is 2, and the ion exchange capacity is 1.05mmol/g molecular weight is 21 ten thousand.
The coated film samples were dried in a drying oven at 100 ℃ for 15 minutes. The coating and drying process can be repeated more than 2 times in order to completely occlude the pores in the membrane. The drying temperature was then raised to 210 ℃ and dried for 5 minutes. Then boiling the mixture in 5 percent sulfuric acid for 60 minutes under normal pressure to obtain the 12 micron composite membrane.
Example 3
A biaxially oriented polyvinylidene fluoride film (porosity 75%, pore diameter 5 μm) 8 μm thick was fixed on a flat plate. Coating 24% perfluorosulfonic acid resin isopropanol-propanol-water solution on two sides of polyvinylidene fluoride membrane by screen printing, wherein the structural formula of the perfluorosulfonic acid resin is shown in the specification
n is 0, p is 2, ion exchange capacity is 1.35mmol/g, molecular weight is 24 ten thousand.
The film was then dried in an oven at 160 ℃ for 40 minutes. Then, the dried film after drying treatment was taken out and boiled in distilled water for 30 minutes to swell the film to obtain a 10-micron composite film.
Example 4
A biaxially oriented polytetrafluoroethylene film (porosity 85%, pore diameter 0.2-3 microns) with the thickness of 12 microns is fixed on a flat plate. Compounding perfluoro sulfonic acid resin precursor with polyvinylidene fluoride membrane by hot pressing, hydrolyzing the composite membrane in 10% KOH solution for 8H, and placing in 5% H2SO4Obtaining the 12-micron composite membrane in 1 h. Wherein the structural formula of the perfluorinated sulfonic acid resin is as follows:
n is 0, p is 2, ion exchange capacity is 1.50mmol/g, molecular weight is 26 ten thousand.
Example 5
A12 μm thick biaxially oriented polyvinylidene fluoride membrane (porosity 75%, pore size 5 μm) was fixed to a flat plate. Coating 24% ethanol-water solution of perfluorosulfonic acid resin on both sides of the polyvinylidene fluoride membrane by spraying, wherein the structural formula of the perfluorosulfonic acid resin is shown in the specification
n is 0, p is 4, ion exchange capacity is 1.20mmol/g, molecular weight is 17 ten thousand. The film was then dried in an oven at 160 ℃ for 1 minute. Then, the dried film after drying treatment was taken out and boiled in distilled water for 30 minutes to obtain a 12-micron composite film.
Example 6
A20 μm thick uniaxially stretched ETFE membrane (porosity 60%, pore size 1 μm) was fixed on a flat plate. Coating 36% of perfluorosulfonic acid resin DMF solution on an ETFE membrane in a tape casting manner, wherein the structural formula of the perfluorosulfonic acid resin is shown in the specification
n is 1, p is 3, ion exchange capacity is 1.10mmol/g, molecular weight is 21 ten thousand. The film was then dried in an oven at 250 ℃ for 30 minutes. Then, the dried film after drying was taken out and boiled in distilled water for 30 minutes to obtain a 20-micron film.
Example 7
A15 micron thick uniaxially stretched PVDF membrane (porosity 85%, pore size 2 micron) was fixed on a flat plate. Coating 10% ethanol solution of perfluorocarboxylic acid resin on a PVDF membrane in a tape casting manner, wherein the structural formula of the perfluorocarboxylic acid resin is shown in the specification
c is 1, d is 2, ion exchange capacity is 1.00mmol/g, molecular weight is 22 ten thousand. The film was then dried in an oven at 120 ℃ for 10 minutes. Then, the dried film after drying treatment was taken out and boiled in distilled water for 30 minutes to obtain a 16-micron composite film.
Example 8
A biaxially oriented polytetrafluoroethylene film (porosity 85%, pore diameter 3 μm) having a thickness of 15 μm was fixed on a flat plate. Coating 5% perfluorocarboxylic acid resin NMP (N-methyl pyrrolidone) alcohol solution on a biaxially oriented polytetrafluoroethylene membrane in a casting mode, wherein the perfluorocarboxylic acid resin has a structural formula shown in the specification
c is 1, d is 3, ion exchange capacity is 1.15mmol/g, molecular weight is 18 ten thousand. The film was then dried in an oven at 100 ℃ for 5 minutes. Then, the dried film after drying treatment was taken out and boiled in distilled water for 30 minutes to obtain a 15-micron composite film.
Example 9
A biaxially oriented polytetrafluoroethylene film (porosity 75%, pore size 0.4 μm) 14 μm thick was fixed to a flat plate. And compounding a precursor of the perfluorinated phosphoric acid resin with a biaxially oriented polytetrafluoroethylene membrane in a hot pressing mode, and then placing the membrane in 10% sulfuric acid for treatment for 5 hours to obtain the acid type 14-micron composite membrane. Wherein the structural formula of the precursor of the perfluoro phosphoric acid resin is shown as
The ion exchange capacity is 1.70mmol/g, and the molecular weight is 25 ten thousand.
Comparative example:
a biaxially oriented polyvinylidene fluoride film (porosity 75%, pore diameter 5 μm) 25 μm thick was fixed on a flat plate. Coating 24% perfluorosulfonic acid resin isopropanol-propanol-water solution on two sides of polyvinylidene fluoride membrane by screen printing, wherein the structural formula of the perfluorosulfonic acid resin is shown in the specification
n is 0, p is 2, ion exchange capacity is 1.35mmol/g, molecular weight is 23 ten thousand.
The film was then dried in an oven at 160 ℃ for 20 minutes. Then, the dried film after drying treatment was taken out and boiled in distilled water for 30 minutes to swell the film to obtain a 25-micron composite film.
Measurement of cell Performance:
the membrane electrode assembly was prepared as follows:
(1) preparation of gas diffusion layer: the carbon paper was subjected to hydrophobic treatment by dipping it into 25 wt% PTFE emulsion. Then the carbon paper soaked with PTFE is placed in a muffle furnace at 340 ℃ for roasting, so that the surfactant soaked in the carbon paper is removed, and a good hydrophobic effect is achieved. Mixing a certain amount of carbon powder, PTFE and a proper amount of isopropanol aqueous solution, oscillating for 15min by ultrasonic waves, coating the mixture on carbon paper by a brush coating process, and respectively baking the coated carbon paper for 30min at 340 ℃ to obtain the gas diffusion layer.
(2) Preparation of membrane electrode MEA: the Pt loading in the catalyst layer is 0.3mg/cm2Mixing a certain amount of 40% Pt/C (JM company) electrocatalyst, deionized water and isopropanol, and ultrasonically oscillating for 15 min; then adding a certain amount of 5% Nafion solution (Dupont company), continuing ultrasonic oscillation for 15min, and after the ultrasonic oscillation is performed to form ink shape, uniformly spraying the ink on the composite membrane of the invention to obtain the membrane electrode MEA.
Two gas diffusion layers were placed on both sides of the MEA at a pressure of 3MPa to obtain a single cell, which was used for testing on a cell station apparatus.
The properties of the various films were measured as described above and the results are shown in Table 1. As can be seen from Table 1, the composite membrane of the invention has the performances of conductivity at 95 ℃, tensile strength, hydrogen permeation current and the like which are superior to or equivalent to those of the composite ionic membrane with the common thickness. But the output performance of a single cell at 95 ℃ is superior to that of the similar composite membrane with the thickness of more than 20 microns.
TABLE 1 various film Properties
Claims (4)
1. A proton exchange composite membrane is characterized in that a fluorine-containing polymer film with a microporous structure is taken as a carrier, and all fluorine resin with an ion exchange function is filled in micropores of a microporous membrane and covers the surface of the microporous membrane, wherein the thickness of the composite membrane is 5-15 microns;
the thickness of the fluoropolymer film carrier with the microporous structure is 5-15 micrometers, the porosity is 80-95%, and the pore diameter is 1-3 micrometers;
the fluoropolymer film with the microporous structure is a unidirectional stretching film or a bidirectional stretching film;
the fluoropolymer film with the microporous structure is a Polytetrafluoroethylene (PTFE) porous film, a polyvinylidene fluoride (PVDF) porous film, a polytrifluorochloroethylene (CTFE) porous film or a polytetrafluoroethylene-ethylene (ETFE) porous film;
the perfluoro resin with ion exchange function is selected from one or the combination of the following: perfluorosulfonic acid resin, perfluorocarboxylic acid resin, or perfluorophosphoric acid resin;
the perfluorosulfonic acid resin has the following general formula:
wherein x is 3-15, n is 0-2, p is 2-5, ion exchange capacity is 0.90-1.60 mmol/g, and molecular weight is 10-60 ten thousand; the perfluorocarboxylic acid resin has the following structural unit:
in the formula (II), c is 0 or 1, d is 1-5, a is 3-11, b is 1-3, the ion exchange capacity is 0.85-1.50 mmol/g, and the molecular weight is 10-60 ten thousand;
the perfluoro phosphoric acid resin has the following structural units:
in the formula (III), e is 3-20, f is 1, the ion exchange capacity is 0.80-2.5 mmol/g, and the molecular weight is 10-60 ten thousand.
2. A method of preparing a proton exchange composite membrane according to claim 1, comprising the steps of:
(1) the full fluorine resin with ion exchange function or the precursor thereof is compounded with the fluorine-containing polymer film with a microporous structure into a film by extrusion, hot pressing, solution casting, tape casting, screen printing, spraying or dipping processes;
(2) and (2) carrying out heat treatment on the membrane prepared in the step (1) at 30-250 ℃ to obtain the high-temperature proton exchange composite membrane.
3. The method for preparing a proton exchange composite membrane according to claim 2, wherein in the step (1), the perfluorinated resin is first dissolved in a solvent to prepare a perfluorinated resin solution by using a solution casting, screen printing, spraying or dipping process, wherein the solvent is selected from one or a combination of the following solvents: one or more of dimethylformamide, dimethylacetamide, methylformamide, dimethyl sulfoxide, N-methylpyrrolidone, hexamethyl ammonium phosphate, acetone, water, ethanol, methanol, propanol, isopropanol, ethylene glycol or glycerol.
4. The method for preparing a proton exchange composite membrane according to claim 3, wherein the perfluoro resin solution has a solid content of 1 to 80% by weight and a viscosity of 1 to 4000 cP.
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| CN102010555B (en) * | 2010-06-18 | 2013-07-31 | 山东华夏神舟新材料有限公司 | Fluorine-containing ionomer composite with ion exchange function as well as preparation method and application thereof |
| CN102649315A (en) * | 2011-02-23 | 2012-08-29 | 北京化工大学 | Polyvinylidene fluoride microporous film prepared through gelatin extrusion tape casting method |
| CN102658645B (en) * | 2012-05-14 | 2014-06-25 | 华北电力大学 | Method for preparing perfluorinated sulfonic acid proton exchange membrane with specifically-oriented structure |
| CN104037431B (en) * | 2014-04-11 | 2017-12-12 | 广东玖美新材料有限公司 | Flow battery amberplex |
| CN111020630B (en) * | 2019-12-31 | 2021-07-13 | 山东东岳高分子材料有限公司 | Ultrathin perfluorocarboxylic acid ion exchange membrane with bubble-dispelling function and preparation method thereof |
| CN117242608A (en) * | 2021-03-29 | 2023-12-15 | 浙江汉丞新能源有限公司 | Composite membrane of special high-enhancement type fluorine-containing proton or ion exchange membrane, composite membrane electrode, special high-enhancement type fluorine-containing chlor-alkali battery membrane, special release membrane and preparation method thereof |
| CN115991820B (en) * | 2021-10-18 | 2024-01-05 | 山东东岳未来氢能材料股份有限公司 | Polymeric phosphonic acid ionic membrane and preparation method thereof |
| CN113736134B (en) * | 2021-11-08 | 2022-02-22 | 国家电投集团氢能科技发展有限公司 | Modified expanded polytetrafluoroethylene, preparation method thereof, composite ion exchange membrane and application thereof |
| CN114976165B (en) * | 2022-06-17 | 2024-02-02 | 上海恩捷新材料科技有限公司 | Composite ion exchange membrane and preparation method thereof |
| WO2024086988A1 (en) * | 2022-10-24 | 2024-05-02 | 四川大学 | Ultra-thin high-strength proton exchange membrane, and preparation method therefor and use thereof |
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| US5834523A (en) * | 1993-09-21 | 1998-11-10 | Ballard Power Systems, Inc. | Substituted α,β,β-trifluorostyrene-based composite membranes |
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