CN114551950A - 包含自组装嵌段共聚物的用于膜-电极组件的电解质膜 - Google Patents
包含自组装嵌段共聚物的用于膜-电极组件的电解质膜 Download PDFInfo
- Publication number
- CN114551950A CN114551950A CN202111203511.XA CN202111203511A CN114551950A CN 114551950 A CN114551950 A CN 114551950A CN 202111203511 A CN202111203511 A CN 202111203511A CN 114551950 A CN114551950 A CN 114551950A
- Authority
- CN
- China
- Prior art keywords
- membrane
- electrode assembly
- electrolyte membrane
- formulae
- block copolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 60
- 239000003792 electrolyte Substances 0.000 title claims abstract description 53
- 229920001400 block copolymer Polymers 0.000 title claims abstract description 37
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 22
- 239000003963 antioxidant agent Substances 0.000 claims description 27
- 229920000554 ionomer Polymers 0.000 claims description 21
- 230000003078 antioxidant effect Effects 0.000 claims description 20
- 239000000446 fuel Substances 0.000 claims description 19
- 239000000654 additive Substances 0.000 claims description 15
- 230000000996 additive effect Effects 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 8
- 239000000693 micelle Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 125000002091 cationic group Chemical group 0.000 claims description 4
- 238000005868 electrolysis reaction Methods 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 7
- -1 hydroxyl radicals Chemical class 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 229920000557 Nafion® Polymers 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000033116 oxidation-reduction process Effects 0.000 description 4
- 239000005518 polymer electrolyte Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000002530 phenolic antioxidant Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 150000003839 salts Chemical group 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical group O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000002144 chemical decomposition reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- IBMCQJYLPXUOKM-UHFFFAOYSA-N 1,2,2,6,6-pentamethyl-3h-pyridine Chemical group CN1C(C)(C)CC=CC1(C)C IBMCQJYLPXUOKM-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- RPVFYIHRKXUWDA-UHFFFAOYSA-N 2,2,6,6-tetramethyl-1-(2,2,6,6-tetramethylpiperidin-1-yl)oxypiperidine Chemical compound CC1(C)CCCC(C)(C)N1ON1C(C)(C)CCCC1(C)C RPVFYIHRKXUWDA-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical group C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- NCQCBVSEIAGHCP-UHFFFAOYSA-N 3-(3-octacosoxy-3-oxopropyl)sulfanylpropanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)O NCQCBVSEIAGHCP-UHFFFAOYSA-N 0.000 description 1
- YNKQCPNHMVAWHN-UHFFFAOYSA-N 4-(benzenecarbonothioylsulfanyl)-4-cyanopentanoic acid Chemical compound OC(=O)CCC(C)(C#N)SC(=S)C1=CC=CC=C1 YNKQCPNHMVAWHN-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 1
- 239000003508 Dilauryl thiodipropionate Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical group O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical group [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 229910000420 cerium oxide Chemical group 0.000 description 1
- 229910000422 cerium(IV) oxide Chemical group 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000000914 diffusion-ordered spectroscopy Methods 0.000 description 1
- 235000019304 dilauryl thiodipropionate Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical group [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical compound FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Images
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
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
- H01M8/1006—Corrugated, curved or wave-shaped MEA
-
- 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
- H01M8/1044—Mixtures of polymers, of which at least one is ionically conductive
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60L—PROPULSION OF ELECTRICALLY-PROPELLED VEHICLES; SUPPLYING ELECTRIC POWER FOR AUXILIARY EQUIPMENT OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRODYNAMIC BRAKE SYSTEMS FOR VEHICLES IN GENERAL; MAGNETIC SUSPENSION OR LEVITATION FOR VEHICLES; MONITORING OPERATING VARIABLES OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRIC SAFETY DEVICES FOR ELECTRICALLY-PROPELLED VEHICLES
- B60L50/00—Electric propulsion with power supplied within the vehicle
- B60L50/50—Electric propulsion with power supplied within the vehicle using propulsion power supplied by batteries or fuel cells
- B60L50/70—Electric propulsion with power supplied within the vehicle using propulsion power supplied by batteries or fuel cells using power supplied by fuel cells
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
- C08F212/26—Nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
- C08F212/30—Sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
- C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/38—Esters containing sulfur
- C08F220/382—Esters containing sulfur and containing oxygen, e.g. 2-sulfoethyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B13/00—Diaphragms; Spacing elements
- C25B13/04—Diaphragms; Spacing elements characterised by the material
- C25B13/08—Diaphragms; Spacing elements characterised by the material based on organic materials
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
- C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded
-
- 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
-
- 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
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
-
- 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
-
- 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
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
-
- 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
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1034—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having phosphorus, e.g. sulfonated polyphosphazenes [S-PPh]
-
- 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
-
- 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
- H01M8/1048—Ion-conducting additives, e.g. ion-conducting particles, heteropolyacids, metal phosphate or polybenzimidazole with phosphoric acid
-
- 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
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
-
- 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
-
- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T90/00—Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02T90/40—Application of hydrogen technology to transportation, e.g. using fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Power Engineering (AREA)
- Transportation (AREA)
- Mechanical Engineering (AREA)
- Fuel Cell (AREA)
- Conductive Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
本发明涉及包含自组装嵌段共聚物的用于膜‑电极组件的电解质膜,所述自组装嵌段共聚物包含亲水域和疏水域。
Description
技术领域
本发明涉及一种包含嵌段共聚物的用于膜-电极组件的电解质膜,所述嵌段共聚物包含亲水域和疏水域。
背景技术
质子交换膜燃料电池(PEMFC)基本上包括阳极(氢气燃料)、阴极(向其供应氧气)和设置在两个电极之间的聚合物电解质膜,这种构造被称为膜-电极组件(MEA)。燃料电池产生电的反应为:将供应至阳极的氢气分离成质子和电子,然后质子通过膜朝向阴极移动,电子通过外电路向阴极移动,使得氧气分子、质子和电子在阴极上反应以产生电和热量,并产生作为反应副产物的水(H2O)。
此处,聚合物电解质膜用于将阳极产生的质子转移到阴极,并用作不使氢气(燃料)与氧气直接接触的隔膜。通常,由全氟磺酸离聚物(PFSA)组成的电解质膜由于在高质子电导率和各种润湿条件下具有高性能和高稳定性,因此是聚合物电解质膜燃料电池领域中最常用的电解质膜。然而,在纯全氟磺酸离聚物电解质膜中存在许多问题:在100℃或更高的温度下容易发生热降解,并且质子电导率也较低,从而迅速降低机械稳定性和尺寸稳定性等。为此,使用一般全氟磺酸离聚物电解质膜的燃料电池的操作通常仅在低于100℃,优选80℃或更低的范围内使用。此外,由于质子电导率取决于在水分存在的情况下通过磺酸供给剂(-SO3H基团)进行的质子交换,因此必须最佳地保持聚合物电解质膜的水合水平。
通常,空气中的氢气和氧气(燃料电池的反应气体)交叉通过电解质膜以促进过氧化氢(HOOH)的产生,其中过氧化氢产生高活性的含氧自由基,例如羟基自由基(·OH)和氢过氧自由基(·OOH)。自由基通过攻击全氟磺酸类电解质膜和电极中的离聚物而导致膜和电极的化学降解,从而最终产生降低燃料电池耐久性的不利影响。
通常,作为减缓化学降解的技术,已经提出了加入各种类型的抗氧化剂的方法。抗氧化剂可分别或可互换地使用具有自由基清除剂或猝灭剂功能的主抗氧化剂和仅具有过氧化氢分解剂功能的次抗氧化剂。在一般聚烯烃类塑料工业中,主抗氧化剂包括酚类抗氧化剂、单酚·双酚·聚合物酚类抗氧化剂和胺类抗氧化剂。作为次抗氧化剂(过氧化物分解剂),报道了硫类抗氧化剂和磷抗氧化剂。例如,由于聚丙烯比聚乙烯更容易氧化,因此已知的做法是组合使用聚丙烯与次抗氧化剂(例如,0.1%至1.0%的2,6-二叔丁基-4-甲基苯酚(BHT)的酚类抗氧化剂、硫代二丙酸二月桂酯和硫代二丙酸二十八醇酯)。
作为在用于燃料电池的全氟磺酸电解质膜和离聚物中使用的代表性主抗氧化剂,已知的是铈基团,例如六水合硝酸铈(III)或铈氧化物或二氧化铈。此外,作为次抗氧化剂,存在锰抗氧化剂(例如锰氧化物)和过渡金属催化剂(例如铂(Pt))。
然而,当使用金属盐形式作为主抗氧化剂或次抗氧化剂时,金属离子会键合到全氟磺酸离聚物的磺酸基的末端,从而阻塞质子可以移动通过的路径。此外,几十至几百纳米尺寸的金属或金属氧化物的颗粒会阻塞电解质膜的水合微通道,从而干扰质子的移动。因此,通常,金属盐或金属形式的抗氧化剂的使用提高了电解质膜的化学耐久性,但是相反地,可能降低电解质膜的质子电导率。
在相关技术中,通过使用标准氧化还原电势在0.68[V]至1.00[V]的范围内的有机氧化-还原化合物作为燃料电池中除了金属或金属盐之外的抗氧化剂来开发抗氧化剂。例如,具有氮氧自由基(N-O·)的TEMPO((2,2,6,6-四甲基哌啶-1-基)氧化物)是主次复合有机抗氧化剂,其用作能够将羟基自由基转化为氢氧根(OH-)(如以下反应式1所示)的主抗氧化剂,并用作次抗氧化剂(过氧化氢分解剂)(如以下反应式2所示)。
[反应式1]
[反应式2]
然而,其缺点在于分子量较低的有机氧化-还原化合物在燃料电池操作的过程中未固定到电解质膜上,因此可能易于通过水合通道而被扩散和洗脱。
本背景技术部分中公开的上述信息仅用于增强对本发明的背景技术的理解,因此,其可以包含不构成在本国已为本领域技术人员所公知的现有技术的信息。
发明内容
在一个优选的方面中,提供了一种能够保持电解质膜的性能并改善其耐久性的添加剂。
在另一个优选的方面中,提供了一种能够同时改善电解质膜的质子电导率和抗氧化性的添加剂。
在另一个优选的方面中,提供了一种能够长时间保持其功能而不会从电解质膜上被洗脱的添加剂。
本发明的实施方案不限于上述目的。本发明的目的将通过以下描述进一步阐明,并通过权利要求书中描述的方法及其组合来实现。
在一个方面中,提供了一种用于膜-电极组件的电解质膜,所述电解质膜可以包含:离聚物和分散在离聚物中的添加剂。具体地,添加剂可以包括嵌段共聚物,所述嵌段共聚物包含亲水域和疏水域。
在相关方面中,提供了一种用于膜-电极组件的电解质膜,所述电解质膜包含:混合物,所述混合物包含:(a)离聚物;和(b)嵌段共聚物,所述嵌段共聚物包含亲水域和疏水域。
本文使用的术语“离聚物”表示包含连接(即共价结合)至聚合物主链的作为侧链基团的离子化基团的聚合物材料或树脂。优选地,这些离子化基团可以进行官能化以具有离子特性,例如,阳离子特性或阴离子特性。离聚物可适当地包括选自氟类聚合物、全氟砜类聚合物、苯并咪唑类聚合物、聚酰亚胺类聚合物、聚醚酰亚胺类聚合物、聚苯硫醚类聚合物、聚砜类聚合物、聚醚砜类聚合物、聚醚酮类聚合物、聚醚-醚酮类聚合物、聚苯基喹喔啉类聚合物以及聚苯乙烯类聚合物中的一种或多种聚合物。
亲水域可以包含阳离子导电性重复单元。例如,亲水域可以包含一种或多种包含酸根(例如磺酸根(-SO3 -)或者磷酸根或其它含P基团)的重复单元。
在特别的方面中,阳离子导电性重复单元可以包含具有以下式1-1至式1-5的重复单元中的至少一种,
[式1-1]
[式1-2]
[式1-3]
[式1-4]
[式1-5]
疏水域可以包含抗氧化重复单元。
例如,疏水域可以包含一种或多种包含氧化氮部分的重复单元,所述氧化氮部分包含氧化胺(胺氧化物),所述氧化胺包含氧化仲胺或氧化叔胺,例如以下式2-1至式2-10中例示的那些氧化氮部分。
抗氧化重复单元可以包含具有以下式2-1至式2-10的重复单元中的至少一种,
[式2-1]
[式2-2]
[式2-3]
[式2-4]
[式2-5]
[式2-6]
[式2-7]
[式2-8]
[式2-9]
[式2-10]
优选地,亲水域的重复单元数(n)与疏水域的重复单元数(m)之间的比例为约20:80至70:30。
嵌段共聚物的数均分子量(Mn)可以为约25000或更小。
嵌段共聚物可以形成为包含内核部分和围绕所述内核部分的外壳部分的胶束。内核部分可以包含疏水域,外壳部分可以包含亲水域。
嵌段共聚物的粒子半径可以为约4nm至6nm。
以100重量份的离聚物计,电解质膜可以包含约1重量份至10重量份的添加剂。
在一个方面中,提供了一种膜-电极组件,所述膜-电极组件可以包含本文描述的电解质膜和位于所述电解质膜的两个表面上的一对电极。
根据各个示例性实施方案,膜-电极组件可适当地用于燃料电池和/或水电解装置中。
在其它实施方案中,提供了一种包括本文公开的膜-电极组件和/或燃料电池的车辆。
根据各个示例性实施方案,本文描述的添加剂可同时改善电解质膜的质子电导率和抗氧化性。
根据各个示例性实施方案,本文描述的添加剂(即包含亲水域和疏水域的嵌段共聚物)可以长时间保持其功能而不会从电解质膜中被洗脱。
本发明的效果不限于上述效果。本发明的效果应理解为包括可从以下描述中推断出的所有效果。
应理解,本文使用的术语“汽车的”或“车辆的”或其它类似术语通常包括机动汽车,例如包括运动型多用途汽车(操作SUV)、大客车、卡车、各种商用汽车的乘用汽车,包括各种舟艇和船舶的船只、航空器等,并且包括混合动力汽车、电动汽车、插电式混合动力电动汽车、氢动力汽车以及其它替代性燃料汽车(例如,源于非石油能源的燃料)。如本文所提及的,混合动力汽车是具有两种或更多种动力源的汽车,例如兼有汽油动力和电力动力的汽车。
下文讨论本发明的其它方面。
附图说明
现将参照在附图中说明的某些实施例详细地描述本发明的上述特征和其它特征,所述附图在下文中仅以说明的方式给出,因此其对本发明是非限制性的,其中:
图1显示了根据本发明的示例性实施方案的示例性嵌段共聚物。
图2显示了根据本发明的嵌段共聚物以胶束形式自组装的状态。
图3显示了根据实验实施例2的抗氧化性评估结果。
应当理解,附图并非按比例绘制,而是显示了说明本申请的基本原理的各个优选特征的略微简化的画法。本文公开的本发明的具体设计特征(包括例如具体尺寸、方向、位置和形状)将部分地由具体预期应用和使用环境来确定。
在附图中,遍及多个附图的附图标记表示本发明的相同或等同的部分。
具体实施方式
如上所述,通过与附图相关的以下优选实施方案将容易地理解根据本发明的目的、其它目的、特征和优点。然而,本发明不限于本文描述的实施例,并且可以以其它形式实施。相反,提供本文介绍的实施例是为了使本发明可以更加彻底和完整,并且可以将根据本发明的精神充分传达给本领域技术人员。
在描述每个附图时,相似的附图标记用于相似的组件。在附图中,为了本申请的清楚起见,与实际尺寸相比,结构的尺寸将被放大。术语“第一”、“第二”等可用于说明各种组件,但是组件不应限制于这些术语。这些术语仅用于区分一个元件与另一个元件。例如,第一组件可以被称为第二组件,相似地,第二组件也可以被称为第一组件,而不偏离本申请的范围。除非上下文明确地相反描述,否则单数形式可以包括复数形式。
在本说明书中,应理解,例如“包括”或“具有”的术语旨在表示存在说明书中描述的特征、数字、步骤、操作、组件、部件或其组合,但不排除预先存在或加入一种或多种其它特征、数字、步骤、操作、组件、部件或其组合的可能性。此外,当部分(例如层、薄膜、区域或板材)被称为在另一个部分“上”时,其不仅包括所述部分“直接在另一个部分上”的情况,而且还包括其它部分插入在其之间的情况。相反地,当部分(例如层、薄膜、区域或板材)被称为在另一个部分“下”时,其不仅包括所述部分“直接在另一个部分下”的情况,而且还包括其它部分插入在其之间的情况。
除非另有说明,否则本文所使用的涉及成分数量、反应条件、聚合物组成和公式的所有数字、数值和/或表达式理解为在一切情况下均由术语“约”修饰,因为这些数字本质上是近似值,其反映了在获得这些数值时所遇到的各种测量不确定性。此外,除非特别声明或者从上下文显而易见,否则本文所使用的术语“约”被理解为在本领域的正常公差范围内,例如,在平均2个标准偏差内。“约”可被理解为在指定值的10%、9%、8%、7%、6%、5%、4%、3%、2%、1%、0.5%、0.1%、0.05%或0.01%之内。除非从上下文显而易见,否则本文提供的所有数值由术语“约”来进行修饰。
此外,如果本文公开了数值范围,除非另有说明,否则该范围是连续的,并且包括该范围的从最小值到最大值(包括最大值)之间的每个数值。此外,如果此类范围涉及整数,除非另有说明,否则包括从最小值到最大值(包括最大值)之间的每个整数。例如,“5至10”的范围应当理解为包括任何子范围,例如,6至10、7至10、6至9、7至9等,以及5、6、7、8、9和10的单独值,并且还应理解为包括所述范围内的有效整数之间的任何值,例如,5.5、6.5、7.5、5.5至8.5、6.5至9等。此外,例如,“10%至30%”的范围应当理解为包括子范围,例如,10%至15%、12%至18%、20%至30%等,以及包括10%、11%、12%、13%等直至30%的值的所有整数,并且还应理解为包括所述范围内的有效整数之间的任何值,例如,10.5%、15.5%、25.5%等。
应当理解,本文所使用的术语“车辆”或“车辆的”或其它类似术语通常包括机动车辆,例如包括运动型多用途车辆(SUV)、大客车、卡车、各种商用车辆的乘用汽车,包括各种舟艇和船舶的船只、和航空器等,并且包括混合动力车辆、电动车辆、可插式混合动力电动车辆、氢动力车辆以及其它替代性燃料车辆(例如源于非石油能源的燃料)。如本文所提到的,混合动力车辆是具有两种或多种动力源的车辆,例如兼有汽油动力和电力动力的车辆。
用于膜-电极组件的电解质膜可以包含离聚物和分散在离聚物中的添加剂。
本文使用的离聚物可以在电解质膜内转移质子。
离聚物可以包括具有能够转移质子的官能团(例如Nafion)的全氟磺酸聚合物。
添加剂可以包括图1所示的嵌段共聚物。嵌段共聚物可以包含亲水域(A)和疏水域(B)。
亲水域(A)可以包含阳离子导电性重复单元。
阳离子导电性重复单元为包含能够转移质子的官能团(例如磺酸基)的重复单元,并且可以包含一种或多种具有以下式1-1至式1-5的重复单元。
[式1-1]
[式1-2]
[式1-3]
[式1-4]
[式1-5]
包含亲水域(A)的嵌段共聚物可以在电解质膜内提供除了离聚物之外的新的质子移动路径,从而显著提高电解质膜的质子电导率。
疏水域(B)可以包含抗氧化重复单元。
抗氧化重复单元可以具有能够通过以下反应式1和反应式2的反应途径将羟基自由基转化为氢氧根或者分解过氧化氢的部分结构。
[反应式1]
[反应式2]
抗氧化重复单元可以包含一种或多种由以下式2-1至式2-10表示的重复单元。
[式2-1]
[式2-2]
[式2-3]
[式2-4]
[式2-5]
[式2-6]
[式2-7]
[式2-8]
[式2-9]
[式2-10]
亲水域的重复单元数(n)与疏水域的重复单元数(m)之间的比例(n:m)可以为约20:80至70:30。当疏水域的重复单元数(m)的比例大于约80时,嵌段共聚物的粒子半径可能变得过大,使得质子电导率可能不会得到改善。
此外,嵌段共聚物的数均分子量(Mn)可以为约25000或更小,约10000或更小,或者约8000或更小。数均分子量(Mn)的下限没有特别限制。当嵌段共聚物的数均分子量大于约25000时,嵌段共聚物的粒子半径可能变得较大,使得质子电导率可能不会得到改善。
电解质膜以润湿状态存在,并且嵌段共聚物在一个分子中包含所有亲水域和疏水域。例如,如图2所示,嵌段共聚物在电解质膜内自组装,从而形成包含内核部分10和围绕所述内核部分10的外壳部分20的胶束形式。
嵌段共聚物的粒子半径可以为约4nm至6nm。在本说明书中,“粒子半径”表示在嵌段共聚物以胶束形式自组装的状态下,从胶束单元的中心点到外壳部分的表面的直线距离。此外,粒子半径表示嵌段共聚物处于水合状态时的粒子半径。例如,根据团簇-网络模型(水合Nafion的精细分子结构),磺酸根(-SO3 -)吸附水形成直径为约4nm的球形团簇,并且质子移动路径被称为窄通道,其具有1nm的宽度并连接连续的团簇。因此,为了增加质子电导率,嵌段共聚物的粒子半径可以为约4nm至6nm,或特别地为约4nm至5nm。
以100重量份的离聚物计,电解质膜可以包含1重量份至10重量份的添加剂。当添加剂的含量小于约1重量份时,改善质子电导率和抗氧化性的效果可能不足,并且当添加剂的含量大于约10重量份时,其量可能是过量的,反而降低电解质膜的质子电导率。
实施例
将通过以下实施例更详细地描述本发明的示例性实施方案。以下示例性实施方案仅用于帮助理解本申请,并且本发明的范围不限于此。
制造实施例1至制造实施例3
通过以下方法制造嵌段共聚物。
作为疏水域的单体,使用下式3表示的2,2,6,6-四甲基-4-哌啶基甲基丙烯酸酯作为疏水单体。
[式3]
作为亲水域的单体,使用下式4表示的对苯乙烯磺酸钠作为亲水单体。
[式4]
通过以下可逆加成-断裂链转移(RAFT)合成嵌段共聚物。
首先,将10g的疏水单体(0.04摩尔)、0.146g的2,2’-偶氮二(2-甲基丙腈)(AIBN)(0.8摩尔)和1.117g的4-氰基-4-(苯基硫代甲酰硫基)戊酸(0.01摩尔)加入到20mL的无水甲苯中,除去溶解的氧,然后进行氩气吹扫。在约55℃至75℃的温度下反应5小时后,在冷却之后完成聚合。在反应物在己烷溶剂中沉淀之后,通过离心获得沉淀物,并在减压烘箱中干燥一天,获得下式5表示的中间体。
[式5]
将0.02摩尔的中间体、亲水单体和0.146g的AIBN(0.8摩尔)加入到混合水与甲醇的溶剂中。此时,分别制造将亲水单体的加入量调节为0.01摩尔(制造实施例1)、0.02摩尔(制造实施例2)和0.04摩尔(制造实施例3)的样品。
在每个样品在约55℃至75℃的温度下反应5小时之后,通过冷却完成聚合。在反应物在己烷溶剂中沉淀之后,通过离心获得沉淀物,并在减压烘箱中干燥一天,从而获得共聚物。
将5g的共聚物和17.25g的间氯过氧苯甲酸(mCPBA)(0.1摩尔)加入到50mL的二氯甲烷中,并在室温下搅拌12小时,从而使共聚物氧化。在反应物在己烷溶剂中沉淀之后,通过离心获得沉淀物,并在减压烘箱中干燥一天,从而获得由下式6表示的根据本发明的示例性实施方案的嵌段共聚物。
[式6]
测量制造实施例1、制造实施例2和制造实施例3的嵌段共聚物的物理性质。结果显示在下表1中。
表1
项目 | m/n<sup>1)</sup> | 数均分子量<sup>2)</sup> | 粒子半径[nm] |
制造实施例1 | 43/57 | 6000 | 2.3 |
制造实施例2 | 31/69 | 8000 | 3.4 |
制造实施例3 | 73/27 | 23000 | 5.2 |
1)亲水域的重复单元数(n)与疏水域的重复单元数(m)的比例(m/n),通过1H-NMR测得
2)通过DOSY-NMR测得
3)通过动态光散射(DLS)测得
实施例1至实施例4和对比实施例
制备Nafion溶液。基于Nafion溶液中包含的100重量份的Nafion(离聚物),通过分别加入1重量份(实施例1)、3重量份(实施例2)、5重量份(实施例3)和10重量份(实施例4)的制造实施例1的嵌段共聚物来制造混合物。
通过将每种混合物施加到隔离纸上,然后干燥和热处理混合物来制造电解质膜。
在不加入嵌段共聚物的情况下,将仅用Nafion溶液制造的电解质膜设为对比实施例。
实验实施例1-质子电导率测量
在80℃和50%的相对湿度的条件下,在面内测量根据实施例1至实施例4和对比实施例的电解质膜的质子电导率。结果显示在下表2中。
表2
项目 | 嵌段共聚物的含量 | 电解质膜的厚度 | 质子电导率 |
对比实施例 | 0重量份 | 28 μm | 45.1mS/cm |
实施例1 | 1重量份 | 24μm | 46.5mS/cm |
实施例2 | 3重量份 | 28μm | 48.6mS/cm |
实施例3 | 5重量份 | 26μm | 51.4mS/cm |
实施例4 | 10重量份 | 31μm | 38.2mS/cm |
如表2所示,实施例3显示了最高的质子电导率,并且与对比实施例相比,该值提高了约6mS/cm。
实验实施例2-抗氧化性评估
通过测量根据实施例1至实施例4和对比实施例的电解质膜的氟离子释放随时间的变化来评估抗氧化性。结果显示在图3中。
如图3所示,与对比实施例相比,实施例1至实施例4显示出显著较低的氟离子释放,从而可以看出,当加入根据本发明的示例性实施方案的嵌段共聚物作为添加剂时,电解质膜的化学耐久性可以得到显著改善。
如上所述,已经详细描述了根据本发明的各个示例性实施方案的实验实施例和实施例,然而本发明的范围不限于上述实验实施例和实施例,并且通过本领域技术人员使用权利要求书限定的本发明的基本概念来改变和改进的各种形式也包括在本发明的范围中。
Claims (15)
1.一种用于膜-电极组件的电解质膜,所述电解质膜包含:
混合物,所述混合物包含:
(a)离聚物;和
(b)嵌段共聚物,所述嵌段共聚物包含亲水域和疏水域。
2.根据权利要求1所述的用于膜-电极组件的电解质膜,
其中,所述亲水域包含阳离子导电性重复单元。
4.根据权利要求1所述的用于膜-电极组件的电解质膜,
其中,所述疏水域包含抗氧化重复单元。
6.根据权利要求1所述的用于膜-电极组件的电解质膜,
其中,亲水域的重复单元数n与疏水域的重复单元数m之间的比例为20:80至70:30。
7.根据权利要求1所述的用于膜-电极组件的电解质膜,
其中,所述嵌段共聚物的数均分子量Mn为25000或更小。
8.根据权利要求1所述的用于膜-电极组件的电解质膜,
其中,所述嵌段共聚物形成为胶束,所述胶束包含内核部分和围绕所述内核部分的外壳部分,并且
所述内核部分包含疏水域,所述外壳部分包含亲水域。
9.根据权利要求1所述的用于膜-电极组件的电解质膜,
其中,所述嵌段共聚物的粒子半径为4nm至6nm。
10.根据权利要求1所述的用于膜-电极组件的电解质膜,
其中,以100重量份的离聚物计,包含1重量份至10重量份的添加剂。
11.一种膜-电极组件,其包括:
权利要求1所述的电解质膜;和
位于所述电解质膜的两个表面上的一对电极。
12.一种燃料电池,其包括权利要求11所述的膜-电极组件。
13.一种水电解装置,其包括权利要求11所述的膜-电极组件。
14.一种车辆,其包括权利要求11所述的膜-电极组件。
15.一种车辆,其包括权利要求12所述的燃料电池。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR10-2020-0158595 | 2020-11-24 | ||
KR1020200158595A KR20220072892A (ko) | 2020-11-24 | 2020-11-24 | 자기조립성 블록 공중합체를 포함하는 막-전극 접합체용 전해질막 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN114551950A true CN114551950A (zh) | 2022-05-27 |
Family
ID=78078058
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202111203511.XA Pending CN114551950A (zh) | 2020-11-24 | 2021-10-15 | 包含自组装嵌段共聚物的用于膜-电极组件的电解质膜 |
Country Status (5)
Country | Link |
---|---|
US (1) | US12113255B2 (zh) |
EP (1) | EP4002530A1 (zh) |
JP (1) | JP2022083399A (zh) |
KR (1) | KR20220072892A (zh) |
CN (1) | CN114551950A (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114478902A (zh) * | 2022-01-07 | 2022-05-13 | 中盐金坛盐化有限责任公司 | 水系正极聚合物及其制备方法、小分子液流电池系统 |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4910310B2 (ja) | 2004-07-09 | 2012-04-04 | 日産自動車株式会社 | 電極用組成物、電極、空気極用組成物、燃料電池用空気極、燃料電池、燃料電池システム及び燃料電池車両 |
JP4876407B2 (ja) | 2005-02-28 | 2012-02-15 | 日産自動車株式会社 | 固体高分子型燃料電池用電解質、固体高分子型燃料電池、固体高分子型燃料電池システム及び燃料電池車両 |
JP5023475B2 (ja) | 2004-12-14 | 2012-09-12 | 日産自動車株式会社 | 電極システム、燃料電池、燃料電池システム、家電機器、携帯機器及び輸送用機器 |
KR101550595B1 (ko) * | 2009-04-10 | 2015-09-07 | 주식회사 동진쎄미켐 | 폴리술폰계 중합체, 이를 포함하는 고분자 전해질막, 이를 포함하는 막-전극 접합체, 이를 채용한 연료전지 및 상기 중합체의 제조방법 |
KR101195910B1 (ko) | 2010-07-26 | 2012-10-30 | 서강대학교산학협력단 | 화학적으로 결합된 인산기를 가지는 고분자 전해질, 그의 제조 방법, 및 그를 이용한 막―전극 어셈블리와 이를 포함하는 연료전지 |
CN103814413B (zh) * | 2011-09-21 | 2017-07-18 | 东丽株式会社 | 高分子电解质组合物成型体和使用它的固体高分子型燃料电池 |
CN104115319B (zh) | 2012-02-15 | 2017-05-03 | 凸版印刷株式会社 | 碳纤维复合材料、其制造方法、催化剂载体以及固体高分子型燃料电池 |
CA2888558C (en) * | 2012-11-27 | 2021-06-15 | Toray Industries, Inc. | Polymer electrolyte composition, and polymer electrolyte membrane, membrane electrode assembly and polymer electrolyte fuel cell each produced using same |
KR101926169B1 (ko) | 2017-03-22 | 2018-12-07 | 한국화학연구원 | 술폰화 셀룰로오스, 이를 이용한 수소이온 전도성 고분자 전해질 막, 및 이를 포함하는 연료전지 |
-
2020
- 2020-11-24 KR KR1020200158595A patent/KR20220072892A/ko active Search and Examination
-
2021
- 2021-10-04 EP EP21200693.6A patent/EP4002530A1/en active Pending
- 2021-10-04 JP JP2021163737A patent/JP2022083399A/ja active Pending
- 2021-10-06 US US17/495,041 patent/US12113255B2/en active Active
- 2021-10-15 CN CN202111203511.XA patent/CN114551950A/zh active Pending
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114478902A (zh) * | 2022-01-07 | 2022-05-13 | 中盐金坛盐化有限责任公司 | 水系正极聚合物及其制备方法、小分子液流电池系统 |
Also Published As
Publication number | Publication date |
---|---|
US20220166044A1 (en) | 2022-05-26 |
JP2022083399A (ja) | 2022-06-03 |
EP4002530A1 (en) | 2022-05-25 |
US12113255B2 (en) | 2024-10-08 |
KR20220072892A (ko) | 2022-06-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Salarizadeh et al. | Novel proton exchange membranes based on proton conductive sulfonated PAMPS/PSSA-TiO2 hybrid nanoparticles and sulfonated poly (ether ether ketone) for PEMFC | |
US9455465B2 (en) | Electrolyte membrane for polymer electrolyte fuel cell, process for its production and membrane-electrode assembly for polymer electrolyte fuel cell | |
JP5287969B2 (ja) | 固体高分子電解質膜及び固体高分子形燃料電池用膜電極接合体 | |
EP1777767B1 (en) | Electrolyte membrane for solid polymer fuel cell, method for producing same and membrane electrode assembly for solid polymer fuel cell | |
US20080118808A1 (en) | Electrolyte membrane for polymer electrolyte fuel cell, process for its production and membrane-electrode assembly for polymer electrolyte fuel cell | |
JP5247974B2 (ja) | 固体高分子形水素・酸素燃料電池用電解質膜の製造方法 | |
US20100261091A1 (en) | Polysulfone polymers and related polymer electrolyte membranes and fuel cells | |
JP4972867B2 (ja) | 固体高分子形燃料電池用電解質膜、その製造方法及び固体高分子形燃料電池用膜電極接合体 | |
Woo et al. | Functionalized nanoclays for improved properties of composite proton exchange membranes | |
CN114551950A (zh) | 包含自组装嵌段共聚物的用于膜-电极组件的电解质膜 | |
JP5286651B2 (ja) | 液状組成物、その製造方法及び固体高分子形燃料電池用膜電極接合体の製造方法 | |
KR100970358B1 (ko) | 액상 조성물, 그 제조 방법 및 고체 고분자형 연료 전지용막 전극 접합체의 제조 방법 | |
JP2007031718A5 (zh) | ||
US20230056498A1 (en) | Antioxidant for fuel cells to improve durability | |
KR102328568B1 (ko) | 카테콜 기반 리간드로 표면 개질된 산화 세륨 나노 입자, 이를 포함하는 연료전지 산화 방지제와 연료전지용 복합강화전해질 막 및 그 제조 방법 | |
JP2008098179A (ja) | 固体高分子形燃料電池用電解質膜、その製造方法及び固体高分子形燃料電池用膜電極接合体 | |
Anis et al. | Fabrication and Characterization of Novel Crosslinked Composite Membranes for Direct Methanol Fuel Cell Application–Part II. Poly (Vinyl Alcohol-Co-Vinyl Acetate-Co-Itaconic Acid)/Silicotungstic Acid Based Membranes | |
US20230327160A1 (en) | Electrolyte membrane having excellent durability and proton conductivity and fuel cell including the same | |
US20110045381A1 (en) | Hydrocarbon PEM Membranes with Perfluorosulfonic Acid Groups for Automotive Fuel Cells | |
CN118216025A (zh) | 聚合物电解质膜、其制造方法和包括其的电化学装置 | |
JP2007280846A (ja) | 電解質膜、並びに、それを使用した膜−電極接合体および燃料電池 | |
Trogadas | Electrolyte degradation and degradation mitigation in polymer electrolyte fuel cells | |
XINHUI | Proton electrolyte membranes with hybrid matrix structures for assembling fuel cells |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination |