CN110492124B - High-conductivity hydrophobic gas diffusion layer and preparation method thereof - Google Patents
High-conductivity hydrophobic gas diffusion layer and preparation method thereof Download PDFInfo
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- CN110492124B CN110492124B CN201910644075.6A CN201910644075A CN110492124B CN 110492124 B CN110492124 B CN 110492124B CN 201910644075 A CN201910644075 A CN 201910644075A CN 110492124 B CN110492124 B CN 110492124B
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- modified graphene
- hydrophobic
- diffusion layer
- gas diffusion
- graphene
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- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 98
- 238000009792 diffusion process Methods 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 184
- 239000000758 substrate Substances 0.000 claims abstract description 51
- 239000000446 fuel Substances 0.000 claims abstract description 46
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 37
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 36
- 239000002131 composite material Substances 0.000 claims abstract description 24
- 238000000576 coating method Methods 0.000 claims abstract description 18
- 239000011248 coating agent Substances 0.000 claims abstract description 17
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 14
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 14
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims description 59
- 239000006185 dispersion Substances 0.000 claims description 43
- 239000002002 slurry Substances 0.000 claims description 40
- 238000001035 drying Methods 0.000 claims description 38
- 239000007788 liquid Substances 0.000 claims description 35
- 229910052799 carbon Inorganic materials 0.000 claims description 31
- 239000011230 binding agent Substances 0.000 claims description 30
- 239000007787 solid Substances 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 13
- 229920000642 polymer Polymers 0.000 claims description 13
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 12
- 239000002033 PVDF binder Substances 0.000 claims description 12
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 9
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- 238000007598 dipping method Methods 0.000 claims description 7
- 229920001600 hydrophobic polymer Polymers 0.000 claims description 7
- 150000002894 organic compounds Chemical class 0.000 claims description 7
- 239000004744 fabric Substances 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 6
- 238000007765 extrusion coating Methods 0.000 claims description 5
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 claims description 4
- JPZYXGPCHFZBHO-UHFFFAOYSA-N 1-aminopentadecane Chemical compound CCCCCCCCCCCCCCCN JPZYXGPCHFZBHO-UHFFFAOYSA-N 0.000 claims description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- 229920002367 Polyisobutene Polymers 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 4
- PLZVEHJLHYMBBY-UHFFFAOYSA-N Tetradecylamine Chemical compound CCCCCCCCCCCCCCN PLZVEHJLHYMBBY-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 claims description 4
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 4
- 239000000839 emulsion Substances 0.000 claims description 4
- KAJZYANLDWUIES-UHFFFAOYSA-N heptadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCN KAJZYANLDWUIES-UHFFFAOYSA-N 0.000 claims description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 4
- BUHXFUSLEBPCEB-UHFFFAOYSA-N icosan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCCCN BUHXFUSLEBPCEB-UHFFFAOYSA-N 0.000 claims description 4
- INAMEDPXUAWNKL-UHFFFAOYSA-N nonadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCCN INAMEDPXUAWNKL-UHFFFAOYSA-N 0.000 claims description 4
- 229920000734 polysilsesquioxane polymer Polymers 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- ABVVEAHYODGCLZ-UHFFFAOYSA-N tridecan-1-amine Chemical compound CCCCCCCCCCCCCN ABVVEAHYODGCLZ-UHFFFAOYSA-N 0.000 claims description 4
- QFKMMXYLAPZKIB-UHFFFAOYSA-N undecan-1-amine Chemical compound CCCCCCCCCCCN QFKMMXYLAPZKIB-UHFFFAOYSA-N 0.000 claims description 4
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 claims description 3
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 claims description 3
- 239000004005 microsphere Substances 0.000 claims description 3
- FJDUDHYHRVPMJZ-UHFFFAOYSA-N nonan-1-amine Chemical compound CCCCCCCCCN FJDUDHYHRVPMJZ-UHFFFAOYSA-N 0.000 claims description 3
- ALXIFCUEJWCQQL-UHFFFAOYSA-N nonan-2-amine Chemical compound CCCCCCCC(C)N ALXIFCUEJWCQQL-UHFFFAOYSA-N 0.000 claims description 3
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 claims description 3
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- NHBKWZCTSMCKDS-UHFFFAOYSA-N undecan-2-amine Chemical compound CCCCCCCCCC(C)N NHBKWZCTSMCKDS-UHFFFAOYSA-N 0.000 claims description 3
- KLNPWTHGTVSSEU-UHFFFAOYSA-N undecane-1,11-diamine Chemical compound NCCCCCCCCCCCN KLNPWTHGTVSSEU-UHFFFAOYSA-N 0.000 claims description 3
- HFACYWDPMNWMIW-UHFFFAOYSA-N 2-cyclohexylethanamine Chemical compound NCCC1CCCCC1 HFACYWDPMNWMIW-UHFFFAOYSA-N 0.000 claims description 2
- UKPLRVAKKXWITN-UHFFFAOYSA-N 2-cyclopentylethanamine Chemical compound NCCC1CCCC1 UKPLRVAKKXWITN-UHFFFAOYSA-N 0.000 claims description 2
- LTHNHFOGQMKPOV-UHFFFAOYSA-N 2-ethylhexan-1-amine Chemical compound CCCCC(CC)CN LTHNHFOGQMKPOV-UHFFFAOYSA-N 0.000 claims description 2
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 claims description 2
- WGTASENVNYJZBK-UHFFFAOYSA-N 3,4,5-trimethoxyamphetamine Chemical compound COC1=CC(CC(C)N)=CC(OC)=C1OC WGTASENVNYJZBK-UHFFFAOYSA-N 0.000 claims description 2
- LYUQWQRTDLVQGA-UHFFFAOYSA-N 3-phenylpropylamine Chemical compound NCCCC1=CC=CC=C1 LYUQWQRTDLVQGA-UHFFFAOYSA-N 0.000 claims description 2
- VKJXAQYPOTYDLO-UHFFFAOYSA-N 4-methylphenethylamine Chemical compound CC1=CC=C(CCN)C=C1 VKJXAQYPOTYDLO-UHFFFAOYSA-N 0.000 claims description 2
- LPULCTXGGDJCTO-UHFFFAOYSA-N 6-methylheptan-1-amine Chemical compound CC(C)CCCCCN LPULCTXGGDJCTO-UHFFFAOYSA-N 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- WJYIASZWHGOTOU-UHFFFAOYSA-N Heptylamine Chemical compound CCCCCCCN WJYIASZWHGOTOU-UHFFFAOYSA-N 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 238000010041 electrostatic spinning Methods 0.000 claims description 2
- PWSKHLMYTZNYKO-UHFFFAOYSA-N heptane-1,7-diamine Chemical compound NCCCCCCCN PWSKHLMYTZNYKO-UHFFFAOYSA-N 0.000 claims description 2
- KYCGURZGBKFEQB-UHFFFAOYSA-N n',n'-dibutylpropane-1,3-diamine Chemical compound CCCCN(CCCC)CCCN KYCGURZGBKFEQB-UHFFFAOYSA-N 0.000 claims description 2
- ZQEQANWXEQSAGL-UHFFFAOYSA-N n',n'-dimethylpentane-1,5-diamine Chemical compound CN(C)CCCCCN ZQEQANWXEQSAGL-UHFFFAOYSA-N 0.000 claims description 2
- HBXNJMZWGSCKPW-UHFFFAOYSA-N octan-2-amine Chemical compound CCCCCCC(C)N HBXNJMZWGSCKPW-UHFFFAOYSA-N 0.000 claims description 2
- QNIVIMYXGGFTAK-UHFFFAOYSA-N octodrine Chemical compound CC(C)CCCC(C)N QNIVIMYXGGFTAK-UHFFFAOYSA-N 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 238000004528 spin coating Methods 0.000 claims description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
- 150000004992 toluidines Chemical class 0.000 claims description 2
- 238000010023 transfer printing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 13
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 230000003993 interaction Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 45
- 238000012360 testing method Methods 0.000 description 17
- 239000012528 membrane Substances 0.000 description 15
- 238000002791 soaking Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 11
- 239000004205 dimethyl polysiloxane Substances 0.000 description 11
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 11
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 10
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 10
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 10
- 238000001132 ultrasonic dispersion Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 241000872198 Serjania polyphylla Species 0.000 description 5
- 239000006258 conductive agent Substances 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000004812 Fluorinated ethylene propylene Substances 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920009441 perflouroethylene propylene Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000004890 Hydrophobing Agent Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000006255 coating slurry Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- ROALYYYPAOVYRD-UHFFFAOYSA-N heptadecan-7-amine Chemical compound CCCCCCCCCCC(N)CCCCCC ROALYYYPAOVYRD-UHFFFAOYSA-N 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- ZDOUPNFGGBDMBJ-UHFFFAOYSA-N octadecan-8-amine Chemical compound CCCCCCCCCCC(N)CCCCCCC ZDOUPNFGGBDMBJ-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003075 superhydrophobic effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 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
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0234—Carbonaceous material
-
- 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
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0241—Composites
- H01M8/0245—Composites in the form of layered or coated products
-
- 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
- H01M8/02—Details
- H01M8/0289—Means for holding the electrolyte
-
- 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)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Inert Electrodes (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to the field of fuel cells, in particular to a high-conductivity hydrophobic gas diffusion layer and a preparation method thereof. The gas diffusion layer is composed of a porous conductive substrate layer treated by hydrophobic modified graphene and a hydrophobic modified graphene/carbon material composite microporous layer coated on one side of the porous conductive substrate layer. By utilizing the high specific surface area of the graphene and the strong interaction between the graphene and the carbon material, the graphene can be tightly combined with the carbon material while coating the conductive substrate and the conductive carbon material, so that the contact resistance is reduced. In addition, the conductivity of the hydrophobically modified graphene is much higher than that of polytetrafluoroethylene, and the use of the hydrophobically modified graphene as a hydrophobic agent further improves the conductivity of the diffusion layer. The invention can obtain the high-conductivity hydrophobic gas diffusion layer, and the preparation process does not need high-temperature treatment, thereby having the characteristics of low energy consumption and environmental protection and having stronger practicability.
Description
Technical Field
The present invention relates to the field of fuel cells, and more particularly to gas diffusion layers in fuel cell critical materials.
Technical Field
The fuel cell is a power generation device which can directly convert chemical energy of fuels such as hydrogen, methanol, ethanol and the like into electric energy, and has the characteristics of high energy conversion efficiency, clean products and the like. The fuel cell stack is formed by stacking a plurality of single fuel cells. The monolithic fuel cell is composed of a membrane electrode in the middle and a bipolar plate sandwiching the membrane electrode. A plurality of monolithic cell stacks are assembled together to form a fuel cell stack. The membrane electrode comprises a proton exchange membrane, a catalyst layer and a gas diffusion layer from the middle to two sides in sequence. The gas diffusion layer plays multiple roles of bearing the pressure stress of the bipolar plate, protecting the catalyst layer, promoting the gas to be uniformly diffused to the catalyst layer, discharging water vapor, conducting current and the like in the membrane electrode, and is one of key components influencing the electrode performance of the fuel cell.
The gas diffusion layer is composed of a support layer made of porous conductive materials such as porous carbon paper, carbon cloth, foamed metal and the like and a microporous layer formed by coating carbon black and graphite powder. Since water is generated at the cathode during operation of the fuel cell, the catalytic layer may be flooded if the water is not discharged in time, thereby reducing the performance of the fuel cell. The hydrophobic surface does not readily adsorb water, enabling water to be rapidly drained, and therefore, a hydrophobic treatment of the porous support layer and the microporous layer is required.
The common practice in the prior art for preparing gas diffusion layers is: soaking carbon paper or carbon cloth in a hydrophobing agent solution with a certain concentration for a period of time, taking out, naturally dripping, airing, slowly drying in an oven, and finally treating at 350 ℃; conductive carbon black, carbon powder and the like are uniformly mixed with a hydrophobic agent in a solvent, then the mixture is coated on a support layer subjected to hydrophobic treatment through processes of spraying, blade coating, screen printing and the like, the mixture is dried and then treated at high temperature for a certain time, and finally, a hydrophobic gas diffusion layer is obtained, see fuel cells compiled by Mao Zong Keng.
The Chinese patent application No. 200610047931.2 (a gas diffusion layer for fuel cells and preparation thereof) mixes acetylene black and a hydrophobic agent, coats the mixture on hydrophobic carbon paper or carbon cloth, heats the mixture at 150-280 ℃, and then burns the mixture for 10-100 min at 300-400 ℃ to obtain the hydrophobic gas diffusion layer, wherein the amount of the hydrophobic agent reaches 10-30%.
The Chinese patent application No. 201810493251.6 (a durable super-hydrophobic gas diffusion layer for fuel cells) mixes a conductive agent, hydrophobic microspheres and a binder in parts by weight of 3-4:1-2:10-15 respectively, then coats the mixture on hydrophobic treated carbon paper, and introduces protective gas at 380 ℃ of 270 ℃ for firing treatment for 20-30min to obtain the hydrophobic treated gas diffusion layer. The method described in this patent improves the surface smoothness and flatness of the microporous layer.
Conventionally, a hydrophobic agent is generally a fluoropolymer such as Polytetrafluoroethylene (PTFE), vinylidene fluoride (PVDF), or Fluorinated Ethylene Propylene (FEP), or a polymer material having hydrophobicity such as polymethylsiloxane. Since these hydrophobicizers are not conductive per se (electrical conductivity)<10-14S/cm), the use of these hydrophobizing agents may reduce the electrical conductivity of the gas diffusion layer.
The graphene is formed by sp carbon atoms2The hybrid tracks form a hexagonal honeycomb-lattice two-dimensional structure material, has high specific surface area, high thermal and electrical conductivity, electrochemical corrosion resistance and excellent mechanical properties, and can be applied to electrode materials of supercapacitors and lithium ion batteries and the like. For example, in order to improve the conductivity of a gas diffusion layer, chinese utility model patent CN207558942U (a gas diffusion layer carbon paper of a proton exchange membrane fuel cell) mixes graphene and PTFE as a microporous layer coating slurry to reduce the contact resistance between the microporous layer and the carbon paper, but the amount of graphene used reaches 60% to 80%, which increases the application cost.
The graphene oxide has rich functional groups, so that the graphene oxide is favorable for the dispersion of the graphene oxide in an organic solvent and a polymer, and simultaneously provides a large number of modification sites, and can be modified according to needs, so that the graphene oxide has higher compatibility in the polymer, and the application of the graphene oxide in a polymer material is expanded. The introduction of graphene or modified graphene can obviously improve the conductivity of the material, for example, the solution blending method is reported to prepare graphene or Graphene Oxide (GO) and a polymer to prepare a conductive high molecular material. The SBS/rGO conductive composite material is prepared by mixing GO with an SBS solution and reducing GO with hydrazine hydrate, see: li H, Wu S, Wu J, et al, enhanced electrical continuity and mechanical property of SBS/graphene nanocomposite, Journal of Polymer Research,2014,21(5) 1-8; liu Y-T, Xie X-M, Ye X-Y.high-concentration organic solutions of poly (styrene-co-butadiene-co-styrene) modified graphene sheets from graphite, Carbon,2011,49(11): 3529-37. Modifying GO with octadecylamine, then mixing with a PP/SEBS composite system in a solution mode, and enabling graphene to be self-assembled in the composite material by a hot pressing forming method to form the anisotropic conductive composite material of PP/SEBS/GO, wherein the steps are as follows: mao C, Huang J, Zhu Y, et al, Tailored Parallel graphics strings in a Plastic Film with a reduced analytical by Shear-Induced Self-Assembly [ J ]. The Journal of Physical Chemistry Letters,2013,4(1): 43-7.
Graphene itself has hydrophilicity, and it is also reported in the literature that it is subjected to hydrophobic modification. PDMS with functionalized double ends, one end of which is grafted to the edge of GO with a water contact angle of 129.5 degrees, see Lei W.W., Li H., Shi L.Y., et al. Ultrahydrophobic materials with oxidized GO modified with octadecylamine to a contact angle of 162 ° are described in shanmughaj a.m., Yoon j.h., Yang w.j., Ryu s.h.synthesis, chromatography, and surface soil properties of aminated graphene oxide ms with modified amine chain length hs.j Colloid Interface Sci,401,148 (2013).
Although the preparation method of the hydrophobically modified graphene as described above is disclosed in the prior art, no application in a gas diffusion layer of a fuel cell is found, and the report of the preparation method of the gas diffusion layer from the hydrophobically modified graphene-coated carbon material is also not disclosed in the prior art.
The use of non-conductive hydrophobic polymers for gas diffusion layers of the prior art reduces the conductivity of the gas diffusion layer; in the preparation process of the microporous layer, the interaction between the carbon-based conductive agent and the macromolecular hydrophobic agent is weaker, so that the carbon-based conductive agent and the macromolecular hydrophobic agent are dispersed unevenly to form aggregates, and the hydrophobic uniformity is reduced; in addition, high-temperature treatment is also needed in the preparation process, so that the energy consumption is increased.
The applicant has found that by utilizing the high specific surface area of graphene and the strong interaction between graphene and carbon materials, the graphene can tightly wrap carbon paper fibers or carbon-based conductive agent particles, so that the amount of a binder can be reduced and high-temperature treatment is not required. In addition, conductivity of hydrophobically modified graphene: (>10-6S/cm) is significantly higher than PTFE ((R)<10-14S/cm), and the like. Therefore, the hydrophobically modified graphene as a hydrophobizing agent may not onlyThe electrical conductivity of the gas diffusion layer is improved, and the preparation process is carried out at low temperature, so that more energy is saved.
Disclosure of Invention
It is an object of the present invention to provide a highly conductive hydrophobic gas diffusion layer, especially a microporous layer in a diffusion layer, which has high electrical conductivity as well as hydrophobicity.
The invention also aims to provide a method for preparing the high-conductivity hydrophobic gas diffusion layer, which has the characteristics of simple preparation process, energy conservation and environmental protection.
It is another object of the present invention to provide a fuel cell using the highly conductive hydrophobic gas diffusion layer of the present invention.
In order to achieve the above object, the present invention adopts the following technical solutions.
One technical scheme is to provide a high-conductivity hydrophobic gas diffusion layer for a fuel cell, which comprises a porous conductive substrate subjected to hydrophobic treatment by modified graphene and a microporous layer constructed by the modified graphene/carbon material, wherein the microporous layer is uniformly coated on one side of the porous conductive substrate.
In one embodiment, the highly conductive hydrophobic gas diffusion layer for a fuel cell is composed of a porous conductive substrate subjected to hydrophobic treatment by modified graphene together with a microporous layer constructed of a modified graphene/carbon material, the microporous layer being uniformly coated on one side of the porous conductive substrate layer.
In one embodiment, the hydrophobization modified graphene of the present invention is prepared by using graphene oxide and a compound containing-NH2The products of the reaction of organic compounds of the radicals, either commercially available or prepared by self-modification with graphene oxide, e.g. by reacting compounds containing-NH2And mixing the primary amine organic matter/ethanol solution of the group with the graphene oxide/water dispersion, and reacting at 80-90 ℃ for 6-12 h to obtain an aminated modified graphene product. Modification methods are known in the art and are described in: li W, Tang X, Zhang H, et al, Simultaneous surface function and reduction of a graphene oxide with an aliphatic derivative for electrically conductive polystyrene compositions, carbon 2011,49(14): 4724-.
Said group containing-NH2The organic compound of the group is selected from one or more of the following compounds: n-heptylamine, 2-cyclopentylethylamine, 2-aminooctane, 2-amino-6-methylheptane, 1-amino-6-methylheptane, 2-ethylhexylamine, 2-cyclohexylethylamine, n-hexylamine, octylamine, 2-aminononane, n-nonylamine, 1-decylamine, n-undecylamine, 2-aminoundecane, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, nonadecylamine, eicosylamine, aniline, toluidine, phenethylamine, p-methylphenethylamine, 3-phenylpropylamine, ethylenediamine, 2-methyl-1, 5-diaminopentane, 1, 6-hexamethylenediamine, 1, 7-heptamethylenediamine, 1, 8-octamethyleneamine, 1, 9-nonanediamine, 1, 10-decanediamine, 1, 11-diaminoundecane, 1, 12-diaminododecane, 1, 16-diaminohexa-alkane, 5- (dimethylamino) pentylamine, 3- (dibutylamino) propylamine.
Preference is given to one or more of n-hexylamine, octylamine, 2-aminononane, n-nonylamine, 1-decylamine, n-undecylamine, 2-aminoundecane, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, nonadecylamine, eicosylamine, 1, 7-heptadecylamine, 1, 8-octadecylamine, 1, 9-nonanediamine, 1, 10-decanediamine, 1, 11-diaminoundecane, 1, 12-diaminododecane, 1, 16-diaminohexaalkane, more preferably one or more of dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, nonadecylamine, eicosylamine, 1, 12-diaminododecane, 1, 16-diaminohexaalkane.
It should be understood that the NH groups containing compounds that may be used in the present invention2The organic compounds of the groups are not limited to the organic compounds listed above, and the skilled person will be able to select other suitable-NH-containing compounds as the case may be2Organic compounds of the group without going beyond the scope of protection of the present invention.
Optionally containing-NH2The organic compound of the group accounts for 20% to 55%, preferably 30% to 50%, more preferably 35% to 45%, still more preferably 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44% of the modified graphene by mass.
In one embodiment, the hydrophobically modified graphene is characterized by: the hydrophobically modified graphene is a product of graphene oxide grafted hydrophobic polymer, and can be prepared by the following method: the GO/water dispersion is slowly dripped into the solution of the polymer containing the amino functional group. The method comprises the following steps of violently stirring and reacting for 0.5-12 hours at 80-150 ℃, precipitating a reacted mixture in ethanol, carrying out suction filtration, and repeatedly washing with a solvent to obtain a black product, namely the graphene grafted polymer, wherein the grafting method is a disclosed prior art and is as follows: ZHao-Hua Mo, ZHEN.Luo, Qiang Huang, Jian Ping.Deng, Yi-Xian Wu Superhydrophic hybrids by grafting arc-like macromolecular hybrids in the hierarchy of photos, Synthesis, characterization and Properties, applied Surf Sci 2018,440,359 and 368.
The hydrophobic polymer is one or more of polymethylsiloxane containing amino functional groups, cage-type polysilsesquioxane, polyisobutylene, polystyrene, polytetrafluoroethylene and polyvinylidene fluoride, the polymethylsiloxane containing amino functional groups, the cage-type polysilsesquioxane, the polyisobutylene and the polystyrene are preferred, and the polymethylsiloxane, the cage-type polysilsesquioxane and the polyisobutylene containing amino functional groups are more preferred.
It is to be understood that the hydrophobic polymers that can be used in the present invention are not limited to those listed above, and that one skilled in the art will be able to select other suitable hydrophobic polymers as the case may be without departing from the scope of the present invention.
The weight of the polymer grafted on the hydrophobically modified graphene accounts for 40-95%, preferably 50-90%, more preferably 60-90%, still more preferably 70-80%, or 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79% of the weight of the hydrophobically modified graphene.
The polymerization degree of the polymer is 15-100, preferably 15-70, more preferably 20-50, and still more preferably 30-40, or 31, 32, 33, 34, 35, 36, 37, 38, 39.
The area of the single graphene of the hydrophobic modified graphene is 1 mu m2～40μm2Preferably 2 μm2～25μm2More preferably 4 μm2～15μm2More preferably 6 μm2-10μm2。
The conductive carbon material is one or a mixture of more of conductive carbon black, activated carbon, carbon microspheres, carbon whiskers, graphite powder, acetylene black or carbon fibers.
It is to be understood that the conductive carbon materials that can be used in the present invention are not limited to those listed above, and those skilled in the art can select other suitable conductive carbon materials according to specific situations without departing from the scope of the present invention.
The particle diameter of the conductive agent particles is 0.01-2.6 μm, preferably 0.05-1.3 μm, more preferably 0.3-0.7 μm, and still more preferably 0.4-0.6 μm.
The porous conductive substrate material is one of carbon paper, carbon cloth and carbon felt. It is understood that one skilled in the art can select other suitable substrate materials for a particular situation without departing from the scope of the present invention.
In another aspect of the present invention, there is provided a method for preparing a highly conductive and hydrophobic gas diffusion layer for a fuel cell, comprising: the method comprises the following steps:
(1) firstly, adding hydrophobically modified graphene into ethanol or isopropanol, and stirring and ultrasonically treating to obtain a hydrophobically modified graphene dispersion liquid with the concentration of 0.1-3.0 mg/mL, preferably 0.3-2.5 mg/mL, more preferably 0.5-2 mg/mL;
(2) dipping a porous conductive substrate material into the dispersion liquid obtained in the step (1), carrying out ultrasonic treatment for a period of time, taking out and drying the porous conductive substrate material, dipping the porous conductive substrate material into the dispersion liquid again, repeating the dipping-drying process for 2-5 times, and finally drying the porous conductive substrate material to obtain the hydrophobic modified graphene-coated porous conductive substrate material;
(3) slowly adding a conductive carbon material into the hydrophobic modified graphene dispersion liquid (1) which is fully dispersed, continuously stirring and then ultrasonically dispersing, slowly dropwise adding a binder and fully stirring to obtain hydrophobic modified graphene/conductive carbon material composite slurry;
(4) and (3) coating the slurry on one side of the hydrophobic modified graphene-coated porous conductive substrate material in the step (2), and then drying in a vacuum oven at the temperature of 60-80 ℃.
The porous conductive substrate material is selected from carbon paper, carbon cloth, carbon felt, and it is understood that one skilled in the art can select other suitable substrate materials as the case may be without departing from the scope of the present invention.
The solid content in the hydrophobically modified graphene/conductive carbon material composite slurry is 1-40%, preferably 2-30%, and more preferably 3-25%; the hydrophobic modified graphene material accounts for 1-10%, preferably 2-8% and more preferably 4-6% of the total solid content; the amount of the binder is 0.1 to 5%, preferably 0.3 to 3%, and more preferably 0.5 to 2% of the total solid content.
The binder is polyvinylidene fluoride (PVDF) or Styrene Butadiene Rubber (SBR) emulsion, and it is understood that one skilled in the art can select other suitable binders as the case may be without departing from the scope of the present invention.
The coating is selected from one of spray coating, blade coating, spin coating, slit extrusion coating, electrostatic spinning or transfer printing, and the like, and those skilled in the art can select other suitable coating modes according to specific situations without departing from the protection scope of the present invention.
Still another aspect of the present invention is to provide a fuel cell using the above-mentioned highly conductive hydrophobic gas diffusion layer or the highly conductive hydrophobic gas diffusion layer prepared by the above-mentioned method.
The scope of use of the present invention is not limited to any fuel cell. Currently, there are 5 known fuel cell types, the names of which relate to the respective electrolytes employed.
(1) Alkaline Fuel Cell (AFC) -using potassium hydroxide solution as the electrolyte;
(2) proton Exchange Membrane Fuel Cell (PEMFC) -using a very thin polymer electrolyte membrane as its electrolyte;
(3) phosphoric Acid Fuel Cell (PAFC) -phosphoric acid at high temperature of 200 ℃ is used as its electrolyte;
(4) molten Carbonate Fuel Cell (MCFC) -molten sodium or potassium carbonate is used as the electrolyte;
(5) solid Oxygen Fuel Cell (SOFC) -a solid electrolyte is used.
Has the advantages that:
compared with the prior art, the invention has the outstanding characteristics and excellent effects that:
(1) the electrical conductivity of the gas diffusion layer is improved by using the porous conductive carbon material and the microporous layer treated by the hydrophobically modified graphene;
(2) the gas diffusion layer and the preparation method thereof can avoid the high-temperature treatment process of the gas diffusion layer and reduce the energy consumption in the preparation process;
the specific implementation mode is as follows:
the present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention. The following materials were used in the examples described below, unless otherwise indicated.
Infrared (FT-IR) testing using Nicolet corporation, Nexsus 6700-FT-IR, ATR, scan range: 4000cm-1～400cm-1。
The thermogravimetric test adopts a nitrogen atmosphere of Q50 of American TA company and the temperature rise rate is from 25 ℃ to 600 ℃ at 10 ℃/min.
Water contact angle test: the surface of the film was tested with a contact angle system OCA (dataphysics) meter at a droplet size of 5. mu.L, and the average value was taken 5 times for each sample.
And (3) testing the membrane electrode performance: polarization curves and AC impedance tests were performed using the scriber 890e Fuel Cell Test Loads, USA.
The preparation method of the invention is basically as follows:
a method for preparing a highly conductive hydrophobic gas diffusion layer for a fuel cell, characterized in that: the method comprises the following steps:
(1) firstly, adding hydrophobically modified graphene into ethanol or isopropanol, and stirring and ultrasonically treating to obtain a hydrophobically modified graphene dispersion liquid with the concentration of 0.1-3.0 mg/mL;
(2) dipping a porous conductive substrate material into the dispersion liquid obtained in the step (1), carrying out ultrasonic treatment for a period of time, taking out and drying the porous conductive substrate material, dipping the porous conductive substrate material into the dispersion liquid again, repeating the dipping-drying process for 2-5 times, and finally drying the porous conductive substrate material to obtain the hydrophobic modified graphene-coated porous conductive substrate material;
(3) slowly adding a conductive carbon material into the hydrophobic modified graphene dispersion liquid subjected to the full dispersion in the step (1), continuously stirring, then carrying out ultrasonic dispersion, slowly dropwise adding a binder, and fully stirring to obtain hydrophobic modified graphene/conductive carbon material composite slurry;
(4) and (3) coating the slurry on one side of the hydrophobic modified graphene-coated porous conductive substrate material in the step (2), and then drying in a vacuum oven at the temperature of 60-80 ℃.
Example 1:
(1) preparing hydrophobic modified graphene: 0.2g of graphene oxide (average area 15 μm) was dispersed in 100mL of water by ultrasonic dispersion to prepare a graphene oxide/water dispersion having a concentration of 2 mg/mL. 0.3g of octadecylamine was dissolved in 30mL of ethanol to prepare a 10mg/mL solution of octadecylamine in ethanol. Adding the octadecylamine/ethanol solution into the graphene oxide/water dispersion, and stirring and refluxing for 12h at 95 ℃. And (3) performing suction filtration, washing filter residues in ethanol, and drying in a vacuum drying oven for 24 hours to obtain 0.27g of octadecylamine modified graphene oxide (GO-ODA), wherein the content of octadecylamine is 46% by TGA test. 20mg of GO-ODA is dispersed in 20mL of isopropanol, and the concentration of the dispersion liquid is 1.0 mg/mL.
(2) Soaking a porous conductive substrate material into the dispersion liquid, performing ultrasonic treatment for a period of time, taking out and drying, soaking the porous conductive substrate material into the dispersion liquid again, repeating the soaking-drying process for 3 times, and finally drying to obtain a hydrophobic modified graphene-coated porous conductive substrate material;
(3) and (2) slowly adding conductive carbon black with the average particle size of 0.7 mu m into the hydrophobic modified graphene dispersion liquid obtained in the step (1), continuously stirring, then carrying out ultrasonic dispersion, then slowly dropping polyvinylidene fluoride (PVDF) as a binder, and fully stirring to obtain the hydrophobic modified graphene/conductive carbon material composite slurry. Adjusting the concentration of the slurry to ensure that the solid content in the hydrophobically modified graphene/conductive carbon material composite slurry is 5%, the hydrophobically modified graphene material accounts for 4% of the total solid content, and the binder accounts for 2% of the total solid content;
(4) spraying the slurry on one side of the hydrophobic modified graphene-coated porous conductive substrate material in the step (2). And then drying in a vacuum oven at 60 ℃ to obtain the high-conductivity hydrophobic gas diffusion layer.
The gas diffusion layer material prepared in the example of the invention was subjected to hydrophobicity, conductivity and fuel cell performance tests. The performance test of the fuel cell is to prepare a membrane-forming electrode by the gas diffusion layer, the catalyst and the proton exchange membrane obtained in the embodiment, and the specific method is as follows: adding a certain amount of Pt/C catalyst into a beaker, adding a small amount of water and isopropanol, stirring and dispersing, adding Nafion solution to obtain catalyst slurry with the concentration of 2%, and spraying the prepared catalyst slurry on a Nafion 212 membrane to ensure that the catalyst loading capacity of a cathode and the catalyst loading capacity of an anode of a proton exchange membrane are respectively 0.5mg/cm2And 0.1mg/cm2And hot-pressing the prepared gas diffusion layer and the membrane sprayed with the catalyst on a flat hot press at 135 ℃ for 2min to obtain the membrane electrode. The membrane electrode was placed in a fuel cell fixture and a single cell performance test was performed using a fuel cell test system, the test results being shown in table 1.
Example 2:
(1) the preparation of hydrophobically modified graphene was the same as in example 1, except that graphene oxide having an average area of 40 μm was used2The content of octadecylamine in GO-ODA is 20%, and the concentration of the dispersion liquid is 0.1 mg/mL.
(2) The same as in example 1, except that the number of impregnation was 5.
(3) Slowly adding graphite powder with the average particle size of 2.6 microns into the hydrophobic modified graphene dispersion liquid obtained in the step (1), continuously stirring, then carrying out ultrasonic dispersion, slowly dropping polyvinylidene fluoride (PVDF) as a binder, and fully stirring to obtain the hydrophobic modified graphene/conductive carbon material composite slurry. Adjusting the concentration of the slurry to enable the solid content in the hydrophobically modified graphene/conductive carbon material composite slurry to be 1%, the hydrophobically modified graphene material to account for 1% of the total solid content, and the binder to account for 5% of the total solid content;
(4) same as in example 1.
Hydrophobicity, conductivity, and fuel cell performance testing were the same as in example 1.
Example 3:
(1) the procedure for preparing hydrophobically modified graphene was the same as in example 1, except that graphene oxide having an average particle size of 10 μm was used2The content of octadecylamine in GO-ODA is 55%, and the concentration of the dispersion liquid is 3.0 mg/mL.
(2) The same as in example 1, except that the number of dipping was 3.
(3) And (2) slowly adding conductive carbon black with the average particle size of 0.3 mu m into the hydrophobic modified graphene dispersion liquid obtained in the step (1), continuously stirring, then carrying out ultrasonic dispersion, then slowly dropping polyvinylidene fluoride (PVDF) as a binder, and fully stirring to obtain the hydrophobic modified graphene/conductive carbon material composite slurry. Adjusting the concentration of the slurry to enable the solid content in the hydrophobically modified graphene/conductive carbon material composite slurry to be 15%, the hydrophobically modified graphene material to account for 5% of the total solid content, and the binder to account for 1% of the total solid content;
(4) and (3) coating the slurry on one side of the hydrophobic modified graphene-coated porous conductive substrate material in the step (2) by adopting a blade coating method. And then drying in a vacuum oven at 60 ℃ to obtain the high-conductivity hydrophobic gas diffusion layer.
Hydrophobicity, conductivity, and fuel cell performance testing were the same as in example 1.
Example 4:
(1) preparing hydrophobic modified graphene: the GO (average 25 μm area)/aqueous dispersion was slowly added dropwise to the amine functional PDMS (Polymer 15). The reaction was stirred vigorously at elevated temperature for a period of time. The final product is the GO-g-PDMS hybrid material. Precipitating the reacted mixture in ethanol, then carrying out suction filtration, ultrasonically dispersing in THF, and carrying out suction filtration. This ultrasonic dispersion-suction filtration process was repeated 5 times to sufficiently remove the unreacted PDMS. The product was dispersed in isopropanol and the dispersion was maintained at a concentration of 0.5 mg/mL. PDMS content 40% by TGA test;
(2) soaking a porous conductive substrate material into the dispersion liquid, performing ultrasonic treatment for a period of time, taking out and drying, soaking the porous conductive substrate material into the dispersion liquid again, repeating the soaking-drying process for 5 times, and finally drying to obtain a hydrophobic modified graphene-coated porous conductive substrate material;
(3) slowly adding graphite powder with the average particle size of 1.3 mu m into the hydrophobic modified graphene dispersion liquid obtained in the step (1), continuously stirring, then carrying out ultrasonic dispersion, slowly dropping polyvinylidene fluoride (PVDF) as a binder, and fully stirring to obtain the hydrophobic modified graphene/conductive carbon material composite slurry. Adjusting the concentration of the slurry to ensure that the solid content in the hydrophobically modified graphene/conductive carbon material composite slurry is 2%, the hydrophobically modified graphene material accounts for 2% of the total solid content, and the binder accounts for 3% of the total solid content;
(4) and (3) coating the slurry on one side of the hydrophobic modified graphene-coated porous conductive substrate material in the step (2) in a spraying manner. And then drying in a vacuum oven at 60 ℃ to obtain the high-conductivity hydrophobic gas diffusion layer.
Hydrophobicity, conductivity, and fuel cell performance testing were the same as in example 1.
Example 5:
(1) hydrophobically modified graphene was prepared by the same method as in example 4, except that the average area of GO was 10 μm2The polymer of the PDMS is 30 percent, the content of the PDMS is 70 percent, and the concentration of the dispersion liquid is still 0.5 mg/mL;
(2) soaking a porous conductive substrate material into the dispersion liquid, performing ultrasonic treatment for a period of time, taking out and drying, soaking the porous conductive substrate material into the dispersion liquid again, repeating the soaking-drying process for 4 times, and finally drying to obtain a hydrophobic modified graphene-coated porous conductive substrate material;
(3) and (2) slowly adding conductive carbon black with the average particle size of 0.1 mu m into the hydrophobic modified graphene dispersion liquid obtained in the step (1), continuously stirring, then carrying out ultrasonic dispersion, then slowly dropping polyvinylidene fluoride (PVDF) as a binder, and fully stirring to obtain the hydrophobic modified graphene/conductive carbon material composite slurry. Adjusting the concentration of the slurry to enable the solid content in the hydrophobically modified graphene/conductive carbon material composite slurry to be 25%, the hydrophobically modified graphene material to account for 6% of the total solid content, and the binder to account for 0.5% of the total solid content;
(4) and (3) coating the slurry on one side of the hydrophobic modified graphene-coated porous conductive substrate material in the step (2) in a blade coating mode. And then drying in a vacuum oven at 80 ℃ to obtain the high-conductivity hydrophobic gas diffusion layer.
Hydrophobicity, conductivity, and fuel cell performance testing were the same as in example 1.
Example 6:
(1) preparation method of hydrophobically modified graphene is the same as example 4, except that the average area of GO is 2 μm2The polymer of PDMS is 65 percent, the content of PDMS is 90 percent, and the concentration of the dispersion liquid is 1.0 mg/mL;
(2) soaking a porous conductive substrate material into the dispersion liquid, performing ultrasonic treatment for a period of time, taking out and drying, soaking the porous conductive substrate material into the dispersion liquid again, repeating the soaking-drying process for 3 times, and finally drying to obtain a hydrophobic modified graphene-coated porous conductive substrate material;
(3) and (2) slowly adding conductive carbon black with the average particle size of 0.05 mu m into the hydrophobic modified graphene dispersion liquid obtained in the step (1), continuously stirring, then carrying out ultrasonic dispersion, then slowly dropping polyvinylidene fluoride (PVDF) as a binder, and fully stirring to obtain the hydrophobic modified graphene/conductive carbon material composite slurry. Adjusting the concentration of the slurry to ensure that the solid content in the hydrophobically modified graphene/conductive carbon material composite slurry is 30%, the hydrophobically modified graphene material accounts for 8% of the total solid content, and the binder accounts for 0.3% of the total solid content;
(4) and (3) coating the slurry on one side of the hydrophobic modified graphene-coated porous conductive substrate material in the step (2) in a slit extrusion coating mode. And then drying in a vacuum oven at 80 ℃ to obtain the high-conductivity hydrophobic gas diffusion layer.
Hydrophobicity, conductivity, and fuel cell performance testing were the same as in example 1.
Example 7:
(1) hydrophobically modified graphene was prepared by the same method as in example 4, except that the average area of GO was 1 μm2The polymer of the PDMS is 100, the content of the PDMS is 95 percent, and the concentration of the dispersion liquid is 3.0 mg/mL;
(2) soaking a porous conductive substrate material into the dispersion liquid, performing ultrasonic treatment for a period of time, taking out and drying, soaking the porous conductive substrate material into the dispersion liquid again, repeating the soaking-drying process for 2 times, and finally drying to obtain a hydrophobic modified graphene-coated porous conductive substrate material;
(3) and (2) slowly adding conductive carbon black with the average particle size of 0.01 mu m into the hydrophobic modified graphene dispersion liquid obtained in the step (1), continuously stirring, then carrying out ultrasonic dispersion, then slowly dropping polyvinylidene fluoride (PVDF) as a binder, and fully stirring to obtain the hydrophobic modified graphene/conductive carbon material composite slurry. Adjusting the concentration of the slurry to ensure that the solid content in the hydrophobically modified graphene/conductive carbon material composite slurry is 40%, the hydrophobically modified graphene material accounts for 10% of the total solid content, and the binder accounts for 0.1% of the total solid content;
(4) and (3) coating the slurry on one side of the hydrophobic modified graphene-coated porous conductive substrate material in the step (2) in a slit extrusion coating mode. And then drying in a vacuum oven at 80 ℃ to obtain the high-conductivity hydrophobic gas diffusion layer.
Hydrophobicity, conductivity, and fuel cell performance testing were the same as in example 1.
Comparative example 1:
(1) soaking Toray TGP-H060 carbon paper into PTFE emulsion with the concentration of 10%, taking out and drying, soaking again and drying, and then annealing for 1H at 350 ℃ under the protection of argon to obtain hydrophobic carbon paper;
(2) adding 450mg of conductive carbon black (with the average particle size of 0.5 mu m) into 500mg of 10% PTFE emulsion, wherein the PTFE accounts for 10% of the solid content, adding a certain amount of isopropanol to ensure that the solid content of the slurry is 30%, and mechanically stirring and ultrasonically dispersing to ensure that the PTFE is uniformly dispersed in the carbon powder to prepare the slurry;
(3) and (2) coating the slurry on one side of the hydrophobic carbon paper (1) by means of slit extrusion coating. And then drying in a vacuum oven at 80 ℃, and annealing the dried gas diffusion layer for 1h under the protection of argon at 350 ℃ to obtain the gas diffusion layer.
Hydrophobicity, conductivity, and fuel cell performance testing were the same as in example 1.
TABLE 1
Remarking:*in the embodiment, the hydrophobic agent is hydrophobically modified graphene, and the binder is PVDF; in the comparative example, PTFE is a hydrophobic agent, and PTFE has cohesiveness and also serves as a binder
As can be seen from the table, the total amount of the hydrophobically modified graphene and the binder used in examples 1 to 6 is lower than that in comparative example 1, but the contact angle is higher than that in comparative example 1, that is, the hydrophobicity of PTFE as the hydrophobic agent and the binder can be achieved or exceeded by using less hydrophobically modified graphene and the binder; the conductivity of examples 1 to 6 was 2 times or more that of comparative example 1. Example 7 compares to comparative example 1 and shows that the hydrophobicity and conductivity of the present invention are higher than the comparative example even with similar hydrophobizing agents and binders. The hydrophobic gas diffusion layer with high conductivity can be prepared by the method.
Although the present invention has been described with reference to specific embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention.
Claims (9)
1. A highly conductive hydrophobic gas diffusion layer for a fuel cell, characterized in that: the conductive film comprises a porous conductive substrate subjected to hydrophobic treatment by modified graphene and a microporous layer constructed by the modified graphene/carbon material, wherein the microporous layer is uniformly coated on one side of the porous conductive substrate;
the hydrophobically modified graphene is prepared from graphene oxide and-NH-containing2The product of the reaction of an organic compound containing a group-NH 2 selected from the group consisting ofOne or more of: n-heptylamine, 2-cyclopentylethylamine, 2-aminooctane, 2-amino-6-methylheptane, 1-amino-6-methylheptane, 2-ethylhexylamine, 2-cyclohexylethylamine, n-hexylamine, octylamine, 2-aminononane, n-nonylamine, 1-decylamine, n-undecylamine, 2-aminoundecane, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, nonadecylamine, eicosylamine, aniline, toluidine, phenethylamine, p-methylphenethylamine, 3-phenylpropylamine, ethylenediamine, 2-methyl-1, 5-diaminopentane, 1, 6-hexamethylenediamine, 1, 7-heptamethylenediamine, 1, 8-octamethyleneamine, 1, 9-nonanediamine, 1, 10-decanediamine, 1, 11-diaminoundecane, 1, 12-diaminododecane, 1, 16-diaminohexaalkane, 5- (dimethylamino) pentylamine, 3- (dibutylamino) propylamine;
or the hydrophobic modified graphene is a product of graphene oxide grafted hydrophobic polymer, and the hydrophobic polymer is one or more of polymethylsiloxane, cage polysilsesquioxane, polyisobutylene, polystyrene, polytetrafluoroethylene and polyvinylidene fluoride.
2. The highly conductive hydrophobic gas diffusion layer according to claim 1, wherein: the mass of the organic compound containing the-NH 2 group accounts for 20-55% of that of the modified graphene.
3. The highly conductive hydrophobic gas diffusion layer according to claim 1, wherein: the polymer grafted on the hydrophobically modified graphene accounts for 40-95% of the weight of the hydrophobically modified graphene, and the polymerization degree of the polymer grafted on the graphene is 15-100.
4. The highly conductive hydrophobic gas diffusion layer according to claim 1, wherein: the area of the single-sheet graphene is 1 mu m2～40μm 2 。
5. The highly conductive hydrophobic gas diffusion layer according to claim 1, wherein: the conductive carbon material is one or a mixture of more of conductive carbon black, activated carbon, carbon microspheres, carbon whiskers, graphite powder, acetylene black or carbon fibers, and the particle size of the conductive carbon material is 0.01-2.60 mu m.
6. The highly conductive hydrophobic gas diffusion layer according to any one of claims 1 to 5, wherein: the porous conductive substrate material is one of carbon paper, carbon cloth and carbon felt.
7. A method for producing a highly conductive hydrophobic gas diffusion layer for a fuel cell according to any of claims 1 to 6, characterized in that: the method comprises the following steps:
(1) firstly, adding hydrophobically modified graphene into an organic solvent, and stirring and ultrasonically treating to obtain a hydrophobically modified graphene dispersion liquid with the concentration of 0.1-3.0 mg/mL;
(2) dipping a porous conductive substrate material into the dispersion liquid obtained in the step (1), performing ultrasonic treatment, taking out and drying, dipping the porous conductive substrate material into the dispersion liquid again, repeating the dipping-drying process for 2-5 times, and finally drying to obtain the hydrophobic modified graphene-coated porous conductive substrate material;
(3) slowly adding a conductive carbon material into the hydrophobic modified graphene dispersion liquid (1) which is fully dispersed, continuously stirring and then ultrasonically dispersing, slowly dropwise adding a binder and fully stirring to obtain hydrophobic modified graphene/conductive carbon material composite slurry;
(4) and (2) coating the slurry on one side of the hydrophobic modified graphene-coated porous conductive substrate material by one of spraying, blade coating, spin coating, slit extrusion coating, electrostatic spinning or transfer printing, and then drying in a vacuum oven at 60-80 ℃.
8. The method of claim 7, wherein: the organic solvent is ethanol or isopropanol, the solid content in the hydrophobically modified graphene/conductive carbon material composite slurry is 1-40%, the hydrophobically modified graphene material accounts for 1-10% of the total solid content, the binder accounts for 0.1-5% of the total solid content, and the binder is polyvinylidene fluoride (PVDF) or Styrene Butadiene Rubber (SBR) emulsion.
9. A fuel cell, characterized by: the fuel cell uses the highly conductive hydrophobic gas diffusion layer of any one of claims 1 to 6 or the highly conductive hydrophobic gas diffusion layer prepared by the method of any one of claims 7 to 8.
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| CN111900416A (en) * | 2020-07-31 | 2020-11-06 | 齐鲁工业大学 | Preparation method and application of carbon paper impregnating resin for fuel cell gas diffusion layer |
| CN113178583A (en) * | 2021-04-28 | 2021-07-27 | 上海电气集团股份有限公司 | Modified composite material applied to gas diffusion layer and preparation method and application thereof |
| CN113809336B (en) * | 2021-08-23 | 2023-10-24 | 安徽大学 | High-strength porous material compounded by carbon fibers and graphene and gas diffusion layer and preparation method thereof |
| CN113948715A (en) * | 2021-10-14 | 2022-01-18 | 一汽解放汽车有限公司 | Fuel cell gas diffusion layer and preparation method and application thereof |
| CN114256469A (en) * | 2021-12-10 | 2022-03-29 | 国家电投集团氢能科技发展有限公司 | Gas diffusion layer for fuel cell, preparation method thereof and fuel cell |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1227674A (en) * | 1996-06-25 | 1999-09-01 | 戴伊斯公司 | Gas diffusion electrode |
| CN102024961A (en) * | 2010-11-29 | 2011-04-20 | 新源动力股份有限公司 | Gaseous diffusion layer of proton exchange membrane fuel cell and preparation method thereof |
| CN104716333A (en) * | 2013-12-15 | 2015-06-17 | 中国科学院大连化学物理研究所 | Ordered gas diffusion electrode, and production method and application thereof |
| CN105664927A (en) * | 2015-12-30 | 2016-06-15 | 厦门大学 | Carbon-paper-supported high-index crystal face platinum nano particle catalyst, preparation method and application thereof |
| CN106876743A (en) * | 2017-03-16 | 2017-06-20 | 厦门大学 | A kind of fuel battery gas diffusion layer structure |
| CN107293765A (en) * | 2017-07-28 | 2017-10-24 | 韦德永 | A kind of fuel battery gas diffusion layer structure |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6399202B1 (en) * | 1999-10-12 | 2002-06-04 | Cabot Corporation | Modified carbon products useful in gas diffusion electrodes |
| KR100878548B1 (en) * | 2002-01-11 | 2009-01-14 | 미꾸니 시끼소 가부시키가이샤 | Carbonaceous material and dispersion containing the same |
| US6890680B2 (en) * | 2002-02-19 | 2005-05-10 | Mti Microfuel Cells Inc. | Modified diffusion layer for use in a fuel cell system |
| CN100423338C (en) * | 2005-10-10 | 2008-10-01 | 新源动力股份有限公司 | Gas diffusion layer for low temp fuel cell and preparing process thereof |
| KR100728181B1 (en) * | 2005-11-30 | 2007-06-13 | 삼성에스디아이 주식회사 | Membrane electrode assembly for fuel cell and fuel cell system comprising same |
| CN101140990A (en) * | 2006-09-08 | 2008-03-12 | 新源动力股份有限公司 | Application of electric pole gaseous diffusion layer in fuel batter with proton exchange film |
| CN100521328C (en) * | 2006-09-29 | 2009-07-29 | 中国科学院大连化学物理研究所 | Gas diffusion layer for fuel cell and its production |
| JP2010102934A (en) * | 2008-10-23 | 2010-05-06 | Toyota Motor Corp | Method for manufacturing gas diffusion layer for fuel cell |
| US9515340B1 (en) * | 2011-04-06 | 2016-12-06 | Sandia Corporation | Conductive polymer layers to limit transfer of fuel reactants to catalysts of fuel cells to reduce reactant crossover |
| DE102011083118A1 (en) * | 2011-09-21 | 2013-03-21 | Future Carbon Gmbh | Gas diffusion layer with improved electrical conductivity and gas permeability |
| CN109301263A (en) * | 2018-09-26 | 2019-02-01 | 成都新柯力化工科技有限公司 | A kind of durable fuel cell gas diffusion layers and preparation method |
| CN109742409A (en) * | 2018-11-30 | 2019-05-10 | 天能电池集团有限公司 | A kind of Hydrogen Proton exchange film fuel battery gas diffusion layers and preparation method thereof |
-
2019
- 2019-07-17 CN CN201910644075.6A patent/CN110492124B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1227674A (en) * | 1996-06-25 | 1999-09-01 | 戴伊斯公司 | Gas diffusion electrode |
| CN102024961A (en) * | 2010-11-29 | 2011-04-20 | 新源动力股份有限公司 | Gaseous diffusion layer of proton exchange membrane fuel cell and preparation method thereof |
| CN104716333A (en) * | 2013-12-15 | 2015-06-17 | 中国科学院大连化学物理研究所 | Ordered gas diffusion electrode, and production method and application thereof |
| CN105664927A (en) * | 2015-12-30 | 2016-06-15 | 厦门大学 | Carbon-paper-supported high-index crystal face platinum nano particle catalyst, preparation method and application thereof |
| CN106876743A (en) * | 2017-03-16 | 2017-06-20 | 厦门大学 | A kind of fuel battery gas diffusion layer structure |
| CN107293765A (en) * | 2017-07-28 | 2017-10-24 | 韦德永 | A kind of fuel battery gas diffusion layer structure |
Non-Patent Citations (1)
| Title |
|---|
| Synthesis，characterization ，and surface wettabilitiy properties of amine functionalized graphene oxide films with varying amine chain lengths;A.M. Shanmugharaj，et al.;《Journal of colloid and interface science》;20130404;全文 * |
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