WO2024086102A1 - Durable, low-swelling reinforced ion exchange membranes - Google Patents
Durable, low-swelling reinforced ion exchange membranes Download PDFInfo
- Publication number
- WO2024086102A1 WO2024086102A1 PCT/US2023/035213 US2023035213W WO2024086102A1 WO 2024086102 A1 WO2024086102 A1 WO 2024086102A1 US 2023035213 W US2023035213 W US 2023035213W WO 2024086102 A1 WO2024086102 A1 WO 2024086102A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- ion exchange
- exchange membrane
- woven reinforcement
- reinforced
- reinforced ion
- Prior art date
Links
- 239000003014 ion exchange membrane Substances 0.000 title claims abstract description 111
- 230000002787 reinforcement Effects 0.000 claims abstract description 95
- 239000012528 membrane Substances 0.000 claims abstract description 80
- 239000000463 material Substances 0.000 claims abstract description 79
- 238000005342 ion exchange Methods 0.000 claims abstract description 66
- 229920000554 ionomer Polymers 0.000 claims abstract description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- 239000002131 composite material Substances 0.000 claims abstract description 25
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 15
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims description 40
- 239000002243 precursor Substances 0.000 claims description 32
- 238000009835 boiling Methods 0.000 claims description 26
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 19
- 229920002530 polyetherether ketone Polymers 0.000 claims description 19
- 229920006260 polyaryletherketone Polymers 0.000 claims description 11
- 229920001643 poly(ether ketone) Polymers 0.000 claims description 9
- -1 ether ketone ketone Chemical class 0.000 claims description 6
- 229920001652 poly(etherketoneketone) Polymers 0.000 claims description 6
- 229920000106 Liquid crystal polymer Polymers 0.000 claims description 5
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 claims description 5
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 5
- 230000009969 flowable effect Effects 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 150000002576 ketones Chemical class 0.000 claims description 5
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 5
- 239000010453 quartz Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000010030 laminating Methods 0.000 claims 2
- 230000008961 swelling Effects 0.000 abstract description 11
- 239000010410 layer Substances 0.000 description 35
- 230000000052 comparative effect Effects 0.000 description 32
- 239000004744 fabric Substances 0.000 description 15
- 239000006185 dispersion Substances 0.000 description 14
- 229920000557 Nafion® Polymers 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 13
- 239000000835 fiber Substances 0.000 description 11
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 11
- 125000000542 sulfonic acid group Chemical group 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 7
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 238000010998 test method Methods 0.000 description 6
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 5
- 238000003475 lamination Methods 0.000 description 5
- 230000010287 polarization Effects 0.000 description 5
- 230000003014 reinforcing effect Effects 0.000 description 5
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical group FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 description 5
- 238000010276 construction Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical class OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229910006095 SO2F Inorganic materials 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000005341 cation exchange Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- 229920003937 Aquivion® Polymers 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000004581 coalescence Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000008204 material by function Substances 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920005596 polymer binder Polymers 0.000 description 2
- 239000002491 polymer binding agent Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- SXYRTDICSOVQNZ-UHFFFAOYSA-N 1-(2-methoxyethoxy)ethanol Chemical compound COCCOC(C)O SXYRTDICSOVQNZ-UHFFFAOYSA-N 0.000 description 1
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 1
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- DYCRDXOGOYSIIA-UHFFFAOYSA-N 1-hexoxyethanol Chemical compound CCCCCCOC(C)O DYCRDXOGOYSIIA-UHFFFAOYSA-N 0.000 description 1
- TUFKHKZLBZWCAW-UHFFFAOYSA-N 2-(1-ethenoxypropan-2-yloxy)ethanesulfonyl fluoride Chemical compound C=COCC(C)OCCS(F)(=O)=O TUFKHKZLBZWCAW-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- MIJDSYMOBYNHOT-UHFFFAOYSA-N 2-(ethylamino)ethanol Chemical compound CCNCCO MIJDSYMOBYNHOT-UHFFFAOYSA-N 0.000 description 1
- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- AFSLDSXYPPTMRO-UHFFFAOYSA-N 4-fluorosulfonyloxybut-1-ene Chemical compound C(=C)CCOS(=O)(=O)F AFSLDSXYPPTMRO-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 1
- 229920008285 Poly(ether ketone) PEK Polymers 0.000 description 1
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910006069 SO3H Inorganic materials 0.000 description 1
- 229910006127 SO3X Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000004815 dispersion polymer Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical group FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000010947 wet-dispersion method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2225—Synthetic macromolecular compounds containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or 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 a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or 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 a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or 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 a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
-
- 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
- H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
-
- 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
- H01M8/1053—Polymer electrolyte composites, mixtures or blends consisting of layers of polymers with at least one layer being ionically conductive
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
- H01M8/106—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties characterised by the chemical composition of the porous support
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
- H01M8/1062—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties characterised by the physical properties of the porous support, e.g. its porosity or thickness
-
- 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
- H01M8/1067—Polymeric electrolyte materials characterised by their physical properties, e.g. porosity, ionic conductivity or thickness
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
Definitions
- Composite ion exchange membranes composed of an extruded ion exchange material and woven reinforcement material have improved swelling in all three dimensions.
- an ion exchange membrane In a water electrolysis system, an ion exchange membrane is fixed between an oxygen electrode and hydrogen electrode, allowing the transport of protons through the pores in the membrane and allowing the hydrolysis of water. Because the ion exchange membrane is in constant contact with water, it must be capable of performing in a wet state.
- Typical ion exchange membranes swell under conditions of contact with water or alcohol, which leads to decreased selectivity of the ion exchange membrane and, ultimately, decreased durability.
- Ionomer membranes using PTFE reinforcements are known for chloralkali applications but have swelling in the range of 7-8% in the machine and transverse directions of the films.
- EW Equivalent Weight
- the present invention describes composite membranes, catalyst coated membranes, and water electrolysis systems having improved swelling and durability when subjected to the conditions of a water electrolysis system.
- the present invention relates to a reinforced ion exchange membrane comprising a woven reinforcement and an ion exchange material, where the woven reinforcement is made from a material with a tensile modulus of at least 1 GPa, measured by ASTM D638; the ion exchange material is a fluorinated ionomer having sulfonate groups and having an ion exchange ratio less than about 13.2; the woven reinforcement has a first side and a second side opposite the first side, and the woven reinforcement has extruded ion exchange material layers on both the first side and second side.
- the reinforced ion exchange membrane expands less than about 60.0% in the Z direction after immersing in boiling water for 1 hour. In another aspect, the reinforced ion exchange membrane has an average thickness of about 30-150 pm.
- the present invention also relates to catalyst coated membranes made from the reinforced ion exchange membranes of the invention, having a cathode catalyst layer on one side of the reinforced ion exchange membrane and an anode catalyst layer on another side of the reinforced ion exchange membrane; and to water electrolysis systems using the catalyst coated membranes.
- the present invention also relates to a process for forming a reinforced ion exchange membrane comprising a woven reinforcement and an ion exchange material, the process comprising extruding fluorinated ionomer precursor in at least one layer, contacting the fluorinated ionomer precursor layer in a flowable state with a woven reinforcement to form a composite membrane precursor, and treating the composite membrane precursor to form a reinforced ion exchange membrane, where the woven reinforcement is made from a material with a tensile modulus of at least 1 GPa, measured by ASTM D638; the ion exchange material is a fluorinated ionomer having sulfonate groups and having an ion exchange ratio less than about 13.2; the woven reinforcement has a first side and a second side opposite the first side, and the woven reinforcement has extruded ion exchange material layers on both the first side and second side.
- the reinforced ion exchange membrane expands less than about 60.0% in the Z direction after immersing in boiling water for 1 hour. In another aspect, the reinforced ion exchange membrane has an average thickness of about 30-150 pm.
- FIG. 1 illustrates the three dimensions of a membrane, as they relate to a film or membrane role.
- FIG. 2 illustrates a cross-section view of a catalyst coated membrane.
- FIG. 3 illustrates the creep performance of Example 1 , Comparative Example A, and Comparative Example H.
- FIG. 4 illustrates the conductivity and water electrolysis performance of Example 4 and Comparative Example K.
- machine direction refers to the in-plane direction of a film parallel to a direction of travel or wind-up on a roll of the membrane during manufacture of the film, as depicted in FIG. 1.
- transverse direction refers to the in-plane direction of a film perpendicular to the machine direction, as depicted in FIG. 1.
- Z direction refers to the direction through the thickness of the film, as depicted in FIG. 1.
- the present invention relates to a reinforced ion exchange membrane comprising a woven reinforcement and an ion exchange material, where the woven reinforcement is made from a material with a tensile modulus of at least 1 GPa, measured by ASTM D638; the ion exchange material is a fluorinated ionomer having sulfonate groups and having an ion exchange ratio less than about 13.2; the woven reinforcement has a first side and a second side opposite the first side, and the woven reinforcement has extruded ion exchange material layers on both the first side and second side.
- the woven reinforcement may be any woven material capable of providing the reinforced ion exchange membrane with a high modulus and low swelling in the machine and transverse directions.
- the woven reinforcement is made from a material with a tensile modulus of at least about 1 GPa, as measured by ASTM D638. If the tensile modulus is too high to be adequately measured by ASTM D638, such as above 20 GPa, an alternative method such as ASTM D3039/3039M.
- the woven reinforcement is made from a material with a tensile modulus of at least about 1 .5 GPa, as measured by ASTM D638; in another aspect, a tensile modulus of at least about 1 .8 GPa; in another aspect, a tensile modulus of at least about 2.0 GPa; in another aspect, a tensile modulus of at least about 2.5 GPa; in another aspect, a tensile modulus of at least about 3.0 GPa; in another aspect, a tensile modulus of at least about 3.5 GPa, and in another aspect, a tensile modulus of at least about 3.8 GPa; or any value, range, or sub-range therebetween.
- Examples of materials having a high enough tensile modulus to provide improvements in swelling in both machine and transverse directions are liquid crystal polymer, polyphenylene sulfide, glass, quartz, or polyaryl ether ketone (PAEK).
- Specific polyaryl ether ketones include, but are not limited to, polyether ketone (PEK), polyether ether ketone (PEEK), polyether ketone ketone (PEKK), polyether ether ketone ketone (PEEKK), or polyether ketone ether ketone ketone (PEKEKK).
- the woven reinforcement is in the form of a plain weave.
- plain weave refers to a style of weave where the weft fiber alternates over and under the warp fiber, such that both sides of the woven material have the same fiber pattern.
- the woven reinforcement has a symmetrical weave pattern, such that the weave has the same fiber spacing in one position as when it is turned 180° in the same plane.
- the distance between fiber centers is about 150-240 pm; in another aspect, about 170-220 pm; in another aspect, about 180-210 pm; and in another aspect, about 190-200 pm; all defined as measuring the average distance from one fiber center to the distance of the next fiber center.
- the woven reinforcement has an open area of about 50- 80%; in another aspect, about 60-75%; and in another aspect, about 65-75%. Open area can be defined as:
- L distance from one fiber center to the next fiber center in one direction
- W is the distance from one fiber center to the next fiber center in a direction orthogonal to L
- CL is the distance from one open area center to the next open area center in one direction
- Gw is the distance from one open area center to the next open area center in a direction orthogonal to CL.
- the ion exchange material is a fluorinated ionomer having sulfonate groups.
- sulfonate or sulfonic acid groups refers to either sulfonic acid groups or salts of sulfonic acid, preferably alkali metal or ammonium salts.
- Preferred functional groups are represented by the formula -SO3X wherein X is H, Li, Na, K or N(R 1 )(R 2 )(R 3 )(R 4 ), where R 1 , R 2 , R 3 , and R 4 are the same or different and are H, CH3, or C2H5.
- the fluorinated ionomer containing sulfonate or sulfonic acid groups is of the type available under the trade name of NationalTM (The Chemours Company FC, LLC, Wilmington, DE).
- the fluorinated ionomer may contain the repeat unit:
- segment ((CF2)b-(O-(CF2CFRf) c ) a -O-(CF2CFR'f)dSO3X) in the structure above is the pendant chain from the perfluorinated polymer backbone. Branched pendant chains having multiple sulfonic acid groups are also emcompassed.
- the fluorinated ionomer is a copolymer made from two or more monomers.
- it is a copolymer of a sulfonic acid-containing monomer with tetrafluoroethylene (TFE), resulting in a repeat unit -[CF2-CF2]-, or with other comonomers.
- TFE tetrafluoroethylene
- monomers having pendant phosphonic acid groups may also be incorporated into the fluorinated ionomer to yield a fluorinated ionomer containing both sulfonic acid groups and phosphonic acid groups.
- Preferred fluorinated ionomers containing sulfonate or sulfonic acid groups may include, for example, polymers disclosed in U.S. Patent No. 3,282,875, in U.S. Patent No. 4,358,545, or in U.S. Patent No. 4,940,525.
- One preferred fluorinated ionomer containing sulfonate or sulfonic acid groups includes a perfluorocarbon backbone and a side chain represented by the formula -O-CF 2 CF(CP3)-O-CF2CF2SO3X, where X is as defined above. When X is H, the side chain is -O-CF2CF(CF3)-O-CF2CF2SO3H. Fluorinated ionomers containing sulfonate or sulfonic acid groups of this type are disclosed in U.S. Patent No.
- TFE tetrafluoroethylene
- PSEPVE perfluorinated vinyl ether
- PSEPVE also called long side-chain or LSC
- One preferred fluorinated ionomer containing sulfonate or sulfonic acid groups is of the type disclosed in U.S. Patent No. 4,358,545 and U.S. Patent No. 4,940,525, which has the side chain -O-CF2CF2SO3X, where X is as defined above.
- PFSVE perfluoro(3 oxa-4-pentenesulfonyl fluoride)
- SSC short side-chain
- the ion exchange material has an ion exchange ratio of less than about 13.2.
- IXR ion exchange ratio
- the ion exchange material has an IXR less than about 13.2; in another aspect, less than about 12.7; in another aspect, less than about 12.1 ; and in another aspect, less than about 11 .7; or any value, range, or sub-range therebetween.
- the ion exchange material has an IXR of at least 7.1 ; in another aspect, at least 8.1 ; in another aspect, at least 9.1 ; and in another aspect, at least 10.1 ; or any value, range, or sub-range therebetween.
- the ion exchange material has an equivalent weight (EW) less than about 1000; alternatively, less than about 980; alternatively, less than about 950; alternatively, less than about 930, or any value, range, or sub-range therebetween.
- the ion exchange material has an EW of at least about 530; alternatively, at least about 580; alternatively, at least about 630; alternatively, at least about 680, or any value, range, or sub-range therebetween.
- EW refers to the weight of the ionomer in proton form required to neutralize one equivalent of NaOH.
- the ion exchange material contains the long side chain and has an EW less than about 1000; alternatively, less than about 980; alternatively, less than about 950; alternatively, less than about 930, or any value, range, or subrange therebetween. In one aspect, the ion exchange material has an EW of at least about 700; alternatively, at least about 750; alternatively, at least about 800; alternatively, at least about 950, or any value, range, or sub-range therebetween.
- the ion exchange material contains the short side chain and has an EW less than about 840; alternatively, less than about 810; alternatively, less than about 785; alternatively, less than about 765, or any value, range, or sub-range therebetween.
- the ion exchange material has an EW of at least about 530; alternatively, at least about 580; alternatively, at least about 630; alternatively, at least about 680, or any value, range, or sub-range therebetween.
- the woven reinforcement has a first side and a second side opposite the first side, where the woven reinforcement has extruded ion exchange material layers on both the first and second sides. As shown in FIG. 2, the woven reinforcement layer 3 has ion exchange material on either side to form the reinforced membrane 1 . In one aspect, the woven reinforcement is centered in the Z direction within the reinforced ion exchange membrane.
- Ion exchange materials having lower IXR values are thought to have difficulty with polymer coalescence due to their low molecular weights, thus leading to decreased durability in alcohol, water, and water/alcohol mixtures, especially at elevated temperatures.
- the ion exchange material layers of the present invention have shown improved durability and swelling, partially due to the processing method.
- the present invention also relates to a process for forming a reinforced ion exchange membrane comprising a woven reinforcement and an ion exchange material, the process comprising extruding fluorinated ionomer precursor in at least one layer, contacting the fluorinated ionomer precursor layer in a flowable state with a woven reinforcement to form a composite membrane precursor, and treating the composite membrane precursor to form a reinforced ion exchange membrane, where the woven reinforcement is made from a material with a tensile modulus of at least 1 GPa, measured by ASTM D638; the ion exchange material is a fluorinated ionomer having sulfonate groups and having an ion exchange ratio less than about 13.2; the woven reinforcement has a first side and a second side opposite the first side, and the woven reinforcement has extruded ion exchange material layers on both the first side and second side.
- the reinforced ion exchange membrane expands less than about 60.0% in the Z direction after
- the ion exchange materials are melt extruded and then laminated in a flowable state with the woven reinforcement, thus improving polymer coalescence and durability.
- the contacting or lamination step occurs above the T g of the fluorinated ionomer precursor.
- the contacting or lamination step occurs above the T g but below the T m of the fluorinated ionomer precursor.
- T g and T m can be measured by rheological measurements, for example, using a parallel plate rheometer.
- the ion exchange materials are extruded in the melt processible form, usually an ion exchange polymer precursor.
- fluorinated ionomer precursor is used to define the melt-processible pre-hydrolyzed form of the fluorinated ionomer, such as the sulfonyl fluoride form.
- the extruded film can then be laminated at elevated temperature with the woven reinforcement to fuse the polymer and woven layer together into a composite film according to typical lamination methods, such as by using a lamination roll, belt laminator, or a vacuum lamination process.
- one layer of fluorinated ionomer precursor is extruded, and the woven reinforcement is laminated with the single layer of precursor such that the woven reinforcement migrates to the interior of the fluorinated ionomer precursor, forming a woven reinforcement with fluorinated ionomer precursor layers on both the first side and second side.
- two or more fluorinated ionomer precursor layers are extruded, and the woven reinforcement is laminated between two or more layers to form a woven reinforcement with fluorinated ionomer precursor layers on both the first side and second side.
- extruded ion exchange material layers is hereby intended to mean ion exchange material layers that have been formed by melt extrusion of the corresponding fluorinated ionomer precursor.
- the composite film may then be treated by hydrolysis in an aqueous alkali metal hydroxide solution and, optionally, subsequently acidified to convert the sulfonyl fluoride groups to sulfonic acid or sulfonate groups.
- Alkali metal hydroxides include but are not limited to NaOH or KOH.
- a water- soluble organic solvent may be employed in the hydrolysis solution, such as dimethyl sulfoxide (DMSO), N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2- pyrrolidinone, N-ethyl-2-pyrrolidone, methanol, ethanol, isopropanol, butanol, methoxyethoxyethanol, butoxyethanol, butylcarbitol, hexyloxyethanol, octanol, propylene glycol methyl ether, ethylene glycol, ethanolamine, N-methylethanolamine, N-ethylethanolamine, 1-amino-2-propanol, 1-amino-3-propanol, 2- aminoethoxyethanol, 2-aminoethoxyethanol, and 2-amino-2-methyl-1 -propanol.
- DMSO dimethyl sulfoxide
- N,N-dimethylformamide N,N-dimethylacetamide
- the final reinforced ion exchange membranes may have an average thickness of about 30-150 pm; in another aspect, an average thickness of about 30-120 pm; in another aspect, an average thickness of about 30-100 pm; in another aspect, an average thickness of about 30-80 pm; and in another aspect, an average thickness of about 30-60 pm.
- the reinforced ion exchange membranes resist expansion in all three dimensions after subjecting to conditions simulating an extreme water electrolysis system environment.
- the reinforced ion exchange membrane expands less than 2% in the machine direction and expands less than 2% in the transverse direction after immersing the reinforced ion exchange membrane in boiling water for 1 hour.
- the % expansion is calculated by comparing lengths of membrane before and after subjecting to boiling water, or in the case of measuring the Z direction, comparing thicknesses of membrane before and after subjecting to boiling water.
- the reinforced ion exchange membrane expands less than 1 .5% in the machine direction and expands less than 1 .5% in the transverse direction after immersing the reinforced ion exchange membrane in boiling water for 1 hour; in another aspect, the ion exchange membrane expands less than 1 .0% in the machine direction and expands less than 1 .0% in the transverse direction; and in yet another aspect, the ion exchange membrane expands less than 0.5% in the machine direction and expands less than 0.5% in the transverse direction. Comparing the % expansion in the Z direction is also an aspect of the invention.
- the reinforced ion exchange membrane expands less than about 60% in the Z direction after immersing in boiling water for 1 hour; in another aspect, the reinforced ion exchange membrane expands less than about 58% in the Z direction; in another aspect, the reinforced ion exchange membrane expands less than about 55% in the Z direction; in another aspect, the reinforced ion exchange membrane expands less than about 53% in the Z direction.
- the reinforced ion exchange membranes are used in catalyst coated membranes, having multiple layers of functional materials. Such catalyst coated membranes may be used in electrolytical systems, for example, a water electrolysis system.
- the invention relates to a catalyst coated membrane comprising the reinforced ion exchange membrane, where the catalyst coated membrane comprises a cathode catalyst layer on one side of the reinforced ion exchange membrane and an anode catalyst layer on another side of the reinforced ion exchange membrane.
- a catalyst coated membrane may comprise a cathode catalyst layer (CCL) on one side of the ion exchange membrane and an anode catalyst layer (ACL) on another side of the ion exchange membrane.
- CCL cathode catalyst layer
- ACL anode catalyst layer
- a cathode catalyst layer 4 is in direct contact with an ion exchange membrane 1
- the reinforced ion exchange membrane 1 is in further direct contact with anode catalyst layer 2 to make catalyst coated membrane 5.
- the ion exchange membrane 1 has a woven reinforcement layer 3 embedded within the ion exchange membrane.
- the catalyst coated membrane may contain multiple layers of the same material, and it may contain additional layers of functional materials, such as gas diffusion layers, porous transport layers, or bipolar plates.
- the CCL and ACL may be applied to the ion exchange membrane in the form of a catalyst ink.
- Catalyst ink compositions often include a catalyst component and a polymer binder, where the polymer binder often includes fluorinated ionomers such as those described above.
- the polymer used in the CCL and ACL may be the same or different from the polymer used as the fluorinated ionomer of the ion exchange membrane.
- Catalyst components may include but are not limited to metal particles or carbon-supported metal particles.
- Specific metals may include but are not limited to platinum, ruthenium, gold, silver, palladium, iridium, rhodium, iron, cobalt, nickel, chromium, tungsten, manganese, vanadium, and alloys thereof.
- Solvents such as those mentioned for use in the ion exchange dispersion, may be used to aid in application of the catalyst ink to the ion exchange membrane.
- the CCL and ACL materials may be applied to the ion exchange membrane by any suitable means, including brushing, spraying, notch bar coating, fluid die coating, rod coating, slot-fed knife coating, three-roll coating, or decal transfer.
- NAFION D2021 and NAFION D2020 are dispersions made from chemically stabilized perfluorosulfonic acid I PTFE copolymers in the acid form having an EW of 1000 g/mol and 920 g/mol, respectively;
- NAFION N2050 is a PTFE-reinforced extruded membrane made from chemically stabilized perfluorosulfonic acid I PTFE copolymers in the acid form having an EW of 920 g/mol;
- NAFION N113 is an unreinforced extruded membrane made from chemically stabilized perfluorosulfonic acid / PTFE copolymers in the acid form having an EW of 1000 g/mol;
- NAFION N115 is an unreinforced extruded membrane made from chemically stabilized perfluorosulfonic acid I PTFE copolymers in the acid form having an EW of 1000 g/mol;
- NAFION N117 is an unreinforced extrude
- FUMASEP FS-990-PK is a PEEK-reinforced short side-chain perfluorinated cation exchange membrane having an EW of 980 g/mol
- FUMASEP F-10120-PK is a PEEK-reinforced long side-chain perfluorinated cation exchange membrane having an EW of 1000 g/mol
- a 150 mm x 150 mm membrane sample was conditioned at 23 °C and 50% relative humidity for 24 hours. Black marks were then placed 100 mm apart from one another in both the machine and transverse direction of the membrane, and the thickness was recorded. The membrane was placed in boiling water for 1 hour and then removed. The distance between the marks in both the machine and transverse direction was recorded along with the new thickness after boiling.
- Samples were pre-soaked in water such that any swelling that occurs in the machine or transverse dimensions was done before fixing in the device.
- a sample holder was used that allowed 8 samples to be measured simultaneously. Samples were loaded and maintained in a fully immersed state for the duration of the test. The samples were then pressurized to a setpoint and the time is recorded for each sample until rupture occurs.
- Catalyst coated membranes were made by decal transferring Greenerity E300 electrodes onto the membranes at 150 °C and 3000 pounds pressure on a 3” x 3” membrane. These catalyst-coated membranes were then run on a Scribner water electrolysis test station at 80 °C and ambient cathode and anode cell pressures.
- the sulfonate ionomer precursor was melt laminated with a PEEK reinforcing fabric to form a composite film.
- the PEEK reinforcing fabric used was a plain weave fabric having fibers of approximately 38 pm in diameter, a center-to-center fiber spacing of about 195 pm, open area of about 70%.
- the laminated films were hydrolyzed in a solution of DMSO I KOH / water as is taught in the art.
- the films were then acidified in a solution of 20% nitric acid in water before being dried to remove excess water.
- the final membranes were tested according to the Test Methods above to give the results of Tables 1 and 3.
- a base layer of NationalTM dispersion D2021 was cast with a doctor blade onto a PET substrate and allowed to dry to form a first layer.
- a PEEK reinforcing fabric was then placed on top of the base layer and two more layers of NationalTM D2021 were applied such that the final dry membrane thickness of the composite was 80.0 pm.
- the PEEK reinforcing fabric used was a plain weave fabric having fibers of approximately 38 pm in diameter, a center-to-center fiber spacing of about 195 pm, open area of about 70%.
- the final composite was then placed into a vacuum oven at 190 °C to coalesce the ionomer.
- the composite membranes were tested according to the Test Methods above to give the results in Tables 2 and 3.
- Example G NAFION N115 (Comparative Example H), NAFION N117 (Comparative Example I), and NAFION NR212 (Comparative Example J) were obtained and tested according to the Test Methods above to give the results of Tables 3 and 4.
- Comparative Examples A and B represent dispersion cast membranes using the same reinforcement as Examples 1-3.
- Comparative Examples C-D represent commercial composite membranes having similar reinforcement to Examples 1-3.
- each sample has low expansion in the machine and transverse directions, the composite membranes of Examples 1-3 show unexpectedly low expansion in the thickness direction of the membranes. This performance is visible in Comparative Examples A, C, and D, having a higher IXR, but it is especially visible in Comparative Example B, which has the same IXR as Examples 1-3.
- Comparative Example B which has the same IXR as Examples 1-3.
- the combination of low IXR and process allow for unexpectedly low expansion in all three dimensions of the membranes.
- Comparative Examples E and G-l represent commercial unreinforced extruded membranes
- Comparative Example J represents a commercial unreinforced dispersion cast membrane
- Comparative Example F represents a composite membrane of similar IXR and process having a different reinforcement material.
- the expansion is relatively low in the Z direction of the membranes of Comparative Examples E-J, the expansion in the machine and transverse directions are high.
- the choice in reinforcement allows for unexpectedly low expansion in all three dimensions of the membranes.
- Example 1 shows the significantly improved creep relative to an unreinforced extruded membrane. Where Example 1 can survive for 848 minutes at 42 psi of applied pressure, unreinforced Comparative example H only lasts 148 minutes at a much lower pressure of 32 psi. Comparative example A, containing a higher IXR polymer dispersion cast membrane, only lasts 329 minutes. This shows the performance benefit of the illustrative example, namely the improved creep performance over an unreinforced extruded film and over a dispersion cast reinforced film that both contain higher IXR polymers. The illustrative examples show improved durability and performance.
- Example 1 was repeated to form a construction where the PEEK cloth was between the 1 .6 mil film above the cloth and a 1 .6 mil film below the cloth.
- the PEEK reinforcing fabric used was a plain weave fabric having fibers of approximately 38 pm in diameter, a center-to-center fiber spacing of about 195 pm, open area of about 70%.
- This construction was placed into an isobaric vacuum press, Lauffer press UVL 50/1.
- a composite membrane was formed by heating the construction to 210 °C and applying 15 psi of pressure to laminate the extruded, sulfonyl fluoride films into the PEEK cloth.
- this material was hydrolyzed using DMSO, KOH, and water and then acid exchanged using 20% nitric acid in water.
- Comparative Example K represents a direct comparison to Example 4, using a dispersion cast membrane rather than extruded membrane.
- a composite membrane was cast using a commercially available PFSA dispersion containing the same 920 EW ionomer as Example 4 in water and alcohol.
- a doctor blade applied a controlled level of dispersion to a polyethylene terephthalate (PET) backer, and the dispersion was dried in a 10% relative humidity chamber without heat.
- PET polyethylene terephthalate
- a second coating layer was applied, and the PEEK cloth was lain into the wet dispersion before placing the composite into a 10% relative humidity chamber.
- This final construction was then annealed at 175 °C for four minutes. This produced a composite membrane of an identical PEEK cloth fabric, 920 equivalent weight polymer, and 1 10 micron thickness as Example 4, but formed through a solution or dispersion casting process.
- Comparative Example K had significantly more swelling in the Z direction than Example 4, indicating an unexpected difference in dispersion cast membranes versus extruded membranes. Additionally, polarization curves were measured from 0.01 A/cm 2 to 4 A/cm 2 on Example 4 and Comparative Example K. Highlighting the difference in resistance of the two membranes, Example 4 shows a voltage of 1 .63 V at 1 A/cm 2 and a voltage of 1 .97 V at 4 A/cm 2 , while Comparative Example K has a voltage of 1 .64 V at 1 A/cm 2 and a voltage of 2.03 at 4 A/cm 2 . The lower voltage at high current density and difference in slope of the polarization curves highlights the unexpectedly higher conductivity and improved performance for Example 4.
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Abstract
The present invention describes composite membranes, catalyst coated membranes, and water electrolysis systems having improved swelling and durability when subjected to the conditions of a water electrolysis system. The reinforced ion exchange membranes have a woven reinforcement and an ion exchange material, where the woven reinforcement is made from a material with a tensile modulus of at least 1 GPa; the ion exchange material is a fluorinated ionomer having sulfonate groups and having an ion exchange ratio less than about 13.2; and the woven reinforcement has extruded ion exchange material layers on both sides.
Description
TITLE
DURABLE, LOW-SWELLING REINFORCED ION EXCHANGE MEMBRANES
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This Application claims the priority benefit of US provisional patent application no. 63/417,173, filed on October 18, 2022, the disclosure of which is hereby incorporated by reference in its entirety.
FIELD OF THE INVENTION
[0002] Composite ion exchange membranes composed of an extruded ion exchange material and woven reinforcement material have improved swelling in all three dimensions.
BACKGROUND
[0003] In a water electrolysis system, an ion exchange membrane is fixed between an oxygen electrode and hydrogen electrode, allowing the transport of protons through the pores in the membrane and allowing the hydrolysis of water. Because the ion exchange membrane is in constant contact with water, it must be capable of performing in a wet state.
[0004] Typical ion exchange membranes swell under conditions of contact with water or alcohol, which leads to decreased selectivity of the ion exchange membrane and, ultimately, decreased durability. Ionomer membranes using PTFE reinforcements are known for chloralkali applications but have swelling in the range of 7-8% in the machine and transverse directions of the films.
[0005] Additionally, low resistance is desired. For this reason, low Equivalent Weight (EW) polymers and membranes have been targeted. However, low EW polymers are consistent with low molecular weight polymers and thus are consistent with lower durability, especially when subjected to water or water/alcohol mixtures.
SUMMARY
[0006] The present invention describes composite membranes, catalyst coated membranes, and water electrolysis systems having improved swelling and durability when subjected to the conditions of a water electrolysis system.
[0007] The present invention relates to a reinforced ion exchange membrane comprising a woven reinforcement and an ion exchange material, where the woven reinforcement is made from a material with a tensile modulus of at least 1 GPa, measured by ASTM D638; the ion exchange material is a fluorinated ionomer having sulfonate groups and having an ion exchange ratio less than about 13.2; the woven reinforcement has a first side and a second side opposite the first side, and the woven reinforcement has extruded ion exchange material layers on both the first side and second side. In one aspect, the reinforced ion exchange membrane expands less than about 60.0% in the Z direction after immersing in boiling water for 1 hour. In another aspect, the reinforced ion exchange membrane has an average thickness of about 30-150 pm. The present invention also relates to catalyst coated membranes made from the reinforced ion exchange membranes of the invention, having a cathode catalyst layer on one side of the reinforced ion exchange membrane and an anode catalyst layer on another side of the reinforced ion exchange membrane; and to water electrolysis systems using the catalyst coated membranes.
[0008] The present invention also relates to a process for forming a reinforced ion exchange membrane comprising a woven reinforcement and an ion exchange material, the process comprising extruding fluorinated ionomer precursor in at least one layer, contacting the fluorinated ionomer precursor layer in a flowable state with a woven reinforcement to form a composite membrane precursor, and treating the composite membrane precursor to form a reinforced ion exchange membrane, where the woven reinforcement is made from a material with a tensile modulus of at least 1 GPa, measured by ASTM D638; the ion exchange material is a fluorinated ionomer having sulfonate groups and having an ion exchange ratio less than about 13.2; the woven reinforcement has a first side and a second side opposite the first side, and the woven reinforcement has extruded ion exchange material layers on both the first side and second side. In one aspect, the reinforced ion exchange membrane expands less than about 60.0% in the Z direction after immersing in boiling water for 1 hour. In another aspect, the reinforced ion exchange membrane has an average thickness of about 30-150 pm.
BRIEF DESCRIPTION OF THE DRAWINGS
[0009] FIG. 1 illustrates the three dimensions of a membrane, as they relate to a film or membrane role.
[0010] FIG. 2 illustrates a cross-section view of a catalyst coated membrane.
[0011] FIG. 3 illustrates the creep performance of Example 1 , Comparative Example A, and Comparative Example H.
[0012] FIG. 4 illustrates the conductivity and water electrolysis performance of Example 4 and Comparative Example K.
DETAILED DESCRIPTION OF THE INVENTION
[0013] Features of the embodiments of the present invention described in the Detailed Description of the Invention can be combined in any manner. All tradenames are designated by capitalization of the brand name.
Definitions
[0014] As used herein, machine direction (MD) refers to the in-plane direction of a film parallel to a direction of travel or wind-up on a roll of the membrane during manufacture of the film, as depicted in FIG. 1.
[0015] As used herein, transverse direction (TD) refers to the in-plane direction of a film perpendicular to the machine direction, as depicted in FIG. 1.
[0016] As used herein, Z direction (ZD) refers to the direction through the thickness of the film, as depicted in FIG. 1.
[0017] The present invention relates to a reinforced ion exchange membrane comprising a woven reinforcement and an ion exchange material, where the woven reinforcement is made from a material with a tensile modulus of at least 1 GPa, measured by ASTM D638; the ion exchange material is a fluorinated ionomer having sulfonate groups and having an ion exchange ratio less than about 13.2; the woven reinforcement has a first side and a second side opposite the first side, and the woven reinforcement has extruded ion exchange material layers on both the first side and second side.
[0018] The woven reinforcement may be any woven material capable of providing the reinforced ion exchange membrane with a high modulus and low swelling in the machine and transverse directions. In one aspect, the woven reinforcement is made
from a material with a tensile modulus of at least about 1 GPa, as measured by ASTM D638. If the tensile modulus is too high to be adequately measured by ASTM D638, such as above 20 GPa, an alternative method such as ASTM D3039/3039M. In another aspect, the woven reinforcement is made from a material with a tensile modulus of at least about 1 .5 GPa, as measured by ASTM D638; in another aspect, a tensile modulus of at least about 1 .8 GPa; in another aspect, a tensile modulus of at least about 2.0 GPa; in another aspect, a tensile modulus of at least about 2.5 GPa; in another aspect, a tensile modulus of at least about 3.0 GPa; in another aspect, a tensile modulus of at least about 3.5 GPa, and in another aspect, a tensile modulus of at least about 3.8 GPa; or any value, range, or sub-range therebetween. Examples of materials having a high enough tensile modulus to provide improvements in swelling in both machine and transverse directions are liquid crystal polymer, polyphenylene sulfide, glass, quartz, or polyaryl ether ketone (PAEK). Specific polyaryl ether ketones include, but are not limited to, polyether ketone (PEK), polyether ether ketone (PEEK), polyether ketone ketone (PEKK), polyether ether ketone ketone (PEEKK), or polyether ketone ether ketone ketone (PEKEKK).
[0019] In one aspect, the woven reinforcement is in the form of a plain weave. As used herein, plain weave refers to a style of weave where the weft fiber alternates over and under the warp fiber, such that both sides of the woven material have the same fiber pattern. In one aspect, the woven reinforcement has a symmetrical weave pattern, such that the weave has the same fiber spacing in one position as when it is turned 180° in the same plane. In another aspect, the distance between fiber centers is about 150-240 pm; in another aspect, about 170-220 pm; in another aspect, about 180-210 pm; and in another aspect, about 190-200 pm; all defined as measuring the average distance from one fiber center to the distance of the next fiber center. In one aspect, the woven reinforcement has an open area of about 50- 80%; in another aspect, about 60-75%; and in another aspect, about 65-75%. Open area can be defined as:
L x w % Open Area = — - — — x 100%
(CL x Cw) where L is distance from one fiber center to the next fiber center in one direction, W is the distance from one fiber center to the next fiber center in a direction orthogonal to L, CL is the distance from one open area center to the next open area center in
one direction, and Gw is the distance from one open area center to the next open area center in a direction orthogonal to CL.
[0020] To optimize resistance of the reinforced ion exchange membranes, it is preferred that the ion exchange material is a fluorinated ionomer having sulfonate groups. As used herein, sulfonate or sulfonic acid groups refers to either sulfonic acid groups or salts of sulfonic acid, preferably alkali metal or ammonium salts. Preferred functional groups are represented by the formula -SO3X wherein X is H, Li, Na, K or N(R1)(R2)(R3)(R4), where R1, R2, R3, and R4 are the same or different and are H, CH3, or C2H5. In exemplary embodiments, the fluorinated ionomer containing sulfonate or sulfonic acid groups is of the type available under the trade name of Nation™ (The Chemours Company FC, LLC, Wilmington, DE).
[0021] For example, the fluorinated ionomer may contain the repeat unit:
-[CF2-CF((CF2)b-(O-(CF2CFRf)c)a-O-(CF2CFR'f)dSO3X)]- where b is 0 or 1 ; c is an integer from 2 to 8; a is 0, 1 , or 2; d is an integer from 1 to 8; Rf and R'f are independently selected from F, Cl or a perfluorinated alkyl group having 1 to 10 carbon atoms; a = 0, 1 or 2; and X is H, Li, Na, K or N(R1)(R2)(R3)(R4) where R1, R2, R3, and R4 are the same or different and are H, CH3 or C2H5. For clarity, it is noted that the segment ((CF2)b-(O-(CF2CFRf)c)a-O-(CF2CFR'f)dSO3X) in the structure above is the pendant chain from the perfluorinated polymer backbone. Branched pendant chains having multiple sulfonic acid groups are also emcompassed.
[0022] In one aspect, the fluorinated ionomer is a copolymer made from two or more monomers. For example, it is a copolymer of a sulfonic acid-containing monomer with tetrafluoroethylene (TFE), resulting in a repeat unit -[CF2-CF2]-, or with other comonomers. For example, monomers having pendant phosphonic acid groups may also be incorporated into the fluorinated ionomer to yield a fluorinated ionomer containing both sulfonic acid groups and phosphonic acid groups.
[0023] A class of preferred fluorinated ionomers containing sulfonate or sulfonic acid groups include a highly fluorinated, most preferably perfluorinated, carbon backbone with a side chain represented by the formula -(O-CF2CFRf)a-O- CF2CFR,fSOsX, where Rf and R,f are independently selected from F, Cl, or a perfluorinated alkyl group having 1 to 10 carbon atoms, a = 0, 1 or 2, and X is H, Li,
Na, K or N(R1)(R2)(R3)(R4), where R1, R2, R3, and R4 are the same or different and are H, CH3, or C2Hs. Preferred fluorinated ionomers containing sulfonate or sulfonic acid groups may include, for example, polymers disclosed in U.S. Patent No. 3,282,875, in U.S. Patent No. 4,358,545, or in U.S. Patent No. 4,940,525.
[0024] One preferred fluorinated ionomer containing sulfonate or sulfonic acid groups includes a perfluorocarbon backbone and a side chain represented by the formula -O-CF2CF(CP3)-O-CF2CF2SO3X, where X is as defined above. When X is H, the side chain is -O-CF2CF(CF3)-O-CF2CF2SO3H. Fluorinated ionomers containing sulfonate or sulfonic acid groups of this type are disclosed in U.S. Patent No. 3,282,875 and may be made by copolymerization of tetrafluoroethylene (TFE) and the perfluorinated vinyl ether CF2=CF-O-CF2CF(CF3)-O-CF2CF2SO2F, perfluoro(3,6 dioxa-4 methyl 7 octenesulfonyl fluoride) (PSEPVE, also called long side-chain or LSC), followed by conversion to sulfonate groups by hydrolysis of the sulfonyl fluoride groups and conversion to the proton form if desired for the particular application.
[0025] One preferred fluorinated ionomer containing sulfonate or sulfonic acid groups is of the type disclosed in U.S. Patent No. 4,358,545 and U.S. Patent No. 4,940,525, which has the side chain -O-CF2CF2SO3X, where X is as defined above. This fluorinated ionomer containing sulfonate or sulfonic acid groups may be made by copolymerization of TFE and the perfluorinated vinyl ether CF2=CF-O- CF2CF2SO2F, perfluoro(3 oxa-4-pentenesulfonyl fluoride) (PFSVE, also called short side-chain or SSC), followed by hydrolysis and conversion to the proton form if desired for the particular application. When X is H, the side chain is -O- CF2CF2SO3H.
[0026] In some embodiments, the ion exchange material has an ion exchange ratio of less than about 13.2. As used herein, ion exchange ratio (IXR) refers to the number of carbon atoms in the ionomer backbone in relation to the number of cation exchange groups. In some embodiments, the IXR of an ionomer can be related to its equivalent weight (EW) by the equation EW = (50 x IXR) + MWSC -19, where MWSC is the molecular weight of the side chain of the ionomer. In one aspect, the ion exchange material has an IXR less than about 13.2; in another aspect, less than about 12.7; in another aspect, less than about 12.1 ; and in another aspect, less than about 11 .7; or any value, range, or sub-range therebetween. In one aspect, the ion
exchange material has an IXR of at least 7.1 ; in another aspect, at least 8.1 ; in another aspect, at least 9.1 ; and in another aspect, at least 10.1 ; or any value, range, or sub-range therebetween.
[0027] In some embodiments, the ion exchange material has an equivalent weight (EW) less than about 1000; alternatively, less than about 980; alternatively, less than about 950; alternatively, less than about 930, or any value, range, or sub-range therebetween. In one aspect, the ion exchange material has an EW of at least about 530; alternatively, at least about 580; alternatively, at least about 630; alternatively, at least about 680, or any value, range, or sub-range therebetween. As used herein, (EW) refers to the weight of the ionomer in proton form required to neutralize one equivalent of NaOH.
[0028] In one aspect, the ion exchange material contains the long side chain and has an EW less than about 1000; alternatively, less than about 980; alternatively, less than about 950; alternatively, less than about 930, or any value, range, or subrange therebetween. In one aspect, the ion exchange material has an EW of at least about 700; alternatively, at least about 750; alternatively, at least about 800; alternatively, at least about 950, or any value, range, or sub-range therebetween. The IXR for a fluorinated ionomer with the side chain -O-CF2-CF(CF3)-O-CF2-CF2- SO3H, i.e. , produced from a copolymer of TFE and PSEPVE, can be related to EW using the following formula: 50 IXR + 344 = EW.
[0029] In another embodiment, the ion exchange material contains the short side chain and has an EW less than about 840; alternatively, less than about 810; alternatively, less than about 785; alternatively, less than about 765, or any value, range, or sub-range therebetween. In one aspect, the ion exchange material has an EW of at least about 530; alternatively, at least about 580; alternatively, at least about 630; alternatively, at least about 680, or any value, range, or sub-range therebetween. The IXR for a fluorinated ionomer with the side chain -O- CF2CF2SO3H, i.e., produced from a copolymer of TFE and PFSVE, can be related to equivalent weight using the following formula: 50 IXR + 178 = EW.
[0030] The woven reinforcement has a first side and a second side opposite the first side, where the woven reinforcement has extruded ion exchange material layers on both the first and second sides. As shown in FIG. 2, the woven reinforcement layer 3 has ion exchange material on either side to form the reinforced membrane 1 .
In one aspect, the woven reinforcement is centered in the Z direction within the reinforced ion exchange membrane.
[0031] Ion exchange materials having lower IXR values are thought to have difficulty with polymer coalescence due to their low molecular weights, thus leading to decreased durability in alcohol, water, and water/alcohol mixtures, especially at elevated temperatures. However, the ion exchange material layers of the present invention have shown improved durability and swelling, partially due to the processing method. The present invention also relates to a process for forming a reinforced ion exchange membrane comprising a woven reinforcement and an ion exchange material, the process comprising extruding fluorinated ionomer precursor in at least one layer, contacting the fluorinated ionomer precursor layer in a flowable state with a woven reinforcement to form a composite membrane precursor, and treating the composite membrane precursor to form a reinforced ion exchange membrane, where the woven reinforcement is made from a material with a tensile modulus of at least 1 GPa, measured by ASTM D638; the ion exchange material is a fluorinated ionomer having sulfonate groups and having an ion exchange ratio less than about 13.2; the woven reinforcement has a first side and a second side opposite the first side, and the woven reinforcement has extruded ion exchange material layers on both the first side and second side. In one aspect, the reinforced ion exchange membrane expands less than about 60.0% in the Z direction after immersing in boiling water for 1 hour. In another aspect, the reinforced ion exchange membrane has an average thickness of about 30-150 pm.
[0032] The ion exchange materials are melt extruded and then laminated in a flowable state with the woven reinforcement, thus improving polymer coalescence and durability. In one aspect, the contacting or lamination step occurs above the Tg of the fluorinated ionomer precursor. In another aspect, the contacting or lamination step occurs above the Tg but below the Tm of the fluorinated ionomer precursor. Tg and Tm can be measured by rheological measurements, for example, using a parallel plate rheometer. The ion exchange materials are extruded in the melt processible form, usually an ion exchange polymer precursor. The term “fluorinated ionomer precursor” is used to define the melt-processible pre-hydrolyzed form of the fluorinated ionomer, such as the sulfonyl fluoride form. The extruded film can then be laminated at elevated temperature with the woven reinforcement to fuse the polymer
and woven layer together into a composite film according to typical lamination methods, such as by using a lamination roll, belt laminator, or a vacuum lamination process. In one aspect, one layer of fluorinated ionomer precursor is extruded, and the woven reinforcement is laminated with the single layer of precursor such that the woven reinforcement migrates to the interior of the fluorinated ionomer precursor, forming a woven reinforcement with fluorinated ionomer precursor layers on both the first side and second side. In another aspect, two or more fluorinated ionomer precursor layers are extruded, and the woven reinforcement is laminated between two or more layers to form a woven reinforcement with fluorinated ionomer precursor layers on both the first side and second side. The term “extruded ion exchange material layers” is hereby intended to mean ion exchange material layers that have been formed by melt extrusion of the corresponding fluorinated ionomer precursor.
[0033] The composite film may then be treated by hydrolysis in an aqueous alkali metal hydroxide solution and, optionally, subsequently acidified to convert the sulfonyl fluoride groups to sulfonic acid or sulfonate groups. Alkali metal hydroxides include but are not limited to NaOH or KOH. During the hydrolysis step, a water- soluble organic solvent may be employed in the hydrolysis solution, such as dimethyl sulfoxide (DMSO), N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2- pyrrolidinone, N-ethyl-2-pyrrolidone, methanol, ethanol, isopropanol, butanol, methoxyethoxyethanol, butoxyethanol, butylcarbitol, hexyloxyethanol, octanol, propylene glycol methyl ether, ethylene glycol, ethanolamine, N-methylethanolamine, N-ethylethanolamine, 1-amino-2-propanol, 1-amino-3-propanol, 2- aminoethoxyethanol, 2-aminoethoxyethanol, and 2-amino-2-methyl-1 -propanol.
[0034] In one aspect, the final reinforced ion exchange membranes may have an average thickness of about 30-150 pm; in another aspect, an average thickness of about 30-120 pm; in another aspect, an average thickness of about 30-100 pm; in another aspect, an average thickness of about 30-80 pm; and in another aspect, an average thickness of about 30-60 pm.
[0035] The reinforced ion exchange membranes resist expansion in all three dimensions after subjecting to conditions simulating an extreme water electrolysis system environment. In one aspect, the reinforced ion exchange membrane expands less than 2% in the machine direction and expands less than 2% in the transverse direction after immersing the reinforced ion exchange membrane in boiling water for
1 hour. The % expansion is calculated by comparing lengths of membrane before and after subjecting to boiling water, or in the case of measuring the Z direction, comparing thicknesses of membrane before and after subjecting to boiling water. In another aspect, the reinforced ion exchange membrane expands less than 1 .5% in the machine direction and expands less than 1 .5% in the transverse direction after immersing the reinforced ion exchange membrane in boiling water for 1 hour; in another aspect, the ion exchange membrane expands less than 1 .0% in the machine direction and expands less than 1 .0% in the transverse direction; and in yet another aspect, the ion exchange membrane expands less than 0.5% in the machine direction and expands less than 0.5% in the transverse direction. Comparing the % expansion in the Z direction is also an aspect of the invention. In one aspect, the reinforced ion exchange membrane expands less than about 60% in the Z direction after immersing in boiling water for 1 hour; in another aspect, the reinforced ion exchange membrane expands less than about 58% in the Z direction; in another aspect, the reinforced ion exchange membrane expands less than about 55% in the Z direction; in another aspect, the reinforced ion exchange membrane expands less than about 53% in the Z direction.
[0036] The reinforced ion exchange membranes are used in catalyst coated membranes, having multiple layers of functional materials. Such catalyst coated membranes may be used in electrolytical systems, for example, a water electrolysis system. In one aspect, the invention relates to a catalyst coated membrane comprising the reinforced ion exchange membrane, where the catalyst coated membrane comprises a cathode catalyst layer on one side of the reinforced ion exchange membrane and an anode catalyst layer on another side of the reinforced ion exchange membrane. A catalyst coated membrane may comprise a cathode catalyst layer (CCL) on one side of the ion exchange membrane and an anode catalyst layer (ACL) on another side of the ion exchange membrane. For example, in one embodiment shown in FIG. 2, a cathode catalyst layer 4 is in direct contact with an ion exchange membrane 1 , and the reinforced ion exchange membrane 1 is in further direct contact with anode catalyst layer 2 to make catalyst coated membrane 5. The ion exchange membrane 1 has a woven reinforcement layer 3 embedded within the ion exchange membrane. The catalyst coated membrane may contain
multiple layers of the same material, and it may contain additional layers of functional materials, such as gas diffusion layers, porous transport layers, or bipolar plates.
[0037] The CCL and ACL may be applied to the ion exchange membrane in the form of a catalyst ink. Catalyst ink compositions often include a catalyst component and a polymer binder, where the polymer binder often includes fluorinated ionomers such as those described above. The polymer used in the CCL and ACL may be the same or different from the polymer used as the fluorinated ionomer of the ion exchange membrane. Catalyst components may include but are not limited to metal particles or carbon-supported metal particles. Specific metals may include but are not limited to platinum, ruthenium, gold, silver, palladium, iridium, rhodium, iron, cobalt, nickel, chromium, tungsten, manganese, vanadium, and alloys thereof. Solvents, such as those mentioned for use in the ion exchange dispersion, may be used to aid in application of the catalyst ink to the ion exchange membrane. The CCL and ACL materials may be applied to the ion exchange membrane by any suitable means, including brushing, spraying, notch bar coating, fluid die coating, rod coating, slot-fed knife coating, three-roll coating, or decal transfer.
EXAMPLES
Test Methods
[0038] The following test methods and materials were used in the examples herein.
[0039] The invention is illustrated in the following examples which do not limit the scope of the invention as described in the claims. The following test methods and materials were used in the examples herein.
[0040] All solvents and reagents, unless otherwise indicated, are available from Sigma-Aldrich, St. Louis, MO.
[0041] NAFION D2021 and NAFION D2020 are dispersions made from chemically stabilized perfluorosulfonic acid I PTFE copolymers in the acid form having an EW of 1000 g/mol and 920 g/mol, respectively; NAFION N2050 is a PTFE-reinforced extruded membrane made from chemically stabilized perfluorosulfonic acid I PTFE copolymers in the acid form having an EW of 920 g/mol; NAFION N113 is an unreinforced extruded membrane made from chemically stabilized perfluorosulfonic acid / PTFE copolymers in the acid form having an EW of 1000 g/mol; NAFION N115
is an unreinforced extruded membrane made from chemically stabilized perfluorosulfonic acid I PTFE copolymers in the acid form having an EW of 1000 g/mol; NAFION N117 is an unreinforced extruded membrane made from chemically stabilized perfluorosulfonic acid I PTFE copolymers in the acid form having an EW of 1000 g/mol; and NAFION NR212 is an unreinforced dispersion cast membrane made from chemically stabilized perfluorosulfonic acid I PTFE copolymers in the acid form having an EW of 1000 g/mol; all available from The Chemours Company, Wilmington, DE. The sulfonate ionomer precursor (copolymer of CF2=CF2 and perfluorinated vinyl ether CF2=CF-O-CF2CF(CF3)-O-CF2CF2SO2F, EW 920, IXR 11 .5) was also under the NAFION brand, available from The Chemours Company, Wilmington, DE.
[0042] FUMASEP FS-990-PK is a PEEK-reinforced short side-chain perfluorinated cation exchange membrane having an EW of 980 g/mol; FUMASEP F-10120-PK is a PEEK-reinforced long side-chain perfluorinated cation exchange membrane having an EW of 1000 g/mol; and AQUIVION E98-09S is a chemically stabilized unreinforced perfluorosulfonic acid ionomer membrane having an EW of 950 g/mol and made of the acid form of a copolymer of TFE/sulfonyl fluoride vinyl ether (CF2=CF-O-CF2CF2-SO2F); all available from The Fuel Cell Store, College Station, TX.
Expansion Testing
[0043] A 150 mm x 150 mm membrane sample was conditioned at 23 °C and 50% relative humidity for 24 hours. Black marks were then placed 100 mm apart from one another in both the machine and transverse direction of the membrane, and the thickness was recorded. The membrane was placed in boiling water for 1 hour and then removed. The distance between the marks in both the machine and transverse direction was recorded along with the new thickness after boiling. % Expansion was calculated as:
where Lb = Length (or thickness) after boiling and La = Length (or thickness) before boiling. Expansion in the Z direction was calculated using the same equation, where the length used corresponds to the thickness before and after boiling. The lengths Lb and La were taken at 3 points and averaged.
[0044] Volumetric expansion was calculated as:
where Vb = volume after boiling and Va = volume before boiling. For example, for a membrane having a starting volume of 1 .00 mm x 1 .00 mm x 1 .00 mm (1 .00 mm3) and a post-boiling volume of 1.10 mm x 1.23 mm x 1.18 mm (1.60 mm3), the volumetric expansion would be 60%.
Creep Performance (Blister Test)
[0045] In order to measure the long term, biaxial creep performance of these membranes in water, an instrument was built functionally equivalent to the one described from the paper of Yongqiang Li et al, “Fatigue and creep to leak tests of proton exchange membranes using pressure-loaded blisters” in the Journal of Power Sources, 194 (2009) 873-879. Of importance is the diameter of the blisters in this design being one inch.
[0046] Samples were pre-soaked in water such that any swelling that occurs in the machine or transverse dimensions was done before fixing in the device. A sample holder was used that allowed 8 samples to be measured simultaneously. Samples were loaded and maintained in a fully immersed state for the duration of the test. The samples were then pressurized to a setpoint and the time is recorded for each sample until rupture occurs.
Thickness
[0047] Three thickness measurements were taken with a ProGage thickness measurement gauge available from Thwing-Albert Instrument Company, West Berlin, NJ. The reported thickness represents an average of the three measurements.
Water Electrolysis Performance Testing
[0048] Catalyst coated membranes were made by decal transferring Greenerity E300 electrodes onto the membranes at 150 °C and 3000 pounds pressure on a 3” x 3” membrane. These catalyst-coated membranes were then run on a Scribner water electrolysis test station at 80 °C and ambient cathode and anode cell pressures.
After an industry-standard 4.5 hours break-in, polarization curves were measured from 0.01 A/cm2 up to 4 A/cm2
Examples 1-3
[0049] A 4 foot (1 .2 meter) wide sulfonate ionomer precursor (copolymer of CF2=CF2 and perfluorinated vinyl ether CF2=CF-O-CF2CF(CF3)-O-CF2CF2SO2F, EW 920, IXR 11 .5) was first extruded at 270 °C using a single-screw extruder, a die block, film die, chill roll, and take-up roll. The sulfonate ionomer precursor was melt laminated with a PEEK reinforcing fabric to form a composite film. The PEEK reinforcing fabric used was a plain weave fabric having fibers of approximately 38 pm in diameter, a center-to-center fiber spacing of about 195 pm, open area of about 70%.
[0050] The laminated films were hydrolyzed in a solution of DMSO I KOH / water as is taught in the art. The films were then acidified in a solution of 20% nitric acid in water before being dried to remove excess water. The final membranes were tested according to the Test Methods above to give the results of Tables 1 and 3.
Comparative Example A
[0051] A base layer of Nation™ dispersion D2021 was cast with a doctor blade onto a PET substrate and allowed to dry to form a first layer. A PEEK reinforcing fabric was then placed on top of the base layer and two more layers of Nation™ D2021 were applied such that the final dry membrane thickness of the composite was 80.0 pm. The PEEK reinforcing fabric used was a plain weave fabric having fibers of approximately 38 pm in diameter, a center-to-center fiber spacing of about 195 pm, open area of about 70%. The final composite was then placed into a vacuum oven at 190 °C to coalesce the ionomer. The composite membranes were tested according to the Test Methods above to give the results in Tables 2 and 3.
[0052] Comparative Example A was repeated, except Nation™ D2020 was used as the dispersion.
Comparative Examples C-J
[0053] Membranes FUMASEP FS-990-PK (Comparative Example C), FUMASEP F-10120-PK (Comparative Example D), AQUIVION E98-09S (Comparative Example E), NAFION N2050 (Comparative Example F), NAFION N113 (Comparative
Example G), NAFION N115 (Comparative Example H), NAFION N117 (Comparative Example I), and NAFION NR212 (Comparative Example J) were obtained and tested according to the Test Methods above to give the results of Tables 3 and 4.
[0054] Comparative Examples A and B represent dispersion cast membranes using the same reinforcement as Examples 1-3. Comparative Examples C-D
represent commercial composite membranes having similar reinforcement to Examples 1-3. Although each sample has low expansion in the machine and transverse directions, the composite membranes of Examples 1-3 show unexpectedly low expansion in the thickness direction of the membranes. This performance is visible in Comparative Examples A, C, and D, having a higher IXR, but it is especially visible in Comparative Example B, which has the same IXR as Examples 1-3. Here it is shown that the combination of low IXR and process allow for unexpectedly low expansion in all three dimensions of the membranes.
[0055] Comparative Examples E and G-l represent commercial unreinforced extruded membranes, Comparative Example J represents a commercial unreinforced dispersion cast membrane, and Comparative Example F represents a composite membrane of similar IXR and process having a different reinforcement material. Although the expansion is relatively low in the Z direction of the membranes of Comparative Examples E-J, the expansion in the machine and transverse directions are high. Here it is shown that the choice in reinforcement allows for unexpectedly low expansion in all three dimensions of the membranes.
[0056] The creep performance of the illustrative examples was shown using the blister test. Example 1 shows the significantly improved creep relative to an unreinforced extruded membrane. Where Example 1 can survive for 848 minutes at 42 psi of applied pressure, unreinforced Comparative example H only lasts 148 minutes at a much lower pressure of 32 psi. Comparative example A, containing a higher IXR polymer dispersion cast membrane, only lasts 329 minutes. This shows the performance benefit of the illustrative example, namely the improved creep performance over an unreinforced extruded film and over a dispersion cast reinforced film that both contain higher IXR polymers. The illustrative examples show improved durability and performance.
Example 4
[0057] Example 1 was repeated to form a construction where the PEEK cloth was between the 1 .6 mil film above the cloth and a 1 .6 mil film below the cloth. The PEEK reinforcing fabric used was a plain weave fabric having fibers of approximately 38 pm in diameter, a center-to-center fiber spacing of about 195 pm, open area of about 70%. This construction was placed into an isobaric vacuum press, Lauffer press UVL 50/1. A composite membrane was formed by heating the construction to
210 °C and applying 15 psi of pressure to laminate the extruded, sulfonyl fluoride films into the PEEK cloth. Afterwards, this material was hydrolyzed using DMSO, KOH, and water and then acid exchanged using 20% nitric acid in water. This produced an extruded, composite membrane consisting of 920 equivalent weight polymer (IXR 11 .5) and a thickness of 110 micron when measured at 50% RH.
[0058] A portion of the sample was measured in the expansion test and showed a swelling of 29.5% in the Z direction. This sample was run in a water electrolysis test station and the polarization curve was measured. The voltage at 2 A/cm2 was 1.754925 V.
Comparative Example K
[0059] Comparative Example K represents a direct comparison to Example 4, using a dispersion cast membrane rather than extruded membrane. A composite membrane was cast using a commercially available PFSA dispersion containing the same 920 EW ionomer as Example 4 in water and alcohol. A doctor blade applied a controlled level of dispersion to a polyethylene terephthalate (PET) backer, and the dispersion was dried in a 10% relative humidity chamber without heat. A second coating layer was applied, and the PEEK cloth was lain into the wet dispersion before placing the composite into a 10% relative humidity chamber. This final construction was then annealed at 175 °C for four minutes. This produced a composite membrane of an identical PEEK cloth fabric, 920 equivalent weight polymer, and 1 10 micron thickness as Example 4, but formed through a solution or dispersion casting process.
[0060] A portion of the sample was measured in the expansion test and showed a swelling of 58.0% in the Z direction. This sample was run in a water electrolysis test station and the polarization curve was measured. The voltage at 2 A/cm2 was 1.782388 V.
[0061] It can be seen that Comparative Example K had significantly more swelling in the Z direction than Example 4, indicating an unexpected difference in dispersion cast membranes versus extruded membranes. Additionally, polarization curves were measured from 0.01 A/cm2 to 4 A/cm2 on Example 4 and Comparative Example K. Highlighting the difference in resistance of the two membranes, Example 4 shows a voltage of 1 .63 V at 1 A/cm2 and a voltage of 1 .97 V at 4 A/cm2, while Comparative Example K has a voltage of 1 .64 V at 1 A/cm2 and a voltage of 2.03 at 4 A/cm2. The
lower voltage at high current density and difference in slope of the polarization curves highlights the unexpectedly higher conductivity and improved performance for Example 4.
Claims
1 . A reinforced ion exchange membrane comprising a woven reinforcement and an ion exchange material, where the woven reinforcement is made from a material with a tensile modulus of at least 1 GPa, measured by ASTM D638; the ion exchange material is a fluorinated ionomer having sulfonate groups and having an ion exchange ratio less than about 13.2; the woven reinforcement has a first side and a second side opposite the first side, and the woven reinforcement has extruded ion exchange material layers on both the first side and second side; and where the reinforced ion exchange membrane expands less than about 60.0% in the Z direction after immersing in boiling water for 1 hour.
2. The reinforced ion exchange membrane of claim 1 , where the woven reinforcement is made from a material with a tensile modulus of at least 1 .5 GPa.
3. The reinforced ion exchange membrane of claim 2, where the woven reinforcement is made from a material with a tensile modulus of at least 1.8 GPa.
4. The reinforced ion exchange membrane of claims 1-3, where the woven reinforcement is selected from liquid crystal polymer, polyphenylene sulfide, glass, quartz, or polyaryl ether ketone.
5. The reinforced ion exchange membrane of claim 4, where the woven reinforcement is a polyaryletherketone selected from polyether ketone, polyether ether ketone, polyether ketone ketone, polyether ether ketone ketone, or polyether ketone ether ketone ketone.
6. The reinforced ion exchange membrane of claims 1-5, where the ion exchange material has an ion exchange ratio less than about 12.7.
7. The reinforced ion exchange membrane of claims 1-6, where the reinforced ion exchange membrane has an average thickness of about 30-150 pm.
8. The reinforced ion exchange membrane of claim 7, where the reinforced ion exchange membrane has an average thickness of about 30-120 pm.
9. The reinforced ion exchange membrane of claims 1-8, where the woven reinforcement is in the form of a plain weave.
10. The reinforced ion exchange membrane of claims 1-9, where the woven reinforcement has a symmetrical weave pattern.
11 . The reinforced ion exchange membrane of claims 1 -10, where the woven reinforcement has an open area of about 50-80%.
12. The reinforced ion exchange membrane of claims 1-11 , where the reinforced ion exchange membrane expands less than 2% in the machine direction and expands less than 2% in the transverse direction, each after immersing in boiling water for 1 hour.
13. The reinforced ion exchange membrane of claims 1-12, where the reinforced ion exchange membrane expands less than about 58.0% in the Z direction after immersing in boiling water for 1 hour.
14. The reinforced ion exchange membrane of claims 1-13, where the woven reinforcement is centered in the Z direction within the reinforced ion exchange membrane.
15. A catalyst coated membrane comprising the reinforced ion exchange membrane of claims 1-14, where the catalyst coated membrane comprises a cathode catalyst layer on one side of the reinforced ion exchange membrane and an anode catalyst layer on another side of the reinforced ion exchange membrane.
16. A water electrolysis system comprising the catalyst coated membrane of claim
15.
17. A process for forming a reinforced ion exchange membrane comprising a woven reinforcement and an ion exchange material, the process comprising extruding fluorinated ionomer precursor in at least one layer, contacting the fluorinated ionomer precursor layer in a flowable state with a woven reinforcement to form a composite membrane precursor, and treating the composite membrane precursor to form a reinforced ion exchange membrane, where the woven reinforcement is made from a material with a tensile modulus of at least 1 GPa, measured by ASTM D638; the ion exchange material is a fluorinated ionomer having sulfonate groups and having an ion exchange ratio less than about 13.2; the woven reinforcement has a first side and a second side opposite the first side, and the woven reinforcement has extruded ion exchange material layers on both the first side and second side; and where the reinforced ion exchange membrane expands less than about 60.0% in the Z direction after immersing in boiling water for 1 hour.
18. The process of claim 17, where the woven reinforcement is made from a material with a tensile modulus of at least 1 .5 GPa.
19. The process of claim 18, where the woven reinforcement is made from a material with a tensile modulus of at least 1 .8 GPa.
20. The process of claims 17-19, where the woven reinforcement is selected from liquid crystal polymer, polyphenylene sulfide, glass, quartz, or polyaryl ether ketone.
21 . The process of claim 20, where the woven reinforcement is a polyaryletherketone selected from polyether ketone, polyether ether ketone, polyether ketone ketone, polyether ether ketone ketone, or polyether ketone ether ketone ketone.
22. The process of claims 17-21 , where the ion exchange material has an ion exchange ratio less than about 12.7.
23. The process of claims 17-22, where the reinforced ion exchange membrane has an average thickness of about 30-150 pm.
24. The process of claim 23, where the reinforced ion exchange membrane has an average thickness of about 30-120 pm.
25. The process of claims 17-24, where the woven reinforcement is in the form of a plain weave.
26. The process of claims 17-25, where the woven reinforcement has a symmetrical weave pattern.
27. The process of claims 17-26, where the woven reinforcement has an open area of about 50-80%.
28. The process of claims 17-28, where the reinforced ion exchange membrane expands less than 2% in the machine direction and expands less than 2% in the transverse direction, each after immersing in boiling water for 1 hour.
29. The process of claims 17-28, where the reinforced ion exchange membrane expands less than about 58.0% in the Z direction after immersing in boiling water for 1 hour.
30. The process of claims 17-29, where the woven reinforcement is centered in the Z direction within the reinforced ion exchange membrane.
31 . The process of claims 17-30, where the step of contacting comprises laminating at least two layers of fluorinated ionomer precursor at elevated temperature.
32. A reinforced ion exchange membrane comprising a woven reinforcement and an ion exchange material, where the woven reinforcement is made from a material with a tensile modulus of at least 1 GPa, measured by ASTM D638; the ion exchange material is a fluorinated ionomer having sulfonate groups and having an ion exchange ratio less than about 13.2; the woven reinforcement has a first side and a second side opposite the first side, and the woven reinforcement has extruded ion exchange material layers on both the first side and second side; and where the reinforced ion exchange membrane has an average thickness of about 30-150 pm.
33. The reinforced ion exchange membrane of claim 32, where the woven reinforcement is made from a material with a tensile modulus of at least 1.5 GPa.
34. The reinforced ion exchange membrane of claim 33, where the woven reinforcement is made from a material with a tensile modulus of at least 1.8 GPa.
35. The reinforced ion exchange membrane of claims 32-34, where the woven reinforcement is selected from liquid crystal polymer, polyphenylene sulfide, glass, quartz, or polyaryl ether ketone.
36. The reinforced ion exchange membrane of claim 35, where the woven reinforcement is a polyaryletherketone selected from polyether ketone, polyether ether ketone, polyether ketone ketone, polyether ether ketone ketone, or polyether ketone ether ketone ketone.
37. The reinforced ion exchange membrane of claims 32-36, where the ion exchange material has an ion exchange ratio less than about 12.7.
38. The reinforced ion exchange membrane of claims 32-37, where the reinforced ion exchange membrane has an average thickness of about 30-120 pm.
39. The reinforced ion exchange membrane of claims 32-38, where the woven reinforcement is in the form of a plain weave.
40. The reinforced ion exchange membrane of claims 32-39, where the woven reinforcement has a symmetrical weave pattern.
41 . The reinforced ion exchange membrane of claims 32-40, where the woven reinforcement has an open area of about 50-80%.
42. The reinforced ion exchange membrane of claims 32-41 , where the reinforced ion exchange membrane expands less than 2% in the machine direction and expands less than 2% in the transverse direction, each after immersing in boiling water for 1 hour.
43. The reinforced ion exchange membrane of claim 42, where the reinforced ion exchange membrane expands less than about 58.0% in the Z direction after immersing in boiling water for 1 hour.
44. The reinforced ion exchange membrane of claims 32-43, where the woven reinforcement is centered in the Z direction within the reinforced ion exchange membrane.
45. A catalyst coated membrane comprising the reinforced ion exchange membrane of claims 32-44, where the catalyst coated membrane comprises a cathode catalyst layer on one side of the reinforced ion exchange membrane and an anode catalyst layer on another side of the reinforced ion exchange membrane.
46. A water electrolysis system comprising the catalyst coated membrane of claim 45.
47. A process for forming a reinforced ion exchange membrane comprising a woven reinforcement and an ion exchange material, the process comprising extruding fluorinated ionomer precursor in at least one layer, contacting the fluorinated ionomer precursor layer in a flowable state with a woven reinforcement to
form a composite membrane precursor, and treating the composite membrane precursor to form a reinforced ion exchange membrane, where the woven reinforcement is made from a material with a tensile modulus of at least 1 GPa, measured by ASTM D638; the ion exchange material is a fluorinated ionomer having sulfonate groups and having an ion exchange ratio less than about 13.2; the woven reinforcement has a first side and a second side opposite the first side, and the woven reinforcement has extruded ion exchange material layers on both the first side and second side; and where the reinforced ion exchange membrane has an average thickness of about 30-150 pm.
48. The process of claim 47, where the woven reinforcement is made from a material with a tensile modulus of at least 1 .5 GPa.
49. The process of claim 48, where the woven reinforcement is made from a material with a tensile modulus of at least 1 .8 GPa.
50. The process of claims 47-49, where the woven reinforcement is selected from liquid crystal polymer, polyphenylene sulfide, glass, quartz, or polyaryl ether ketone.
51 . The process of claim 50, where the woven reinforcement is a polyaryletherketone selected from polyether ketone, polyether ether ketone, polyether ketone ketone, polyether ether ketone ketone, or polyether ketone ether ketone ketone.
52. The process of claims 47-51 , where the ion exchange material has an ion exchange ratio less than about 12.7.
53. The process of claim 47-52, where the reinforced ion exchange membrane has an average thickness of about 30-120 pm.
54. The process of claims 47-53, where the woven reinforcement is in the form of a plain weave.
55. The process of claims 47-54, where the woven reinforcement has a symmetrical weave pattern.
56. The process of claims 47-55, where the woven reinforcement has an open area of about 50-80%.
57. The process of claims 47-56, where the reinforced ion exchange membrane expands less than 2% in the machine direction and expands less than 2% in the transverse direction, each after immersing in boiling water for 1 hour.
58. The process of claims 47-57, where the reinforced ion exchange membrane expands less than about 58.0% in the Z direction after immersing in boiling water for 1 hour.
59. The process of claims 47-58, where the woven reinforcement is centered in the Z direction within the reinforced ion exchange membrane.
60. The process of claims 47-59, where the step of contacting comprises laminating at least two layers of fluorinated ionomer precursor at elevated temperature.
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US202263417173P | 2022-10-18 | 2022-10-18 | |
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Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3282875A (en) | 1964-07-22 | 1966-11-01 | Du Pont | Fluorocarbon vinyl ether polymers |
US4358545A (en) | 1980-06-11 | 1982-11-09 | The Dow Chemical Company | Sulfonic acid electrolytic cell having flourinated polymer membrane with hydration product less than 22,000 |
EP0305155A2 (en) * | 1987-08-26 | 1989-03-01 | Asahi Kasei Kogyo Kabushiki Kaisha | A reinforced ion exchange membrane and a process for producing the same |
US4940525A (en) | 1987-05-08 | 1990-07-10 | The Dow Chemical Company | Low equivalent weight sulfonic fluoropolymers |
EP3266903A1 (en) * | 2015-03-03 | 2018-01-10 | Asahi Glass Company, Limited | Ion exchange membrane for alkali chloride electrolysis, and alkali chloride electrolysis apparatus |
EP3284848A1 (en) * | 2015-04-13 | 2018-02-21 | Asahi Glass Company, Limited | Method of manufacturing ion exchange membrane for electrolysis, and ion exchange membrane for electrolysis |
EP3527697A1 (en) * | 2016-10-13 | 2019-08-21 | AGC Inc. | Diaphragm for electrolyzing alkaline water, and device for electrolyzing alkaline water |
WO2020168023A1 (en) * | 2019-02-14 | 2020-08-20 | The Chemours Company Fc, Llc | Multilayer cation exchange chloralkali membrane |
-
2023
- 2023-10-16 WO PCT/US2023/035213 patent/WO2024086102A1/en unknown
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3282875A (en) | 1964-07-22 | 1966-11-01 | Du Pont | Fluorocarbon vinyl ether polymers |
US4358545A (en) | 1980-06-11 | 1982-11-09 | The Dow Chemical Company | Sulfonic acid electrolytic cell having flourinated polymer membrane with hydration product less than 22,000 |
US4940525A (en) | 1987-05-08 | 1990-07-10 | The Dow Chemical Company | Low equivalent weight sulfonic fluoropolymers |
EP0305155A2 (en) * | 1987-08-26 | 1989-03-01 | Asahi Kasei Kogyo Kabushiki Kaisha | A reinforced ion exchange membrane and a process for producing the same |
EP3266903A1 (en) * | 2015-03-03 | 2018-01-10 | Asahi Glass Company, Limited | Ion exchange membrane for alkali chloride electrolysis, and alkali chloride electrolysis apparatus |
EP3284848A1 (en) * | 2015-04-13 | 2018-02-21 | Asahi Glass Company, Limited | Method of manufacturing ion exchange membrane for electrolysis, and ion exchange membrane for electrolysis |
EP3527697A1 (en) * | 2016-10-13 | 2019-08-21 | AGC Inc. | Diaphragm for electrolyzing alkaline water, and device for electrolyzing alkaline water |
WO2020168023A1 (en) * | 2019-02-14 | 2020-08-20 | The Chemours Company Fc, Llc | Multilayer cation exchange chloralkali membrane |
Non-Patent Citations (1)
Title |
---|
YONGQIANG LI ET AL.: "Fatigue and creep to leak tests of proton exchange membranes using pressure-loaded blisters", JOURNAL OF POWER SOURCES, vol. 194, 2009, pages 873 - 879, XP026499675, DOI: 10.1016/j.jpowsour.2009.06.083 |
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