WO2022131666A1 - 폴리플루오렌계 음이온교환 복합막 및 그 제조방법 - Google Patents
폴리플루오렌계 음이온교환 복합막 및 그 제조방법 Download PDFInfo
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- WO2022131666A1 WO2022131666A1 PCT/KR2021/018582 KR2021018582W WO2022131666A1 WO 2022131666 A1 WO2022131666 A1 WO 2022131666A1 KR 2021018582 W KR2021018582 W KR 2021018582W WO 2022131666 A1 WO2022131666 A1 WO 2022131666A1
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- Prior art keywords
- anion exchange
- polyfluorene
- formula
- composite membrane
- exchange composite
- Prior art date
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- 239000012528 membrane Substances 0.000 title claims abstract description 102
- 239000002131 composite material Substances 0.000 title claims abstract description 86
- 238000005349 anion exchange Methods 0.000 title claims abstract description 82
- 229920002098 polyfluorene Polymers 0.000 title claims abstract description 72
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims description 15
- 229920000642 polymer Polymers 0.000 claims abstract description 75
- 239000003011 anion exchange membrane Substances 0.000 claims abstract description 41
- 239000000446 fuel Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 8
- 229920001577 copolymer Polymers 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 31
- 229920000554 ionomer Polymers 0.000 claims description 29
- 239000004698 Polyethylene Substances 0.000 claims description 22
- -1 polyethylene Polymers 0.000 claims description 20
- 239000006184 cosolvent Substances 0.000 claims description 18
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000004132 cross linking Methods 0.000 claims description 12
- 229920000573 polyethylene Polymers 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 6
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- 238000005266 casting Methods 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000003431 cross linking reagent Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 239000004305 biphenyl Substances 0.000 claims description 3
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 10
- 239000001569 carbon dioxide Substances 0.000 abstract description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 5
- 230000007774 longterm Effects 0.000 abstract description 5
- 230000009467 reduction Effects 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 23
- 238000002360 preparation method Methods 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 6
- 230000035699 permeability Effects 0.000 description 5
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229920000557 Nafion® Polymers 0.000 description 3
- 238000003682 fluorination reaction Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000005518 polymer electrolyte Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- PAMIQIKDUOTOBW-UHFFFAOYSA-N N-methylcyclohexylamine Natural products CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical group C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- IBODDUNKEPPBKW-UHFFFAOYSA-N 1,5-dibromopentane Chemical compound BrCCCCCBr IBODDUNKEPPBKW-UHFFFAOYSA-N 0.000 description 1
- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical compound BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 description 1
- HUUPVABNAQUEJW-UHFFFAOYSA-N 1-methylpiperidin-4-one Chemical compound CN1CCC(=O)CC1 HUUPVABNAQUEJW-UHFFFAOYSA-N 0.000 description 1
- ZHQNDEHZACHHTA-UHFFFAOYSA-N 9,9-dimethylfluorene Chemical compound C1=CC=C2C(C)(C)C3=CC=CC=C3C2=C1 ZHQNDEHZACHHTA-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910002848 Pt–Ru Inorganic materials 0.000 description 1
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229960003638 dopamine Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000110 poly(aryl ether sulfone) Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
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- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C—CHEMISTRY; METALLURGY
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- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/08—Fuel cells with aqueous electrolytes
- H01M8/083—Alkaline fuel cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
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- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
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- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1053—Polymer electrolyte composites, mixtures or blends consisting of layers of polymers with at least one layer being ionically conductive
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- H01M8/1081—Polymeric electrolyte materials characterised by the manufacturing processes starting from solutions, dispersions or slurries exclusively of polymers
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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
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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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- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a polyfluorene-based anion exchange composite membrane and a method for manufacturing the same, and more particularly, to a porous polymer support; and a polyfluorene-based anion exchange membrane or a polyfluorene-based anion exchange membrane having a cross-linked structure impregnated in the porous polymer support, and prepared an anion exchange composite membrane comprising an alkali fuel cell, water electrolysis, carbon dioxide reduction, metal-air battery It relates to the technology applied to, etc.
- PEMFCs polymer electrolyte membrane fuel cells
- Nafion a perfluorocarbon-based proton exchange membrane, represented by Nafion
- Nafion membrane has excellent chemical stability and high ionic conductivity, while the price is very high and the glass transition temperature is low, so research that can replace Nafion, including the development of an aromatic hydrocarbon-based polymer electrolyte membrane, is being actively conducted.
- alkaline membrane fuel cell using an anion exchange membrane operating in an alkaline environment has recently been attracting attention.
- alkaline membrane fuel cells can use inexpensive non-precious metals such as nickel and manganese as electrode catalysts instead of platinum. the current situation.
- Polymers having an aryl ether main chain such as polyaryl ether sulfone, polyphenyl ether, and polyether ether ketone, have been mainly used as anion exchange membranes for application to alkaline membrane fuel cells.
- an anion exchange membrane having a crosslinked structure using a hydrophobic crosslinking agent such as 1,5-dibromopentane, 1,6-dibromohexane, and 1,6-hexanediamine
- the hydrophobic anion exchange membrane is an anion exchange fuel cell.
- problems such as low ionic conductivity, limited flexibility, and low solubility for application.
- conventional anion exchange membranes have limited chemical stability (less than 500 hours at 80 ° C, 1M NaOH solution) and mechanical properties (tensile strength less than 30 Mpa). It has the disadvantage of poor durability.
- the conventional conventional anion exchange membrane has poor dimensional stability due to high water uptake and swelling ratio.
- the anion exchange composite membrane there is a disadvantage in that the polymer solution is not easily impregnated into the porous support during the manufacturing process, so improvement is required.
- Patent Document 1 Korean Patent Application Laid-Open No. 10-2018-0121961
- Patent Document 2 International Patent Publication WO 2019/068051
- Patent Document 3 Chinese Registered Patent Publication CN 106784946
- Patent Document 4 China Registered Patent Publication CN 108164724
- the present invention has been devised in view of the above problems, and a first object of the present invention is to provide a polyfluorene-based anion exchange composite membrane with significantly improved mechanical properties, dimensional stability, durability and long-term stability, and a method for manufacturing the same will do
- a second object of the present invention is to apply the polyfluorene-based anion exchange composite membrane to alkaline fuel cells, water electrolysis, carbon dioxide reduction, and metal-air batteries.
- the present invention for achieving the above object is a porous polymer support; and a polyfluorene-based anion exchange membrane impregnated in the porous polymer support or a polyfluorene-based anion exchange membrane having a crosslinked structure; provides a polyfluorene-based anion exchange composite membrane comprising a.
- the porous polymer support is characterized in that it is selected from the group consisting of polyethylene, polypropylene, polytetrafluoroethylene, polyvinylidene fluoride, polyhexafluoropropylene and polyperfluoroalkyl vinyl ether.
- the porous polymer support has a pore size of 0.01 to 0.5 ⁇ m and a porosity of 50 to 90%.
- the porous polymer support is characterized by being fluorinated or hydrophilized.
- the polyfluorene-based anion exchange membrane is characterized in that it is a polyfluorene-based copolymer ionomer having a repeating unit represented by the following ⁇ Formula 1>.
- A, B, C and D segments are each independently selected from compounds represented by the following structural formula, and may be the same or different,
- the polyfluorene-based anion exchange membrane having the cross-linked structure is characterized in that it is a polyfluorene-based cross-linked copolymer selected from copolymers having a cross-linked structure represented by the following ⁇ Formula 2> to ⁇ Formula 6>.
- aryl-1 and aryl-2 are each independently selected from the group consisting of fluorenyl, phenyl, biphenyl, terphenyl and quaterphenyl, at least one of which is is fluorenyl,
- R H or CH 3 ,
- x represents the degree of crosslinking
- n an integer from 1 to 15
- the present invention comprises the steps of (I) preparing a porous polymer support; (II) the polyfluorene-based copolymer represented by the ⁇ Formula 1> or the polyfluorene-based cross-linked copolymer selected from those represented by the ⁇ Formula 2> to ⁇ Formula 6> in a polymer solution dissolved in an organic solvent adding medium to obtain an ionomer solution; and (III) casting the ionomer solution on a porous polymer support, impregnating it, and drying the polyfluorene-based anion exchange composite membrane.
- the porous polymer support of step (I) is characterized in that the surface is fluorinated or hydrophilized.
- the organic solvent of step (II) is N-methylpyrrolidone, dimethylacetamide, dimethylsulfoxide or dimethylformamide.
- the cosolvent in step (II) is characterized in that methanol, ethanol or isopropyl alcohol.
- the cosolvent added in step (II) is characterized in that it is 2 to 25 wt% based on the polymer solution.
- the present invention provides a membrane electrode assembly for an alkaline fuel cell comprising the polyfluorene-based anion exchange composite membrane.
- the present invention provides an alkaline fuel cell including the polyfluorene-based anion exchange composite membrane.
- the present invention provides a water electrolysis device including the polyfluorene-based anion exchange composite membrane.
- the polyfluorene-based anion exchange composite membrane including the porous polymer support has significantly improved mechanical properties, dimensional stability, durability and long-term stability.
- polyfluorene-based anion exchange composite membrane including the porous polymer support of the present invention can be applied to alkaline fuel cells, water electrolysis devices, carbon dioxide reduction, metal-air batteries, and the like.
- the degree of impregnation of the ionomer polymer solution is improved by surface treatment of the support and the use of a cosolvent, thereby enabling mass production as a high concentration product.
- FIG. 1 is a real photograph of a polyfluorene-based anion exchange composite membrane obtained according to an embodiment of the present invention.
- [Correction 05.01.2022 under Rule 91] 2 is an anion exchange composite membrane prepared from Examples 1 to 3 of the present invention, an anion exchange membrane prepared from Comparative Example 1, and a graph and images showing the transparency of a porous polyethylene support (thickness 20 ⁇ m) as a control [( a) UV-transmittance measurement result graph, (b) real photograph and (c) scanning electron microscope (SEM) image].
- Example 3 is a scanning electron microscope (SEM) image of the surface and cross-section of the anion exchange composite membrane prepared in Example 2 of the present invention.
- FIG 4 is a graph showing the mechanical properties of the anion exchange composite membrane prepared from Examples 2 to 5 of the present invention, the anion exchange membrane prepared from Comparative Example 1, the anion exchange composite membrane prepared from Comparative Example 2, and a porous polyethylene support as a control; .
- thermogravimetric analysis (TGA) graph showing the thermal stability of the anion exchange composite membrane prepared in Example 2 of the present invention, the anion exchange composite membrane prepared in Comparative Example 2 and a porous polyethylene support as a control.
- Example 6 is a graph showing the dimensional stability of the anion exchange composite membrane prepared in Example 3 and the anion exchange membrane prepared in Comparative Example 1 of the present invention.
- Example 7 is a graph showing the hydrogen permeability and water permeability of the anion exchange composite membrane prepared in Example 2 of the present invention, the anion exchange membrane prepared in Comparative Example 1 and a conventionally commercialized anion exchange membrane (FAA-3-50) as a control.
- Example 8 is a graph evaluating the fuel cell performance of the anion exchange composite membrane prepared in Example 2 of the present invention and the anion exchange composite membrane prepared in Comparative Examples 2 and 3;
- Example 9 is a graph evaluating the fuel cell performance of the anion exchange composite membrane prepared in Example 1 and the anion exchange membrane prepared in Comparative Example 1 of the present invention.
- a porous polymer support and a polyfluorene-based anion exchange membrane impregnated in the porous polymer support or a polyfluorene-based anion exchange membrane having a crosslinked structure; provides a polyfluorene-based anion exchange composite membrane comprising a.
- the porous polymer support may be selected from the group consisting of polyethylene, polypropylene, polytetrafluoroethylene, polyvinylidene fluoride, polyhexafluoropropylene and polyperfluoroalkyl vinyl ether, but is limited thereto not.
- porous polymer support having a pore size of 0.01 to 0.5 ⁇ m and a porosity of 50 to 90% is more preferable because it can stably impregnate the polyfluorene-based copolymer or the polyfluorene-based cross-linked copolymer ionomer solution. .
- the porous polymer support is mostly hydrophobic, the affinity between the porous polymer support and the polyfluorene-based copolymer or polyfluorene-based cross-linked copolymer is improved, and the ionomer polymer solution is stably impregnated with an anion without defects.
- the surface of the porous polymer support may be fluorinated or hydrophilized.
- the porous polymer support is immersed in an ethanol solution, ultrasonically dispersed at -10°C to 25°C, and then the porous polymer support is taken out and dried at room temperature. Then, the dried porous polymer support is placed in a vacuum chamber and the inside of the chamber is purged with nitrogen gas to create an inert atmosphere. Thereafter, fluorine gas (500 ⁇ 15 ppm F 2 /N 2 at atmospheric pressure) was supplied to the vacuum chamber at a rate of 1 L/min, and the surface was directly fluorinated for 5 to 60 minutes at room temperature to obtain a fluorinated porous polymer support. It can be obtained, and the residual fluorine gas is removed by using nitrogen gas with a scrubber filled with activated carbon.
- fluorine gas 500 ⁇ 15 ppm F 2 /N 2 at atmospheric pressure
- a hydrophilic alkyl alcohol having 1 to 3 carbon atoms may be applied to the surface of the porous polymer support, or may be coated with a hydrophilic polymer such as dopamine or polyvinyl alcohol.
- polyfluorene-based anion exchange membrane may be a polyfluorene-based copolymer ionomer having a repeating unit represented by the following ⁇ Formula 1>.
- A, B, C and D segments are each independently selected from compounds represented by the following structural formula, and may be the same or different,
- the inventors of the present invention have already disclosed a novel polyfluorene-based copolymer in an earlier patent application (Patent Publication No. 10-2021-0071810).
- An ionomer, an anion exchange membrane, and a method for manufacturing the same have been disclosed, and in the present invention, the polyfluorene-based copolymer ionomer obtained in the same manner as the manufacturing method is used.
- polyfluorene-based anion exchange membrane having the crosslinked structure may be a polyfluorene-based crosslinked copolymer selected from copolymers having a crosslinked structure represented by the following ⁇ Formula 2> to ⁇ Formula 6>.
- aryl-1 and aryl-2 are each independently selected from the group consisting of fluorenyl, phenyl, biphenyl, terphenyl and quaterphenyl, at least one of which is is fluorenyl,
- R H or CH 3 ,
- x represents the degree of crosslinking
- n an integer from 1 to 15
- Polyfluorene-based copolymer such as poly(fluorene-co-terphenyl N-methylpiperidine) [PFTM] disclosed in the previous application patent (Patent Publication No. 10-2021-0071810) is prepared by reacting at least one ammonium cation
- a polyfluorene-based crosslinked copolymer having a crosslinked structure selected from those represented by the ⁇ Formula 2> to ⁇ Formula 6> having a crosslinked structure different from the conventional one was prepared by crosslinking with a compound having a crosslinking structure.
- x represents a degree of crosslinking and can be controlled by the amount of a polyammonium compound having at least one ammonium cation used as a crosslinking agent, and the degree of crosslinking is preferably 5 to 20% Bar, if the degree of crosslinking is less than 5%, the effect of increasing physical properties due to crosslinking is insignificant, and if the degree of crosslinking exceeds 20%, the crosslinking copolymer may not be completely dissolved in the organic solvent and thus the crosslinking reaction may not proceed.
- the present invention comprises the steps of (I) preparing a porous polymer support; (II) the polyfluorene-based copolymer represented by the ⁇ Formula 1> or the polyfluorene-based cross-linked copolymer selected from those represented by the ⁇ Formula 2> to ⁇ Formula 6> in a polymer solution dissolved in an organic solvent adding medium to obtain an ionomer solution; and (III) casting the ionomer solution on a porous polymer support, impregnating it, and drying the polyfluorene-based anion exchange composite membrane.
- the porous polymer support in step (I) may have a surface treated with fluorination or hydrophilization, and the fluorination treatment or hydrophilization treatment is the same as described above.
- organic solvent in step (II) may be N-methylpyrrolidone, dimethylacetamide, dimethylsulfoxide or dimethylformamide, and dimethylsulfoxide is preferably used.
- the polyfluorene-based copolymer represented by the ⁇ Formula 1> or the ⁇ Formula 2> > to ⁇ Formula 6> to obtain an ionomer polymer solution by adding a cosolvent to a polymer solution in which a polyfluorene-based cross-linked copolymer selected from those represented by Formula 6 is dissolved in an organic solvent, which is an anion exchange composite membrane manufacturing method according to the present invention
- a key technical feature is that a composite membrane can be obtained by a simple method of casting a polymer solution on a porous polymer support, so the manufacturing process is simple and it can be manufactured even with a high-concentration solution, so it has the advantage of being able to mass-produce.
- the interfacial tension with the porous polymer support was calculated by measuring the contact angles of various organic solvents. Accordingly, methanol, ethanol or isopropyl alcohol can be used as the co-solvent, and ethanol is more preferable. use it sparingly
- the cosolvent added in step (II) is preferably 2 to 25% by weight relative to the polymer solution. If the content of the added cosolvent is less than 2% by weight relative to the polymer solution, the ionomer polymer solution is easily impregnated into the porous polymer support. It may not be possible, and if the content exceeds 25% by weight, it may be difficult to obtain a high-concentration polymer solution.
- the present invention provides a membrane electrode assembly for an alkaline fuel cell comprising the polyfluorene-based anion exchange composite membrane.
- the present invention provides an alkaline fuel cell including the polyfluorene-based anion exchange composite membrane.
- the present invention provides a water electrolysis device including the polyfluorene-based anion exchange composite membrane.
- 9,9'-dimethylfluorene (0.2914 g, 1.5 mmol) as a monomer
- terphenyl (3.105 g, 13.5 mmol) as a comonomer
- 1-methyl-4-piperidone (1.919 mL, 16.5 mmol, 1.1 eq) was added to a two-neck flask, and dichloromethane (13 mL) was added thereto to dissolve the monomers while stirring to form a solution.
- a porous polyethylene support (W-PE) was prepared (purchased from W-Scope, 10 ⁇ m or 20 ⁇ m thick).
- An ionomer solution was obtained by adding 3.3 wt% of ethanol as a cosolvent to a polymer solution having a concentration of 10 wt% in which the PFTP obtained in Preparation Example was dissolved in dimethyl sulfoxide.
- the porous polyethylene support (which may have been fluorinated or hydrophilized according to the method described above) was fixed to a glass plate, the ionomer solution was impregnated on the support, and then spread evenly with a dropper. Thereafter, after drying in an oven at 80° C. for 24 hours, repeatedly drying at 80° C. in a vacuum oven for 24 hours to prepare an anion exchange composite membrane (3.3% PFTP@W-PE).
- An anion exchange composite membrane was prepared in the same manner as in Example 1, except that an ionomer solution was obtained by adding 10% by weight of ethanol to the polymer solution (10% PFTP@W-PE).
- An anion exchange composite membrane was prepared in the same manner as in Example 1, except that an ionomer solution was obtained by adding 15% by weight of ethanol to the polymer solution (15% PFTP@W-PE).
- An anion exchange composite membrane was prepared in the same manner as in Example 1, except that an ionomer solution was obtained by adding 20% by weight of ethanol to the polymer solution (20% PFTP@W-PE).
- An anion exchange composite membrane was prepared in the same manner as in Example 1, except that an ionomer solution was obtained by adding 25% by weight of ethanol to the polymer solution (25% PFTP@W-PE).
- the PFTP obtained in Preparation Example was dissolved in dimethyl sulfoxide to form a polymer solution having a concentration of 3.2 wt%. Then, the polymer solution was collected with a syringe, filtered through a 0.4 ⁇ m filter, and the transparent solution was cast on a 14 x 21 cm glass plate. The casting solution was dried in an oven at 85° C. for 24 hours to slowly remove the solvent, and then heated in a vacuum oven at 150° C. for 24 hours to completely remove the solvent, thereby preparing a polyfluorene-based anion exchange membrane (PFTP single membrane).
- An anion exchange composite membrane was prepared in the same manner as in Example 1 except that the process of adding ethanol as a cosolvent was not performed (PFTP@W-PE).
- An anion exchange composite membrane was prepared in the same manner as in Example 1 except that a porous polymer support was purchased from S-(?) and used (PFTP@S-PE).
- Test data such as mechanical properties, morphology, ion exchange performance, moisture content, expansion rate, ion conductivity and fuel cell performance of the anion exchange composite membranes prepared in Examples 1 to 3 and Comparative Examples 1 to 3 of the present invention are the inventors of the present invention, etc. It was measured and evaluated by the method described in Korean Patent Publication No. 10-2021-0071810.
- FIG. 1 shows an actual photograph of the polyfluorene-based anion exchange composite membrane obtained according to an embodiment of the present invention, it can be confirmed with the naked eye that a transparent and uniform membrane was prepared.
- the anion exchange composite membrane prepared from Examples 1 to 3 of the present invention, the anion exchange membrane prepared from Comparative Example 1, and a porous polyethylene support (W-PE, thickness 20 ⁇ m) as a control are related to the transparency (transmittance) As shown in graphs and images [(a) UV-transmittance measurement result graph, (b) real photo and scanning electron microscope (SEM) image], when ethanol is used as a cosolvent, transparency increases and the degree of impregnation is improved. can check that
- Example 3 shows a scanning electron microscope (SEM) image of the surface and cross-section of the anion exchange composite membrane prepared in Example 2 of the present invention.
- Example 2 of the present invention As shown in FIG. 3, it can be seen that the surface of the anion exchange composite membrane prepared in Example 2 of the present invention was uniformly coated without cracks at the top and bottom. In addition, from the cross-sectional image, it can be confirmed repeatedly that the support is located in the middle and is uniformly coated with the same thickness above and below.
- IEC ion exchange capacity of the anion exchange composite membrane prepared in Example 2 and the anion exchange membrane prepared in Comparative Example 1 of the present invention
- WU moisture content
- SR expansion rate
- ⁇ ionic conductivity
- TS tensile strength
- EB elongation
- T transparency
- Figure 4 shows the mechanical properties of the anion exchange composite membrane prepared from Examples 2 to 5 of the present invention, the anion exchange membrane prepared from Comparative Example 1, the anion exchange composite membrane prepared from Comparative Example 2 and the porous polyethylene support as a control,
- Example 5 shows the thermal stability of the anion exchange composite membrane prepared in Example 2 of the present invention, the anion exchange composite membrane prepared in Comparative Example 2 and the porous polyethylene support as a control.
- Example 2a 2.36 25 17 7 15 91/49 100%
- Example 2b 2.35 20 16 5 32 121/53 ⁇ 84% Comparative Example 2 2.78 76 24 27 65 68/30 ⁇ 100%
- a W-PE thickness 20 ⁇ m
- b W-PE thickness 10 ⁇ m
- the anion exchange composite membrane prepared according to the present invention has a tensile strength of 1.7 times or more and an elongation of 2.5 times or more compared to a conventional anion exchange composite membrane or a single membrane type anion exchange membrane.
- excellent mechanical properties are exhibited, which can be interpreted as the effect of greatly improving the degree of impregnation by the addition of a cosolvent such as ethanol in the manufacturing process of the composite membrane.
- thermogravimetric analysis result of FIG. 5 it can be confirmed that the anion exchange composite membrane prepared according to the present invention is thermally stable.
- Example 6 shows the dimensional stability of the anion exchange composite membrane prepared in Example 3 and the anion exchange membrane prepared in Comparative Example 1 of the present invention. Compared to the anion exchange membrane in the form of a single membrane, the moisture content is 1/3 or less, It can be seen that the expansion rate is reduced to 1/5 or less and shows very good dimensional stability.
- FIG. 7 shows the hydrogen permeability and water permeability of the anion exchange composite membrane prepared in Example 2 of the present invention, the anion exchange membrane prepared in Comparative Example 1, and a conventionally commercialized anion exchange membrane (FAA-3-50) as a control.
- FFA-3-50 a conventionally commercialized anion exchange membrane
- the anion exchange composite membrane is a platinum group metal catalyst electrode (Pt-Ru/C anode, Pt/C cathode) and 80°C, A/C 1.3/1.3 backpressure, H 2 -O 2 or It shows excellent performance and ideal curve even in H 2 -air (CO 2 free) atmosphere, and this result is also due to the smooth ion transfer as the degree of impregnation was greatly improved by the addition of a cosolvent such as ethanol during the composite membrane manufacturing process. interpreted as doing
- FIG. 9 shows a graph evaluating the fuel cell performance of the anion exchange composite membrane prepared in Example 1 of the present invention and the anion exchange membrane prepared in Comparative Example 1 of the present invention. From the result of maintaining the high voltage without voltage drop for about 130 hours or more, it can be seen that the anion exchange composite membrane according to the present invention has excellent durability.
- the anion exchange composite membrane according to the present invention can be mass-produced as a high-concentration product by greatly improving the degree of impregnation by the addition of a co-solvent in the manufacturing process, and mechanical properties, dimensional stability, durability and long-term stability, etc. are remarkably improved, alkali fuel It can be applied to batteries, water electrolysis devices, carbon dioxide reduction, metal-air batteries, and the like.
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Abstract
Description
도 2는 본 발명의 실시예 1 내지 3으로부터 제조한 음이온교환 복합막, 비교예 1로부터 제조한 음이온교환막 및 대조군으로서 다공성 폴리에틸렌 지지체(두께 20㎛)의 투명도(transmittance)를 나타낸 그래프 및 이미지[(a) UV-transmittance 측정결과 그래프, (b) 실물 사진 및 (c)주사전자현미경(SEM) 이미지].
샘플 | IEC (mmolg-1) |
WU(%) | In plane SR (%) |
Through-place SR(%) | σ | TS(Mpa)/ EB(%) |
T(%) |
실시예 2a | 2.36 | 25 | 17 | 7 | 15 | 91/49 | 100% |
실시예 2b | 2.35 | 20 | 16 | 5 | 32 | 121/53 | ~84% |
비교예 2 | 2.78 | 76 | 24 | 27 | 65 | 68/30 | ~100% |
Claims (14)
- 다공성 고분자 지지체; 및상기 다공성 고분자 지지체에 함침된 폴리플루오렌계 음이온교환막 또는 가교구조의 폴리플루오렌계 음이온교환막;을 포함하는 폴리플루오렌계 음이온교환 복합막.
- 제1항에 있어서, 상기 다공성 고분자 지지체는 폴리에틸렌, 폴리프로필렌, 폴리테트라플루오로에틸렌, 폴리비닐리덴플루오라이드, 폴리헥사플루오로프로필렌 및 폴리퍼플루오로알킬비닐에테르로 이루어진 군으로부터 선택된 것을 특징으로 하는 폴리플루오렌계 음이온교환 복합막.
- 제1항에 있어서, 상기 다공성 고분자 지지체는 기공크기가 0.01~0.5㎛, 기공률이 50~90%인 것을 특징으로 하는 폴리플루오렌계 음이온교환 복합막.
- 제1항에 있어서, 상기 다공성 고분자 지지체는 불소화 처리 또는 친수화 처리된 것을 특징으로 하는 폴리플루오렌계 음이온교환 복합막.
- 제1항에 있어서, 상기 가교구조의 폴리플루오렌계 음이온교환막은 하기 <화학식 2> 내지 <화학식 6>으로 표시되는 가교구조의 공중합체로부터 선택된 폴리플루오렌계 가교 공중합체인 것을 특징으로 하는 폴리플루오렌계 음이온교환 복합막.<화학식 2><화학식 3><화학식 4><화학식 5><화학식 6>(상기 <화학식 2> 내지 <화학식 6>에서, aryl-1, aryl-2는 각각 독립적으로 플루오레닐, 페닐, 바이페닐, 터페닐 및 쿼터페닐로 이루어진 군으로부터 선택된 것이고, 그 중 적어도 하나는 플루오레닐이며,R=H 또는 CH3,x는 가교도를 나타내는 것이고,n=1 내지 15의 정수이다)
- (I) 다공성 고분자 지지체를 준비하는 단계;(II) 제5항의 상기 <화학식 1>로 표시되는 폴리플루오렌계 공중합체 또는 제6항의 상기 <화학식 2> 내지 <화학식 6>으로 표시되는 것에서 선택된 폴리플루오렌계 가교 공중합체를 유기용매에 용해시킨 중합체 용액에 공용매를 첨가하여 이오노머 용액을 얻는 단계; 및(III) 상기 이오노머 용액을 다공성 고분자 지지체 위에 캐스팅하여 함침, 및 건조하는 단계;를 포함하는 폴리플루오렌계 음이온교환 복합막의 제조방법.
- 제7항에 있어서, 상기 (I) 단계의 다공성 고분자 지지체는 표면을 불소화 처리 하거나 친수화 처리한 것을 특징으로 하는 폴리플루오렌계 음이온교환 복합막의 제조방법.
- 제7항에 있어서, 상기 (II) 단계의 유기용매는 N-메틸피롤리돈, 디메틸아세트아미드, 디메틸술폭시드 또는 디메틸포름아미드인 것을 특징으로 하는 폴리플루오렌계 음이온교환 복합막의 제조방법.
- 제7항에 있어서, 상기 (II) 단계의 공용매는 메탄올, 에탄올 또는 이소프로필알코올인 것을 특징으로 하는 폴리플루오렌계 음이온교환 복합막의 제조방법.
- 제7항에 있어서, 상기 (II) 단계에서 첨가하는 공용매는 중합체 용액 대비 2~25 중량%인 것을 특징으로 하는 폴리플루오렌계 음이온교환 복합막의 제조방법.
- 제1항 내지 제6항 중 어느 한 항에 따른 폴리플루오렌계 음이온교환 복합막을 포함하는 알칼리 연료전지용 막전극접합체.
- 제1항 내지 제6항 중 어느 한 항에 따른 폴리플루오렌계 음이온교환 복합막을 포함하는 알칼리 연료전지.
- 제1항 내지 제6항 중 어느 한 항에 따른 폴리플루오렌계 음이온교환 복합막을 포함하는 수전해 장치.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US18/268,454 US20240100490A1 (en) | 2020-12-18 | 2021-12-09 | Polyfluorene-based anion exchange composite membrane and method for preparing same |
CN202180085796.3A CN116636055A (zh) | 2020-12-18 | 2021-12-09 | 基于聚芴的阴离子交换复合膜及其制备方法 |
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CHEN NANJUN, LU CHUANRUI, LI YUNXI, LONG CHUAN, ZHU HONG: "Robust poly(aryl piperidinium)/N-spirocyclic poly(2,6-dimethyl-1,4-phenyl) for hydroxide-exchange membranes", JOURNAL OF MEMBRANE SCIENCE, ELSEVIER BV, NL, vol. 572, 1 February 2019 (2019-02-01), NL , pages 246 - 254, XP055942827, ISSN: 0376-7388, DOI: 10.1016/j.memsci.2018.10.067 * |
CHEN NANJUN; LU CHUANRUI; LI YUNXI; LONG CHUAN; LI ZIMING; ZHU HONG: "Tunable multi-cations-crosslinked poly(arylene piperidinium)-based alkaline membranes with high ion conductivity and durability", JOURNAL OF MEMBRANE SCIENCE, ELSEVIER BV, NL, vol. 588, 18 May 2019 (2019-05-18), NL , XP085765162, ISSN: 0376-7388, DOI: 10.1016/j.memsci.2019.05.044 * |
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