CN108075160B - A kind of the glass base fuel battery proton exchange membrane and preparation method of high-temperature stable - Google Patents
A kind of the glass base fuel battery proton exchange membrane and preparation method of high-temperature stable Download PDFInfo
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- CN108075160B CN108075160B CN201711472582.3A CN201711472582A CN108075160B CN 108075160 B CN108075160 B CN 108075160B CN 201711472582 A CN201711472582 A CN 201711472582A CN 108075160 B CN108075160 B CN 108075160B
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- glass
- proton exchange
- exchange membrane
- sulfonation
- fuel battery
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- 239000011521 glass Substances 0.000 title claims abstract description 144
- 239000012528 membrane Substances 0.000 title claims abstract description 76
- 239000000446 fuel Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 55
- 239000004696 Poly ether ether ketone Substances 0.000 claims abstract description 34
- 229920002530 polyetherether ketone Polymers 0.000 claims abstract description 34
- 239000000843 powder Substances 0.000 claims abstract description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 24
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 12
- MPPQGYCZBNURDG-UHFFFAOYSA-N 2-propionyl-6-dimethylaminonaphthalene Chemical compound C1=C(N(C)C)C=CC2=CC(C(=O)CC)=CC=C21 MPPQGYCZBNURDG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 11
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 11
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004642 Polyimide Substances 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 10
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000010436 fluorite Substances 0.000 claims abstract description 10
- 239000003365 glass fiber Substances 0.000 claims abstract description 10
- 238000002844 melting Methods 0.000 claims abstract description 10
- 230000008018 melting Effects 0.000 claims abstract description 10
- 229920001721 polyimide Polymers 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 239000010408 film Substances 0.000 claims description 66
- 239000000463 material Substances 0.000 claims description 39
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 32
- 239000002131 composite material Substances 0.000 claims description 24
- 239000012530 fluid Substances 0.000 claims description 21
- 239000011347 resin Substances 0.000 claims description 17
- 229920005989 resin Polymers 0.000 claims description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 16
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000004513 sizing Methods 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 11
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 11
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 150000004985 diamines Chemical class 0.000 claims description 10
- 238000011049 filling Methods 0.000 claims description 10
- 238000007711 solidification Methods 0.000 claims description 9
- 230000008023 solidification Effects 0.000 claims description 9
- 239000010409 thin film Substances 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical class CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- 230000008595 infiltration Effects 0.000 claims description 8
- 238000001764 infiltration Methods 0.000 claims description 8
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical class CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- -1 4,4'- diaminodiphenyl ethers Chemical class 0.000 claims description 5
- 229910021540 colemanite Inorganic materials 0.000 claims description 5
- 239000001294 propane Substances 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- VACCAVUAMIDAGB-UHFFFAOYSA-N sulfamethizole Chemical compound S1C(C)=NN=C1NS(=O)(=O)C1=CC=C(N)C=C1 VACCAVUAMIDAGB-UHFFFAOYSA-N 0.000 claims description 4
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical class C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 claims description 4
- WECDUOXQLAIPQW-UHFFFAOYSA-N 4,4'-Methylene bis(2-methylaniline) Chemical compound C1=C(N)C(C)=CC(CC=2C=C(C)C(N)=CC=2)=C1 WECDUOXQLAIPQW-UHFFFAOYSA-N 0.000 claims description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 3
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 claims description 3
- 239000000404 calcium aluminium silicate Substances 0.000 claims description 3
- 235000012215 calcium aluminium silicate Nutrition 0.000 claims description 3
- WNCYAPRTYDMSFP-UHFFFAOYSA-N calcium aluminosilicate Chemical compound [Al+3].[Al+3].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O WNCYAPRTYDMSFP-UHFFFAOYSA-N 0.000 claims description 3
- 229940078583 calcium aluminosilicate Drugs 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 claims description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellityc acid Natural products OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims description 2
- 150000003457 sulfones Chemical class 0.000 claims description 2
- 150000003462 sulfoxides Chemical class 0.000 claims description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 claims 2
- 150000008065 acid anhydrides Chemical class 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 239000000284 extract Substances 0.000 claims 1
- 238000004080 punching Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 6
- 230000007547 defect Effects 0.000 abstract description 5
- 239000000178 monomer Substances 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 238000001816 cooling Methods 0.000 abstract description 2
- 238000007493 shaping process Methods 0.000 abstract description 2
- 239000002585 base Substances 0.000 description 26
- 238000000605 extraction Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229940043430 calcium compound Drugs 0.000 description 3
- 229920006260 polyaryletherketone Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- BREXUOXCEDKPCA-UHFFFAOYSA-N [Ca].OB(O)O Chemical compound [Ca].OB(O)O BREXUOXCEDKPCA-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000306 component Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 2
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical group OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment 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
- 150000002466 imines Chemical class 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000010220 ion permeability Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- YTZKOQUCBOVLHL-UHFFFAOYSA-N p-methylisopropylbenzene Natural products CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1046—Mixtures of at least one polymer and at least one additive
- H01M8/1051—Non-ion-conducting additives, e.g. stabilisers, SiO2 or ZrO2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
- H01M8/106—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties characterised by the chemical composition of the porous support
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M2008/1095—Fuel cells with polymeric electrolytes
-
- 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
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Composite Materials (AREA)
- Fuel Cell (AREA)
Abstract
The present invention proposes a kind of the glass base fuel battery proton exchange membrane and preparation method of high-temperature stable,By fluorite powder,Boracic raw material,Aluminum-containing raw material,Prodan powder and manganese dioxide put into glass furnace and are melted after mixing,Then the glass metal of melting is drained to glass fiber net and forms film,Pass through the prefabricated micropore glass of laser after cooling and shaping,Fixed network is provided for sulfonated polyether-ether-ketone,The process of polyimides is formed by sulfonation silica by monomer polymerization simultaneously,Sulfonation kaolin is fixed in micropore glass,It is prepared and is protected by polyimides,The glass base fuel battery proton exchange membrane of the fixed high-temperature stable of micropore glass,The present invention provides the above method and overcomes the defect that existing sulfonated polyether-ether-ketone is easily swollen breakage for proton exchange membrane under high temperature operating conditions,So that the water-retaining property of proton exchange membrane,Proton-conducting and mechanical strength improve,It is suitble to steady operation at a high temperature of 150-200 DEG C.
Description
Technical field
The present invention relates to fuel cell material fields, and in particular to a kind of glass base fuel battery proton friendship of high-temperature stable
Change film and preparation method.
Background technology
Due to non-renewable for traditional fossil fuel, and environmental pollution caused by during use is serious, seeks ring
The renewable sources of energy of guarantor's type are the severe tasks of 21 century facing mankind.Fuel cell (Fuel cell) is a kind of novel energy
Source technology directly converts the chemical energy of fuel to electric energy by electrochemical reaction, and fuel used is hydrogen, methanol and hydrocarbon
The hydrogen-rich materials such as class, there are no pollution to the environment and with high energy efficiency and high power density, therefore, fuel cell has
Have broad application prospects.
Proton Exchange Membrane Fuel Cells (Proton Exchange Membrane Fuel Cell, PEMFC)) it is after alkali
Property fuel cell (AFC), phosphoric acid fuel cell (PAFC), molten carbonate fuel cell (MCFC) and solid oxide fuel electricity
Pond (SOFC) and the 5th Replacing fuel battery to grow up have energy conversion rate using polymeric membrane as solid electrolyte
The features such as high and low temperature starts, electroless matter is revealed, is widely used in light-duty vehicle, portable power and small drive device.
PEMFC is mainly made of components such as end plate, bipolar plates and membrane electrodes.Membrane electrode is the core component of PEMFC, main
It to be made of gas diffusion layers, Catalytic Layer and proton exchange membrane.Proton exchange membrane (PEM) is Proton Exchange Membrane Fuel Cells
Critical component directly affects battery performance and service life.Currently, common proton exchange membrane is perfluoro sulfonic acid membrane, but by temperature
It is affected, when high temperature can reduce the energy conversion efficiency of battery.In order to overcome these disadvantages, various countries researcher to have been devoted to
Research and develop Novel polymer proton exchange membrane.Polyether-ether-ketone (PEEK) is a kind of special engineering plastics haveing excellent performance, with it
His special engineering plastics, which are compared, has more significant advantages, 260 DEG C of resistance to positive high temperature, fusing point be up to 334 DEG C of mechanical performances it is excellent, from
Lubricity is good, chemicals-resistant burn into is fire-retardant, peel resistance, wearability, intolerant to strong nitric acid, the concentrated sulfuric acid, radioresistance, superpower machine
It is scientific and technological that tool performance can be used for high-end machinery, nuclear engineering and aviation etc..Polyether-ether-ketone after sulfonation modifying not only maintains original
Excellent mechanical property, heat resistance and chemical resistance also improves the hydrophily and ion exchange capacity of polymer, improves
Its ion permeability and vapor separating effect, make it have broad application prospects in terms of fuel cell and membrane separation technique,
But the defects of sulfonated polyether-ether-ketone easily causes membrane swelling in hot operation for proton exchange membrane, embrittlement, influences service life.
Chinese invention patent 200910198236.X discloses binary doped modified sulfonated poly-ether-ether-ketone (SPEEK) proton exchange membrane (PEM)
And preparation method thereof, the composition and mass percent of the proton exchange membrane are：Sulfonation degree is the sulfonated polyether-ether-ketone of 40%-80%
80%-99%, binary doped solid 1%-20%, the binary doped solid are cerium oxide or yttrium oxide and phosphotungstic acid,
Middle cerium oxide or yttrium oxide and phosphotungstic acid molar ratio are 1: (1-3).Although program composite membrane has preferable comprehensive performance,
But the use of thulium increases battery production cost burden.
Chinese invention patent number 201110232366.8 discloses a kind of organic-inorganic ternary hybrid sulfonated poly aryl ether ketone matter
Proton exchange and preparation method thereof forms new network structure, and and sulfonation by the addition of POSS and sulfonated polyimide
The network of poly(aryl ether ketone) carries out interpenetrating, prepares the organic-inorganic ternary hybrid proton exchange membrane of water stability, although prepare
Proton exchange membrane can keep the proton conductivity of matrix while have good water stability, but the high-temperature stable of the structure
Property is poor, influences battery performance.
It is therefore proposed that a kind of fuel battery proton exchange film stablized in high temperature operating conditions lower structure, overcomes existing sulphur
Change polyether-ether-ketone and be easily swollen damaged defect under high temperature operating conditions for proton exchange membrane, to pushing novel polymeric substance
Proton exchange development is of great significance.
Invention content
Easily it is swollen the defect of breakage under high temperature operating conditions for proton exchange membrane for existing sulfonated polyether-ether-ketone,
The present invention proposes a kind of the glass base fuel battery proton exchange membrane and preparation method of high-temperature stable so that the guarantor of proton exchange membrane
Aqueous, proton-conducting and mechanical strength improve, and are suitble to steady operation at a high temperature of 150-200 DEG C.
To solve the above problems, the present invention uses following technical scheme：
A kind of glass base fuel battery proton exchange membrane of high-temperature stable, the structure of the proton exchange membrane are：Internal layer is adopted
Use micropore glass as microcellular structure network bracket, fill sulfonation proton transport material in network hole, the micropore glass with
Infiltration filling sulfonated polyether-ether-ketone resin, outer layer surrounding are wrapped up using Kapton between the sulfonation proton transport material
The structure of protection.
Preferably, the raw material of the micropore glass be fluorite powder, boracic raw material, aluminum-containing raw material, prodan powder and
Manganese dioxide powder, wherein the mixing of one or more of the boracic raw material boromagnesite, line borate, colemanite,
Aluminum-containing raw material is the mixing of one or more of aluminium oxide, calcium aluminate, alumina silicate, calcium aluminosilicate.
Preferably, it is 1 that the sulfonation proton transport material, which is mass ratio,:The sulfonation silica of 0.5-1.5 and sulfonation are high
Ridge soil.
Preferably, the preparation method of the glass base fuel battery proton exchange membrane of a kind of high-temperature stable, specially：
（1）By 8-13 mass parts fluorites powder, 4-9 mass parts boracics raw material, 8-10 mass parts aluminum-containing raw material, 65-80 matter
Amount part prodan powder and 0.1-2 mass parts manganese dioxide put into glass furnace after mixing, the temperature in glass furnace
It is 800-950 DEG C, is melted, the glass metal of melting, which is drained to glass fiber net, forms film, and the thickness for controlling glass film is
0.1-3 mm are cooled to room temperature sizing, obtain glass film presoma；
（2）The glass film presoma after sizing is punched using laser scanning again, it is 200-700 microns micro- to form aperture
Hole glass film material skeleton；
（3）Sulfonated polyether-ether-ketone resin is dissolved in organic solvent, the sulfonated polyether-ether-ketone sulfonation degree is 50-
85%, until completely dissolved, sulfonation proton transport material is added, it is evenly dispersed after high-speed stirred, obtain composite proton exchange it is viscous
Magma；
（4）Composite proton exchange viscous fluid is coated uniformly on following table on the micropore glass thin-film material skeleton
Face waits for that the composite proton exchanges viscous fluid and is sufficiently submerged in after micropore glass, and under the lower pressure of 8-20Pa, extraction is organic
Solvent, solidification obtain cured film；
（5）Molten diamines and dianhydride are soaked in the cured film upper and lower surface, 40-50 DEG C is heated to and obtains being protected by polyimides
Layer forms the fixed glass base fuel battery proton exchange membrane of micropore glass.
Preferably, the laser power of the laser boring is 100-600W, and laser facula is 120-500 microns, pitch of holes
It is 0.1-0.3 millimeters.
Preferably, the organic solvent is acetone and N, N- dimethylacetylamides, N, N- dimethylformamides, diformazan
The mixed solution of base sulfoxide or tetrahydrofuran composition, wherein acetone and N, N- dimethylacetylamides, N, N- dimethylformamides,
The molar ratio of dimethyl sulfoxide (DMSO) or tetrahydrofuran is 10:0.1-0.5.
Preferably, the molar ratio of the diamines and dianhydride is 1:1.
Preferably, the diamines is that bis- (the 3- aminopropans alkyl) tetramethyl disiloxanes of diamines, 1,3-, 1,3- are bis- by 1,6-
(4- amino-benzene oxygens methane) -1,1,3,3- tetramethyl disiloxanes, 3,4'- diaminodiphenyl ethers, 4,4'- diamino hexichol
Ether, 4,4' diaminodiphenyl sulfone, 1,4- are bis-（4- amino-benzene oxygens）It is bis- [(4- amino-benzene oxygens) phenyl] propane of benzene, 2,2-, double
[4- (4- phenoxy groups) phenyl] sulfone, 3,3'- dimethyl -4,4'- diaminodiphenylmethane, 1.4- are bis-（4- amino-benzene oxygens）-2-
Tert-butyl benzene, 1.4- are bis-（4-nitrophenoxy）One kind in -2- tert-butyl benzenes.
Preferably, the dianhydride is PMDA pyromellitic acid dianhydrides, 3,3', 4,4'- biphenyltetracarboxylic dianhydride, 3,3', 4,4'-
Benzophenone tetracarboxylic dianhydride, 3,3', bis- [4- (the 3,4- dicarboxyls phenoxy group) phenyl] propane of 4,4'- diphenyl ether tetracid dianhydrides, 2,2'-
One kind in bis- (bis- carboxy phenyls of 3,4-) the hexafluoropropane tetracid dianhydrides of tetracid dianhydride, 2,2'-.
Existing sulfonated polyether-ether-ketone is for proton exchange membrane easily by the damaged defect of swelling, this hair under high temperature operating conditions
It is bright to propose a kind of the glass base fuel battery proton exchange membrane and preparation method of high-temperature stable, by fluorite powder, boracic raw material, contain
Aluminum feedstock, prodan powder and manganese dioxide put into glass furnace and are melted after mixing, then by the glass of melting
Liquid is drained to glass fiber net and forms film, utilizes laser scanning pore-creating after cooling and shaping, forms micropore glass film；Using organic solvent
Sulfonated polyether-ether-ketone resin is dissolved, is uniformly dispersed with sulfonation silica, sulfonation kaolin, is sufficiently submerged in micropore glass, is arranged
Solvent solidifies, and obtains cured film, then will soak molten diamines and dianhydride in solidification film surface, and heating obtains being protected by polyimides,
The glass base fuel battery proton exchange membrane of the fixed high-temperature stable of micropore glass.The present invention by the prefabricated micropore glass of laser,
There is provided fixed network for sulfonated polyether-ether-ketone, at the same by monomer polymerization formed the process of polyimides by sulfonation silica,
Sulfonation kaolin is fixed in micropore glass so that water-retaining property, proton-conducting and the mechanical strength of proton exchange membrane improve, and fit
Close steady operation at a high temperature of 150-200 DEG C.
A kind of glass base fuel battery proton exchange membrane of high-temperature stable prepared by the present invention and existing pure sulfonated polyether
Ether ketone proton exchange membrane efficiency has apparent excellent in the water-retaining property of proton exchange membrane, proton-conducting and mechanical strength etc.
Gesture, as shown in table 1.
Table 1：
The present invention provides a kind of the glass base fuel battery proton exchange membrane and preparation method of high-temperature stable, with the prior art
It compares, the feature and excellent effect protruded is：
1, the present invention proposes a kind of the glass base fuel battery proton exchange membrane and preparation method of high-temperature stable, passes through laser
Prefabricated micropore glass provides fixed network for sulfonated polyether-ether-ketone, while will by the process of monomer polymerization formation polyimides
Sulfonation silica, sulfonation kaolin are fixed in micropore glass, and preparation of the invention goes out the friendship of glass base fuel battery proton
Change film compared with pure sulfonated poly aryl ether ketone, the water-retaining property of proton exchange membrane, proton-conducting and mechanical strength improve, and are suitble to
Steady operation at a high temperature of 150-200 DEG C.
2, the glass base fuel battery proton exchange membrane of high-temperature stable proposed by the present invention can extensively be answered as membrane material
For in fuel cell field.
3, the method for the present invention is simple, and the glass base fuel battery proton exchange film properties prepared are stablized, and are easy to be produced
Industryization develops.
Specific implementation mode
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
（1）By 8 mass parts fluorite powders, 9 mass parts boromagnesites, 8 mass parts aluminium oxide, 65 mass parts prodan powders
Glass furnace is put into after mixing with 0.1 mass parts manganese dioxide, and the temperature in glass furnace is 950 DEG C, is melted, will
The glass metal of melting is drained to glass fiber net and forms film, and the thickness for controlling glass film is 3 mm, is cooled to room temperature sizing, obtains
Glass film presoma；
（2）The glass film presoma after sizing is punched using laser scanning again, laser power 600W, laser facula
It it is 120 microns, pitch of holes is 0.1 millimeter, and it is 700 micrometer Millipore glass film material skeletons to form aperture；
（3）The sulfonated polyether-ether-ketone resin that sulfonation degree is 50% is dissolved in acetone and N, N- dimethylacetylamides composition
Mixed solution, wherein acetone and N, N- dimethylacetylamide molar ratios are 10:0.1, until completely dissolved, mass ratio is added
It is 1:0.5 sulfonation silica and sulfonation kaolin, it is evenly dispersed after high-speed stirred, it obtains composite proton and exchanges viscous fluid；
（4）Composite proton exchange viscous fluid is coated uniformly on following table on the micropore glass thin-film material skeleton
Face waits for that the composite proton exchanges viscous fluid and is sufficiently submerged in after micropore glass, and under the lower pressure of 20Pa, extraction is organic molten
Agent, solidification obtain cured film；
（5）Soaking molten 1,6- in the cured film upper and lower surface, diamines and 3,3', 4,4'- biphenyltetracarboxylic dianhydride have been heated to
40 DEG C of glass base fuel battery proton exchange membrane for obtaining high-temperature stable, proton exchange membrane are that internal layer uses micropore glass as micro-
Pore structure network bracket, network hole is interior to fill sulfonation proton transport material, the micropore glass and the sulfonation proton transport
Infiltration filling sulfonated polyether-ether-ketone resin between material, the structure that outer layer surrounding is protected using Kapton package.
The glass base fuel battery proton exchange membrane of the high-temperature stable prepared in the present embodiment is subjected to proton exchange membrane
Water-retaining property, proton-conducting and mechanical strength etc. are tested, and test result is as shown in table 2.
Embodiment 2
（1）By 12 mass parts fluorite powders, 5 mass parts boromagnesites and boric acid calcium compound, 9 mass parts calcium aluminates, 80 matter
Amount part prodan powder and 2 mass parts manganese dioxide put into glass furnace after mixing, and the temperature in glass furnace is 860
DEG C, it is melted, the glass metal of melting, which is drained to glass fiber net, forms film, and the thickness for controlling glass film is 0.7 mm, cold
But it shapes to room temperature, obtains glass film presoma；
（2）The glass film presoma after sizing is punched using laser scanning again, laser power 400W, laser facula
It it is 170 microns, pitch of holes is 0.2 millimeter, and it is 260 micrometer Millipore glass film material skeletons to form aperture；
（3）The sulfonated polyether-ether-ketone resin that sulfonation degree is 85% is dissolved in acetone and N, N- dimethylformamides composition
Mixed solution, the molar ratio of wherein acetone and N, N- dimethylformamides is 10:0.5, until completely dissolved, quality is added
Than being 1:1.5 sulfonation silica and sulfonation kaolin, it is evenly dispersed after high-speed stirred, obtain composite proton exchange it is sticky
Liquid；
（4）Composite proton exchange viscous fluid is coated uniformly on following table on the micropore glass thin-film material skeleton
Face waits for that the composite proton exchanges viscous fluid and is sufficiently submerged in after micropore glass, and under the lower pressure of 15Pa, extraction is organic molten
Agent, solidification obtain cured film；
（5）Bis- (the 3- aminopropans alkyl) tetramethyl disiloxanes of molten 1,3- and 3,3' are soaked in the cured film upper and lower surface,
4,4'- benzophenone tetracarboxylic dianhydrides, are heated to 42 DEG C of glass base fuel battery proton exchange membrane for obtaining high-temperature stable, and proton is handed over
It is that internal layer uses micropore glass as microcellular structure network bracket to change film, and network hole is interior to fill sulfonation proton transport material, institute
It states infiltration filling sulfonated polyether-ether-ketone resin, outer layer surrounding between micropore glass and the sulfonation proton transport material and uses polyamides
The structure of imines film package protection.
The glass base fuel battery proton exchange membrane of the high-temperature stable prepared in the present embodiment is subjected to proton exchange membrane
Water-retaining property, proton-conducting and mechanical strength etc. are tested, and test result is as shown in table 2.
Embodiment 3
（1）By 13 mass parts fluorite powders, 4 mass parts boromagnesites, line borate, colemanite, 8 mass parts aluminium oxide, aluminium
Sour calcium, alumina silicate, calcium aluminosilicate, 72 mass parts prodan powders and 1 mass parts manganese dioxide put into glass after mixing
Kiln, the temperature in glass furnace is 880 DEG C, is melted, and the glass metal of melting, which is drained to glass fiber net, forms film, control
The thickness of glass film is 1.8 mm, is cooled to room temperature sizing, obtains glass film presoma；
（2）The glass film presoma after sizing is punched using laser scanning again, laser power 560W, laser facula
It it is 450 microns, pitch of holes is 0.25 millimeter, and it is 650 micrometer Millipore glass film material skeletons to form aperture；
（3）It is molten that the sulfonated polyether-ether-ketone resin that sulfonation degree is 73% is dissolved in the mixing that acetone and tetrahydrofuran form
The molar ratio of liquid, wherein acetone and tetrahydrofuran is 10:0.35, until completely dissolved, it is 1 that mass ratio, which is added,:0.9 sulfonation two
Silica and sulfonation kaolin, it is evenly dispersed after high-speed stirred, it obtains composite proton and exchanges viscous fluid；
（4）Composite proton exchange viscous fluid is coated uniformly on following table on the micropore glass thin-film material skeleton
Face waits for that the composite proton exchanges viscous fluid and is sufficiently submerged in after micropore glass, and under the lower pressure of 14Pa, extraction is organic molten
Agent, solidification obtain cured film；
（5）It is bis- with 2,2'- that molten 3,3'- dimethyl -4,4'- diaminodiphenylmethane is soaked in the cured film upper and lower surface
[4- (3,4- dicarboxyl phenoxy group) phenyl] propane tetracid dianhydride, is heated to 47 DEG C of glass base fuel battery matter for obtaining high-temperature stable
Proton exchange, proton exchange membrane are that internal layer uses micropore glass as microcellular structure network bracket, and network hole is interior to fill sulfonation
Proton transport material, infiltration filling sulfonated polyether-ether-ketone resin between the micropore glass and the sulfonation proton transport material,
The structure that outer layer surrounding is protected using Kapton package.
The glass base fuel battery proton exchange membrane of the high-temperature stable prepared in the present embodiment is subjected to proton exchange membrane
Water-retaining property, proton-conducting and mechanical strength etc. are tested, and test result is as shown in table 2.
Embodiment 4
（1）By 10 mass parts fluorite powders, 6 mass parts boromagnesites, line borate and colemanite mixture, 9 mass parts oxygen
Change aluminium and aluminic acid calcium compound, 69 mass parts prodan powders and 0.8 mass parts manganese dioxide put into glass after mixing
Kiln, the temperature in glass furnace is 900 DEG C, is melted, and the glass metal of melting, which is drained to glass fiber net, forms film, control
The thickness of glass film is 1.5 mm, is cooled to room temperature sizing, obtains glass film presoma；
（2）The glass film presoma after sizing is punched using laser scanning again, laser power 200W, laser facula
It it is 350 microns, pitch of holes is 0.25 millimeter, and it is 450 micrometer Millipore glass film material skeletons to form aperture；
（3）The sulfonated polyether-ether-ketone resin that sulfonation degree is 75% is dissolved in acetone and N, N- dimethylacetylamides composition
Mixed solution, wherein acetone and N, N- dimethylacetylamide molar ratios are 10:0.35, until completely dissolved, mass ratio is added
It is 1:1.3 sulfonation silica and sulfonation kaolin, it is evenly dispersed after high-speed stirred, it obtains composite proton and exchanges viscous fluid；
（4）Composite proton exchange viscous fluid is coated uniformly on following table on the micropore glass thin-film material skeleton
Face waits for that the composite proton exchanges viscous fluid and is sufficiently submerged in after micropore glass, and under the lower pressure of 18Pa, extraction is organic molten
Agent, solidification obtain cured film；
（5）Molten 4,4' diaminodiphenyl sulfone and 2,2'- bis- (bis- carboxy phenyls of 3,4-) are soaked in the cured film upper and lower surface
Hexafluoropropane tetracid dianhydride is heated to 47 DEG C of glass base fuel battery proton exchange membrane for obtaining high-temperature stable, proton exchange membrane
For internal layer using micropore glass as microcellular structure network bracket, the interior filling sulfonation proton transport material of network hole is described micro-
Infiltration filling sulfonated polyether-ether-ketone resin, outer layer surrounding use polyimides between hole glass and the sulfonation proton transport material
The structure of film package protection.
The glass base fuel battery proton exchange membrane of the high-temperature stable prepared in the present embodiment is subjected to proton exchange membrane
Water-retaining property, proton-conducting and mechanical strength etc. are tested, and test result is as shown in table 2.
Embodiment 5
（1）By 13 mass parts fluorite powders, 4 mass parts colemanite, 10 mass parts alumina silicate, 80 mass parts prodans
Powder and 2 mass parts manganese dioxide put into glass furnace after mixing, and the temperature in glass furnace is 800 DEG C, is melted,
The glass metal of melting is drained to glass fiber net and forms film, the thickness for controlling glass film is 0.1 mm, is cooled to room temperature sizing,
Obtain glass film presoma；
（2）The glass film presoma after sizing is punched using laser scanning again, laser power 100W, laser facula
It it is 500 microns, pitch of holes is 0.3 millimeter, and it is 200 micrometer Millipore glass film material skeletons to form aperture；
（3）It is molten that the sulfonated polyether-ether-ketone resin that sulfonation degree is 75% is dissolved in the mixing that acetone and dimethyl sulfoxide (DMSO) form
Liquid, wherein acetone are 10 with dimethyl sulfoxide (DMSO) molar ratio:0.3, until completely dissolved, it is 1 that mass ratio, which is added,:1.2 sulfonation two
Silica and sulfonation kaolin, it is evenly dispersed after high-speed stirred, it obtains composite proton and exchanges viscous fluid；
（4）Composite proton exchange viscous fluid is coated uniformly on following table on the micropore glass thin-film material skeleton
Face waits for that the composite proton exchanges viscous fluid and is sufficiently submerged in after micropore glass, and under the lower pressure of 12Pa, extraction is organic molten
Agent, solidification obtain cured film；
（5）Bis- (the 3- aminopropans alkyl) tetramethyl disiloxanes of molten 1,3- and PMDA are soaked in the cured film upper and lower surface
Pyromellitic acid dianhydride is heated to 48 DEG C of glass base fuel battery proton exchange membrane for obtaining high-temperature stable, and proton exchange membrane is interior
For layer using micropore glass as microcellular structure network bracket, network hole is interior to fill sulfonation proton transport material, the micropore glass
Infiltration filling sulfonated polyether-ether-ketone resin, outer layer surrounding use Kapton between glass and the sulfonation proton transport material
Wrap up the structure of protection.
The glass base fuel battery proton exchange membrane of the high-temperature stable prepared in the present embodiment is subjected to proton exchange membrane
Water-retaining property, proton-conducting and mechanical strength etc. are tested, and test result is as shown in table 2.
Comparative example 1
Pure sulfonated poly-ether-ether-ketone (SPEEK) proton exchange membrane (PEM).
Comparative example 2
（1）By 12 mass parts fluorite powders, 5 mass parts boromagnesites and boric acid calcium compound, 9 mass parts calcium aluminates, 80 matter
Amount part prodan powder and 2 mass parts manganese dioxide put into glass furnace after mixing, and the temperature in glass furnace is 860
DEG C, it is melted, the glass metal of melting, which is drained to glass fiber net, forms film, and the thickness for controlling glass film is 0.7 mm, cold
But it shapes to room temperature, obtains glass film presoma；
（2）The glass film presoma after sizing is punched using laser scanning again, laser power 400W, laser facula
It it is 170 microns, pitch of holes is 0.2 millimeter, and it is 260 micrometer Millipore glass film material skeletons to form aperture；
（3）The sulfonated polyether-ether-ketone resin that sulfonation degree is 85% is dissolved in acetone and N, N- dimethylformamides composition
Mixed solution, the molar ratio of wherein acetone and N, N- dimethylformamides is 10:0.5, until completely dissolved, quality is added
Than being 1:1.5 sulfonation silica and sulfonation kaolin, it is evenly dispersed after high-speed stirred, obtain composite proton exchange it is sticky
Liquid；
（4）Composite proton exchange viscous fluid is coated uniformly on following table on the micropore glass thin-film material skeleton
Face waits for that the composite proton exchanges viscous fluid and is sufficiently submerged in after micropore glass, and under the lower pressure of 15Pa, extraction is organic molten
Agent, obtains the glass base fuel battery proton exchange membrane of high-temperature stable after solidification is dry, proton exchange membrane is using micropore glass
As microcellular structure network bracket, sulfonation proton transport material, the micropore glass and the sulfonation matter are filled in network hole
Infiltration filling sulfonated polyether-ether-ketone resin between sub- transmission material.
The fuel battery proton exchange film prepared in this example is carried out to water-retaining property, proton-conducting and the machine of proton exchange membrane
Tool intensity etc. is tested, and test result is as shown in table 2.
Table 2
Claims (7)
1. a kind of glass base fuel battery proton exchange membrane of high-temperature stable, which is characterized in that the structure of the proton exchange membrane
For：For internal layer using micropore glass as microcellular structure network bracket, the interior filling sulfonation proton transport material of network hole is described micro-
Infiltration filling sulfonated polyether-ether-ketone resin, outer layer surrounding use polyimides between hole glass and the sulfonation proton transport material
The structure of film package protection；
The raw material of the micropore glass is fluorite powder, boracic raw material, aluminum-containing raw material, prodan powder and manganese dioxide powder
Body, wherein the mixing of one or more of the boracic raw material boromagnesite, line borate, colemanite, aluminum-containing raw material are
The mixing of one or more of aluminium oxide, calcium aluminate, alumina silicate, calcium aluminosilicate；The sulfonation proton transport material is
Mass ratio is 1:The sulfonation silica and sulfonation kaolin of 0.5-1.5.
2. a kind of preparation method of the glass base fuel battery proton exchange membrane of high-temperature stable described in claim 1, specific to make
Preparation Method is：
（1）By 8-13 mass parts fluorites powder, 4-9 mass parts boracics raw material, 8-10 mass parts aluminum-containing raw material, 65-80 mass parts
Prodan powder and 0.1-2 mass parts manganese dioxide put into glass furnace after mixing, and the temperature in glass furnace is
It 800-950 DEG C, is melted, the glass metal of melting, which is drained to glass fiber net, forms film, and the thickness for controlling glass film is
0.1-3 mm are cooled to room temperature sizing, obtain glass film presoma；
（2）The glass film presoma after sizing is punched using laser scanning again, it is 200-700 micrometer Millipore glass to form aperture
Glass thin-film material skeleton；
（3）Sulfonated polyether-ether-ketone resin is dissolved in organic solvent, the sulfonated polyether-ether-ketone sulfonation degree is 50-85%, is waited for
After being completely dissolved, sulfonation proton transport material is added, it is evenly dispersed after high-speed stirred, it obtains composite proton and exchanges viscous fluid；
（4）Composite proton exchange viscous fluid is coated uniformly on the micropore glass thin-film material skeleton upper and lower surface, is waited for
The composite proton exchanges viscous fluid and is sufficiently submerged in after micropore glass, under the lower pressure of 8-20Pa, extracts organic solvent out,
Solidification obtains cured film；
（5）Molten diamines and dianhydride are soaked in the cured film upper and lower surface, 40-50 DEG C is heated to and obtains by polyimide covercoat,
Form the fixed glass base fuel battery proton exchange membrane of micropore glass.
3. a kind of preparation method of the glass base fuel battery proton exchange membrane of high-temperature stable according to claim 2,
It is characterized in that, the laser power of the laser scanning punching is 100-600W, and laser facula is 120-500 microns, and pitch of holes is
0.1-0.3 millimeters.
4. a kind of preparation method of the glass base fuel battery proton exchange membrane of high-temperature stable according to claim 2,
It is characterized in that, the organic solvent is acetone and N, N- dimethylacetylamides, N, N- dimethylformamides, dimethyl sulfoxide (DMSO)
Or the mixed solution of tetrahydrofuran composition, wherein acetone and N, N- dimethylacetylamides, N, N- dimethylformamides, dimethyl
The molar ratio of sulfoxide or tetrahydrofuran is 10:0.1-0.5.
5. a kind of preparation method of the glass base fuel battery proton exchange membrane of high-temperature stable according to claim 2,
It is characterized in that, the molar ratio of the diamines and dianhydride is 1:1.
6. a kind of preparation method of the glass base fuel battery proton exchange membrane of high-temperature stable according to claim 2,
It is characterized in that, the diamines is 1,6- bis- (the 3- aminopropans alkyl) tetramethyl disiloxanes of diamines, 1,3-, bis- (the 4- ammonia of 1,3-
Phenoxyl methane) -1,1,3,3- tetramethyl disiloxanes, 3,4'- diaminodiphenyl ethers, 4,4'- diaminodiphenyl ethers, 4,
4'- diaminodiphenylsulfones, 1,4- are bis-（4- amino-benzene oxygens）Bis- [(4- amino-benzene oxygens) phenyl] propane of benzene, 2,2-, bis- [4-
(4- phenoxy groups) phenyl] sulfone, 3,3'- dimethyl -4,4'- diaminodiphenylmethane, 1.4- be bis-（4- amino-benzene oxygens）- 2- uncles
Butyl benzene, 1.4- are bis-（4-nitrophenoxy）One kind in -2- tert-butyl benzenes.
7. a kind of preparation method of the glass base fuel battery proton exchange membrane of high-temperature stable according to claim 2,
It is characterized in that, the dianhydride is PMDA pyromellitic acid dianhydrides, 3,3', 4,4'- biphenyltetracarboxylic dianhydride, 3,3', 4,4'- hexichol first
Ketone tetracid dianhydride, 3,3', bis- [4- (3,4- dicarboxyls phenoxy group) phenyl] the propane tetracids two of 4,4'- diphenyl ether tetracid dianhydrides, 2,2'-
One kind in bis- (bis- carboxy phenyls of 3,4-) the hexafluoropropane tetracid dianhydrides of acid anhydride, 2,2'-.
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