WO2007114406A1 - 強酸性基で架橋されたイミドネットワークポリマを有する複合電解質膜、その製造方法、及び燃料電池 - Google Patents
強酸性基で架橋されたイミドネットワークポリマを有する複合電解質膜、その製造方法、及び燃料電池 Download PDFInfo
- Publication number
- WO2007114406A1 WO2007114406A1 PCT/JP2007/057343 JP2007057343W WO2007114406A1 WO 2007114406 A1 WO2007114406 A1 WO 2007114406A1 JP 2007057343 W JP2007057343 W JP 2007057343W WO 2007114406 A1 WO2007114406 A1 WO 2007114406A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- monomer
- reactive functional
- electrolyte membrane
- group
- composite electrolyte
- Prior art date
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 258
- 239000002131 composite material Substances 0.000 title claims abstract description 145
- 239000003792 electrolyte Substances 0.000 title claims abstract description 128
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 101
- 239000000446 fuel Substances 0.000 title claims abstract description 37
- 150000003949 imides Chemical class 0.000 title claims abstract description 14
- 230000002378 acidificating effect Effects 0.000 title claims description 90
- 238000004519 manufacturing process Methods 0.000 title claims description 45
- 238000000034 method Methods 0.000 title claims description 42
- 239000005518 polymer electrolyte Substances 0.000 claims abstract description 55
- 238000011049 filling Methods 0.000 claims abstract description 42
- 239000000178 monomer Substances 0.000 claims description 428
- 125000000524 functional group Chemical group 0.000 claims description 253
- 229920000642 polymer Polymers 0.000 claims description 87
- 238000006243 chemical reaction Methods 0.000 claims description 57
- 239000011148 porous material Substances 0.000 claims description 57
- 125000005462 imide group Chemical group 0.000 claims description 56
- -1 polyethylene Polymers 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 239000000126 substance Substances 0.000 claims description 28
- 238000004132 cross linking Methods 0.000 claims description 25
- 229910052731 fluorine Inorganic materials 0.000 claims description 24
- 229910021645 metal ion Inorganic materials 0.000 claims description 20
- 239000004698 Polyethylene Substances 0.000 claims description 19
- 229920000573 polyethylene Polymers 0.000 claims description 19
- 239000004642 Polyimide Substances 0.000 claims description 12
- 229920001721 polyimide Polymers 0.000 claims description 12
- 229910052794 bromium Inorganic materials 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 10
- 229910052740 iodine Inorganic materials 0.000 claims description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 9
- 150000003457 sulfones Chemical class 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 229920002492 poly(sulfone) Polymers 0.000 claims description 8
- 229920001296 polysiloxane Polymers 0.000 claims description 8
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 7
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 230000003197 catalytic effect Effects 0.000 claims description 7
- 229920002530 polyetherether ketone Polymers 0.000 claims description 7
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 7
- 230000008961 swelling Effects 0.000 claims description 7
- 229920003020 cross-linked polyethylene Polymers 0.000 claims description 6
- 239000004703 cross-linked polyethylene Substances 0.000 claims description 6
- 238000009792 diffusion process Methods 0.000 claims description 6
- 239000004743 Polypropylene Substances 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 239000007784 solid electrolyte Substances 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 239000013256 coordination polymer Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 230000009257 reactivity Effects 0.000 claims description 4
- 238000001311 chemical methods and process Methods 0.000 claims description 3
- 239000010411 electrocatalyst Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000000962 organic group Chemical group 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 239000004020 conductor Substances 0.000 claims description 2
- 230000006837 decompression Effects 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 238000009832 plasma treatment Methods 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000007787 solid Substances 0.000 abstract description 44
- 230000015572 biosynthetic process Effects 0.000 abstract description 12
- 238000003786 synthesis reaction Methods 0.000 abstract description 10
- 239000002001 electrolyte material Substances 0.000 abstract description 4
- 239000010408 film Substances 0.000 description 38
- 150000004820 halides Chemical group 0.000 description 33
- 230000001588 bifunctional effect Effects 0.000 description 31
- 239000000203 mixture Substances 0.000 description 29
- 239000000243 solution Substances 0.000 description 27
- 239000002904 solvent Substances 0.000 description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 17
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 15
- 239000002253 acid Substances 0.000 description 15
- 229920006037 cross link polymer Polymers 0.000 description 15
- 229910052739 hydrogen Inorganic materials 0.000 description 14
- 238000003756 stirring Methods 0.000 description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 11
- 230000008859 change Effects 0.000 description 11
- 239000000412 dendrimer Substances 0.000 description 11
- 229920000736 dendritic polymer Polymers 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 11
- 239000011259 mixed solution Substances 0.000 description 10
- 229910021642 ultra pure water Inorganic materials 0.000 description 9
- 239000012498 ultrapure water Substances 0.000 description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 239000007858 starting material Substances 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 125000000542 sulfonic acid group Chemical group 0.000 description 6
- 230000002194 synthesizing effect Effects 0.000 description 6
- 229920000557 Nafion® Polymers 0.000 description 5
- 150000007514 bases Chemical class 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 238000010382 chemical cross-linking Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229920001903 high density polyethylene Polymers 0.000 description 3
- 239000004700 high-density polyethylene Substances 0.000 description 3
- 229920000554 ionomer Polymers 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 3
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 2
- WADSJYLPJPTMLN-UHFFFAOYSA-N 3-(cycloundecen-1-yl)-1,2-diazacycloundec-2-ene Chemical compound C1CCCCCCCCC=C1C1=NNCCCCCCCC1 WADSJYLPJPTMLN-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 229920000491 Polyphenylsulfone Polymers 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001652 poly(etherketoneketone) Polymers 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical group FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- SMYMJHWAQXWPDB-UHFFFAOYSA-N (2,4,5-trichlorophenoxy)acetic acid Chemical compound OC(=O)COC1=CC(Cl)=C(Cl)C=C1Cl SMYMJHWAQXWPDB-UHFFFAOYSA-N 0.000 description 1
- FOYUGSIADQEOEK-UHFFFAOYSA-N 1,1,2,2-tetrafluoro-2-({1,1,1,2,3,3-hexafluoro-3-[(trifluoroethenyl)oxy]propan-2-yl}oxy)ethanesulfonic acid; tetrafluoroethylene Chemical group FC(F)=C(F)F.OS(=O)(=O)C(F)(F)C(F)(F)OC(F)(C(F)(F)F)C(F)(F)OC(F)=C(F)F FOYUGSIADQEOEK-UHFFFAOYSA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- YIWGJFPJRAEKMK-UHFFFAOYSA-N 1-(2H-benzotriazol-5-yl)-3-methyl-8-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carbonyl]-1,3,8-triazaspiro[4.5]decane-2,4-dione Chemical compound CN1C(=O)N(c2ccc3n[nH]nc3c2)C2(CCN(CC2)C(=O)c2cnc(NCc3cccc(OC(F)(F)F)c3)nc2)C1=O YIWGJFPJRAEKMK-UHFFFAOYSA-N 0.000 description 1
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- SXAMGRAIZSSWIH-UHFFFAOYSA-N 2-[3-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,2,4-oxadiazol-5-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NOC(=N1)CC(=O)N1CC2=C(CC1)NN=N2 SXAMGRAIZSSWIH-UHFFFAOYSA-N 0.000 description 1
- 101100257262 Caenorhabditis elegans soc-1 gene Proteins 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910006080 SO2X Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 206010042135 Stomatitis necrotising Diseases 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- FHKPLLOSJHHKNU-INIZCTEOSA-N [(3S)-3-[8-(1-ethyl-5-methylpyrazol-4-yl)-9-methylpurin-6-yl]oxypyrrolidin-1-yl]-(oxan-4-yl)methanone Chemical compound C(C)N1N=CC(=C1C)C=1N(C2=NC=NC(=C2N=1)O[C@@H]1CN(CC1)C(=O)C1CCOCC1)C FHKPLLOSJHHKNU-INIZCTEOSA-N 0.000 description 1
- QQIRAVWVGBTHMJ-UHFFFAOYSA-N [dimethyl-(trimethylsilylamino)silyl]methane;lithium Chemical compound [Li].C[Si](C)(C)N[Si](C)(C)C QQIRAVWVGBTHMJ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011243 crosslinked material Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- VBZWSGALLODQNC-UHFFFAOYSA-N hexafluoroacetone Chemical compound FC(F)(F)C(=O)C(F)(F)F VBZWSGALLODQNC-UHFFFAOYSA-N 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- YNESATAKKCNGOF-UHFFFAOYSA-N lithium bis(trimethylsilyl)amide Chemical compound [Li+].C[Si](C)(C)[N-][Si](C)(C)C YNESATAKKCNGOF-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- NNOYMOQFZUUTHQ-UHFFFAOYSA-N n,n-dimethylsulfamoyl fluoride Chemical compound CN(C)S(F)(=O)=O NNOYMOQFZUUTHQ-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 201000008585 noma Diseases 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920005548 perfluoropolymer Polymers 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- 229920003055 poly(ester-imide) Polymers 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920000636 poly(norbornene) polymer Polymers 0.000 description 1
- 229920002627 poly(phosphazenes) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000120 polyethyl acrylate Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- OETNSIFETJNLBD-UHFFFAOYSA-M sodium;benzenesulfonate;hydrate Chemical compound O.[Na+].[O-]S(=O)(=O)C1=CC=CC=C1 OETNSIFETJNLBD-UHFFFAOYSA-M 0.000 description 1
- 230000000392 somatic effect Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- WITXPSHEXVRIHX-UHFFFAOYSA-K trisodium benzene-1,2,3-trisulfonate Chemical compound [Na+].[Na+].[Na+].[O-]S(=O)(=O)c1cccc(c1S([O-])(=O)=O)S([O-])(=O)=O WITXPSHEXVRIHX-UHFFFAOYSA-K 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/122—Ionic conductors
-
- 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
- C08J5/2275—Heterogeneous membranes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1023—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes
-
- 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
- H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
- H01M8/106—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties characterised by the chemical composition of the porous support
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. insitu polymerisation or insitu crosslinking
-
- 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
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
- H01M2300/0091—Composites in the form of mixtures
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a composite electrolyte membrane having an imid network polymer crosslinked with strongly acidic groups, a method for producing the same, and a fuel cell technical field.
- the present invention relates to a composite electrolyte membrane having an imido network polymer cross-linked with a strongly acidic group, a method for producing the same, and a fuel cell comprising the composite electrolyte membrane.
- composite electrolyte membranes used in various electrochemical devices such as fuel cells, water electrolysis devices, hydrohalic acid electrolysis devices, salt electrolysis devices, oxygen and rice field Z or hydrogen concentrators, humidity sensors, gas sensors, etc.
- the present invention relates to a production method, and a fuel cell using this composite electrolyte membrane as a polymer electrolyte. Background art
- a solid polymer electrolyte is a solid polymer material having an electrolyte group such as a sulfonic acid group in a polymer chain.
- Solid polymer electrolytes have the property of binding tightly to specific ions or selectively permeating cations or anions. Therefore, they are molded into particles, fibers, or membranes, and electrodialyzed. It is used for various applications such as diffusion dialysis and battery diaphragm.
- the polymer electrolyte is formed into a membrane and is in the form of a membrane electrode assembly (MEA) in which electrodes are bonded to both sides.
- MEA membrane electrode assembly
- the electrode In a solid polymer fuel cell, the electrode generally has a two-layer structure of a diffusion layer and a catalyst layer.
- the diffusion layer is for supplying reaction gas and electrons to the catalyst layer, and carbon fiber, carbon paper, etc. are used.
- the catalyst layer is a part that becomes a reaction field of the electrode reaction, and generally consists of a composite of an electrode catalyst and a solid polymer electrolyte.
- Solid polymer electrolytes used in such various electrochemical devices For example, various fluorine-based electrolytes represented by DuPont Nafion (registered trademark) and various hydrocarbon-based electrolytes are known.
- the performance of an electrochemical device depends on the performance of the solid polymer electrolyte used for this. In general, the higher the electrical conductivity of the solid polymer electrolyte, the better the performance of the electrochemical device.
- the electrolyte membrane before starting is in a dry state.
- the membrane swells due to humidified water contained in the reaction gas and generated water generated by the cell reaction. Therefore, if the polymer electrolyte fuel cell is repeatedly started and stopped, the membrane repeatedly swells and contracts. As a result, the solid polymer electrolyte membrane is torn, or the electrode is peeled off from the solid polymer electrolyte membrane, which causes performance degradation.
- various proposals have conventionally been made.
- Patent Document 1 describes a polymer electrolyte membrane obtained by adding hexamethylenediamine (polyfunctional basic compound) to an ethanol solution containing a polymer electrolyte and casting it. ing.
- polyfunctional basic compound hexamethylenediamine
- the polyfunctional basic compound is ion-bonded to a part of the sulfonic acid group of ionomer to form a three-dimensional network. And that this suppresses the flow of ionomers.
- a perfluoro-based polymer compound has a strongly acidic cross-linking group composed of a bissulfuronoleimide group, a sulfonylcarbonylimide group, a biscarboximide group, or a bissulfonylmethylene group.
- a highly heat-resistant polymer electrolyte that is crosslinked via is described.
- Patent Document 3 a sulfonated polyether ether Ke tons chloride (PE EK- S_ ⁇ 2 C 1), by reacting the NH 2 S_ ⁇ 2 (CF 2) 4 S 0 2 NH 2 It is described that a crosslinked polymer in which the polymer main chain is crosslinked with a bissulfo-rimide group is obtained.
- the document states that the water absorption capacity of such crosslinked polymers is reduced compared to non-crosslinked materials and that the conductivity measured at room temperature is 0.065 SZ cm. Has been.
- Patent Document 4 described below describes a method for modifying an electrolyte in which an amine compound is brought into contact with a perfluoropolymer electrolyte or a precursor thereof.
- an amine compound such as ammonia or lithium bis (trimethylsilyl) amide
- a naphthion (registered trademark) film the cleave resistance is improved while maintaining a relatively high electric conductivity. It is described that it is possible.
- Patent Document 1 prevents elution by crosslinking the electrolyte by ionic crosslinking.
- a multifunctional basic compound is added to the solid polymer electrolyte, the polymer chains can be ionically cross-linked via the acidic group of the solid polymer electrolyte.
- ionic bonds are easily broken in environments where water is present. Therefore, when this is used for a long period of time as an electrolyte membrane for fuel cells, an electrolyte in a catalyst layer, etc., ionic bonds may be broken by water present in the system, and the polymer may flow out.
- Patent Documents 2 and 3 are those in which a bridging group between ionomers has a strong acidity and a swelling suppressing function.
- a bridging group between ionomers has a strong acidity and a swelling suppressing function.
- the method of cross-linking solid polymer electrolytes has a limit in the cross-link density that can be reached.
- E W equivalent weight
- the self-supporting membrane configuration in which the electrolyte membrane has a self-supporting structure is very important in consideration of the use of fuel cells and the like.
- Patent Document 5 as a solid polymer electrolyte having both high crosslink density and high electrical conductivity, the molecular weight is 1 000 0 0 or less, and n (n ⁇ 2) in one molecule.
- a second monomer comprising the reactive functional groups A and Z or the reactive functional group B, and in any of these: at least one of the reactive functional groups A and at least one of the aforementioned functional groups.
- a solid polymer electrolyte obtained by reacting a compound containing a reactive functional group B. It is.
- one or more of the first monomers and one or more of the second monomers are either one of these, at least two reactive functional groups A, and at least two. Those containing the reactive functional group B are preferred.
- the solid polymer electrolyte disclosed in Patent Document 5 is an excellent solid polymer electrolyte that has both high crosslink density and high electrical conductivity, but the solid polymer electrolyte that is this high density electrolyte material is used. Are combined,
- Patent Document 1
- Patent Document 2
- Patent Document 3
- Patent Document 4
- Patent Document 5
- Non-patent document 1
- the present invention performs compounding using an imid network polymer that is a high-density electrolyte material
- the present inventors have found that the above problems can be solved by improving the degree of filling of the imid network polymer into the porous film, and have reached the present invention.
- the present invention is an invention of a composite electrolyte membrane in which the pores of a porous membrane are filled with an imide network polymer crosslinked with a strong acidic group, and the imide network polymer comprises: It is obtained by reacting one or more first monomers satisfying the above condition with one or more second monomers.
- the first monomer has a molecular weight of 100000 or less, and includes n (n2) reactive functional groups A and / or reactive functional groups B in one molecule.
- the second monomer has a molecular weight of 100000 or less, and m (m ⁇ 3, 'm ⁇ n) of the reactive functional groups A and Z or the reactivity Contains functional group B.
- the reactive functional group A and the reactive functional group B are bissulfonimide groups (one S 0 2 NHS 0 2 —), sulfone carbonimido groups (one One or more strong acidic bonds selected from S 0 2 NHCO—) or a biscarbonimide group (one CONHCO—) can be formed.
- the one or more two or more first monomers and the one or two or more second monomers each include at least one reactive functional group A and at least 1 And said reactive functional group B.
- the composite electrolyte membrane of the present invention is a composite electrolyte of a porous membrane and an imid network polymer, it is possible to reduce the film thickness to several tens of im or less, which is brittle and difficult to form with the imid network polymer alone. It became. Also porous High degree of packing of imid network polymer crosslinked with strongly acidic groups in the pores of the porous membrane and high proton conductivity.
- the reactive functional group A and the reactive functional group B that form a strongly acidic bond either one is one S 0 2 X or one C OX (where X is F, C 1, Br, I, or OH), and the other is one S 0 2 NZ 1 Z 2 or one CONZ 1 Z 2 (however, Z or Z 2 is One or more kinds selected from H, M, or Si Me 3 are preferred, and M is a metal ion.
- the electrolyte is produced.
- the degree of crosslinking is different, the Young's modulus is different, and a hard polymer and a soft polymer are appropriately blended.
- the reactive functional group A and the reactive functional group B are included in either the first monomer or the second monomer.
- the one or more types of the first monomer and the one or more types of the second monomer may be any one of these, at least two of the reactive functional groups A, and at least two. It is preferable that the reactive functional group B is included.
- first monomer which is the starting compound of the imid network polymer in the composite electrolyte membrane of the present invention
- second monomer include a monomer (5) to a monomer (8) represented by the following chemical formula
- monomers (1 5) ′ to monomers (1 8) represented by the following chemical formulas are preferably exemplified.
- X is F, G, Br, L, or 0H.
- Z ls Z 2 is H, M or SiMe 3 and M are metal ions, respectively.
- Z 3 is H or F.
- the first monomer and the second monomer are used together. Even when the functional group A and / or the reactive functional group B are included in the third monomer, the characteristics of the composite electrolyte membrane of the present invention are also produced. That is, the invention is a composite electrolyte membrane in which a pore of the porous membrane is filled with an imid network polymer crosslinked with a strongly acidic group, and the imid network polymer satisfies the following conditions: It can be obtained by reacting one or more third monomers.
- the third monomer has a molecular weight of 100000 or less and includes p (p ⁇ 3) reactive functional groups A and Z or reactive functional group B in one molecule.
- the reactive functional group A and the reactive functional group B are converted into a bissulfonimide group (one S 0 2 NH S 0 2 —), a sulfone carbonimido group (by the reaction of both reactive functional groups ( It is possible to form one or more strongly acidic bonds selected from one S 0 2 NHCO—) or a biscarbonimide group (one CONHCO—).
- the one type or two or more types of third monomers may include at least one reactive functional group A and at least one reactive functional group B. Including.
- the third monomer is two or more kinds of monomers including a total of three reactive functional groups A and / or reactive functional groups B in one molecule, and any of these monomers.
- Preferred examples include a case where at least two of the reactive functional groups A and at least two of the reactive functional groups B are included.
- the third monomer is one or more monomers including a total of 4 or more of the reactive functional groups A and // or the reactive functional groups B in one molecule, A case where at least two of the reactive functional groups A and at least two of the reactive functional groups B and at least two of the reactive functional groups B are preferably exemplified.
- the reactive functional group A and the reactive functional group B that form a strongly acidic bond one of them is: 1 S0 2 X, or _COX (where X is F, C 1 , Br, I, or OH), and the other is-SO 2 NZ! Z 2 , or one CONZ i Z (where Z 1, Z 2 are one or more selected from H, M, or S i Me 3 , respectively).
- M is a metal ion.
- a strongly acidic bissulfonimide group one S 0 2 NH S 0 2 —
- a sulfone carboxylic imide group one S 0 2 NHCO—
- a bis carboxylic imide group One or more strongly acidic bonds selected from (one CONHCO—) are formed.
- the third monomer which is a starting compound of the polymer network polymer in the composite electrolyte membrane of the present invention, include monomers (5) to monomers (8), and monomers (15) shown in the following chemical formula. ) One or more selected from the group consisting of power and monomer (18) are preferred.
- Pi, P2, P3, 4 S0 2 NZ 1 Z 2.
- l Z 2 is H, M, or SiMe 3t M is a metal ion, respectively.
- Z 3 is H or F.
- ZZ 2 is H, M, or SiMe 3o M is a metal ion, respectively.
- Z 3 is H or F.
- the crosslink density of the imid network polymer in the composite electrolyte membrane of the present invention is preferably 0.1 mm 0 1 Zg or more.
- porous membrane that is the main component of the composite electrolyte membrane of the present invention
- inorganic materials such as silica and alumina and various polymer porous materials can be used.
- porous membrane polyimide (PI), polyether ether ketone (PE EK), polyethylene imide (PE 1), polysulfone (PSF), polyphenylsulfone (PPSU), polyphenylene One selected from lens sulfide (PPS) and cross-linked polyethylene (CLPE)
- PI polyimide
- PE EK polyether ether ketone
- PE 1 polyethylene imide
- PSF polysulfone
- PPSU polyphenylsulfone
- PPS polyphenylsulfone
- CLPE cross-linked polyethylene
- a polytetrafluoroethylene (PTFE) represented by the following general formula or a tetrafluoroethylene copolymer containing 10 mol% or less of a copolymer component is preferably exemplified.
- the porous film is polysiloxane
- the organic group in the polysiloxane is at least one group selected from methyl group, phenyl group, hydrogen group or hydroxyl group. Those are preferably exemplified.
- the present invention is an invention of a method for producing the composite electrolyte membrane.
- a step of filling the first monomer and the second monomer as raw materials for the imidone: y-work polymer that is crosslinked in the pores of the porous membrane with a strongly acidic group, and the pores of the porous membrane A porous membrane having pores, comprising a step of forming an imid network polymer and a step of producing the imid network polymer, and the imid network polymer is filled in the pores
- a method for producing a composite electrolyte membrane comprising an imido network polymer crosslinked with a strongly acidic group, one or more first monomers satisfying the following conditions, and one or two or more second monomers It is obtained by reacting with a monomer.
- the first monomer has a molecular weight of 1 000 0 0 0 or less, Includes n (n ⁇ 2) reactive functional groups A and / or reactive functional groups B.
- the second monomer has a molecular weight of 100000 or less, and m (m ⁇ 3, m ⁇ n) of the reactive functional group A and / or the reactive functional group in one molecule. Contains group B.
- the reactive functional group A and the reactive functional group B are converted into a bissulfonimide group (one S 0 2 NHS 0 2 —), a sulfone carbonimido group (one S 0 2 NHCO—), or one or more strongly acidic bonds selected from a biscarponimide group (one CONHCO—).
- the one or more kinds of the first monomers and the one or more kinds of the second monomers are any one of these, at least one of the reactive functional groups A, and at least 1 And said reactive functional group B.
- first monomer one or more of monomers (1) to monomers (18) shown in the following chemical formula are preferably exemplified, and specific examples of the second monomer are shown in the following chemical formula.
- second monomer any one or more of (5) to 'monomer (8) and monomers (15) to (18) represented by the following chemical formula are exemplified.
- Z 2 is H, M or SiMe 3 , respectively.
- M is a metal ion.
- Z 3 is H or F.
- X is F, G and Br, or 0H. ⁇
- l Z 2 is H, M, or SiMe 3 or metal ion, respectively.
- Z 3 is H or F.
- the first monomer and the second monomer are used together, but when the specific reactive functional group A and / or the reactive functional group B is included in the third monomer,
- the characteristics of the composite electrolyte membrane of the present invention are produced. That is, a step of filling the pores of the porous membrane with a third monomer that is a raw material of an imid network polymer crosslinked with strongly acidic groups, and the imid network polymer in the pores of the porous membrane A porous membrane having pores, and a method for producing a composite electrolyte membrane in which pores are filled with an imidonetwork polymer.
- the imid network polymer bridged by the strongly acidic group can be obtained by reacting one or more third monomers satisfying the following conditions.
- the third monomer has a molecular weight of 100000 or less and includes p (p ⁇ 3) reactive functional groups A and / or reactive functional groups B in one molecule.
- the reactive functional group A and the reactive functional group B are converted into a bissulfonimide group (one S 0 2 NH S 0 2 _), a sulfone carboxyl group ( It is possible to form one or more strongly acidic bonds selected from one S 0 2 NHCO—) or a biscarbonimide group (—CONHCO—).
- the one or more third monomers may include at least one reactive functional group A and at least one reactive functional group B. Including.
- the third monomer is two or more kinds of monomers including a total of three reactive functional groups A and Z or the reactive functional group B in one molecule, and any one of these monomers. Further, a case where at least two reactive functional groups A and at least two reactive functional groups B are included is preferably exemplified.
- the third monomer is one or two or more monomers including a total of 4 or more of the reactive functional groups A and Z or the reactive functional group B in one molecule, and both these reactions.
- a case where at least two of the reactive functional groups A and at least two of the reactive functional groups B are included in any of the functional functional groups is preferably exemplified.
- Specific examples of the reactive functional group A and the reactive functional group B are as described above.
- Specific examples of the third monomer include the monomer (5) shown in the chemical formula below.
- Preferred examples include at least one selected from Noma (8) and Monomer (15) to Monomer (18).
- P 3. P4 S0 2 ZiZ 2. S0 2 X, ⁇ N3 ⁇ 4 Z 2 , or
- X is F, CU Br, or 0H. ⁇
- Z 2 is H, M, or Si e 3o M is a metal ion, respectively.
- Z 3 is H or F.
- the manufacturing method of the composite electrolyte membrane of the present invention includes several modified examples.
- the basic method of the production method of the present invention includes a step of filling the first monomer and the second monomer, and a step of forming an imid network polymer in the pores of the porous membrane once. Even when the process of filling the first monomer and the second monomer and the process of forming the imid network polymer in the pores of the porous membrane are repeated two or more times, the formation of the imid network polymer is also possible. This is preferable. In addition to the step of filling the first monomer and the second monomer, and the step of forming an imid network polymer in the pores of the porous membrane, It is also preferable to repeat the step of prototyping the imid network polymer two or more times.
- the basic method of the production method of the present invention includes a step of filling the third monomer and a step of forming an imid network polymer in the pores of the porous membrane once.
- the step of filling the third monomer and the step of forming the imid network polymer in the pores of the porous membrane are also preferred from the viewpoint of forming the imid network polymer.
- the step of converting the imid network polymer into a proton is repeated two or more times. It is also preferable.
- the filling monomer is changed each time and two or more types of polymers are changed.
- Producing is also included in the method for producing a composite electrolyte membrane of the present invention.
- the method for producing a composite electrolyte membrane of the present invention includes a step of crosslinking the molecules of two or more kinds of produced polymers.
- the two or more types of polymers have any of the following physical properties (1) to (3).
- the ionic conductivity of the two or more types of polymers is different.
- the volume swelling ratio of the two or more kinds of polymers with respect to water is different.
- the volume swelling ratio of the polymer with respect to water is preferably 10 to 400%, more preferably 100 to 300%.
- the polymer produced at the second time or later than the polymer produced at the first time has a lower elastic modulus, higher elongation, and higher viscosity.
- the step of filling the monomer in the step of filling the monomer, it is effective to employ one or more methods selected from ultrasonic, deaeration, decompression, and interface treatment (plasma treatment).
- the bridge density of the imid network polymer in the composite electrolyte membrane is 0.1 mmo 1 Zg or more.
- Crosslink density is 0.0.
- High proton conductivity can be obtained by using 1 mmo 1 Zg or more.
- porous membrane used in the method for producing a composite electrolyte membrane of the present invention are as described above.
- the present invention is an electrolyte membrane for a fuel cell comprising the above composite electrolyte membrane.
- the present invention is a chemical process film comprising the above composite electrolyte film.
- the present invention is a fuel cell using the above composite electrolyte membrane. That is, a gas diffusion electrode (a) comprising a polymer solid electrolyte membrane (a) and an electrocatalyst composed of a conductive carrier carrying a catalytic metal and a proton conducting material, which are joined to the electrolyte membrane, as main constituent materials ( and b) a polymer electrolyte fuel cell having a membrane electrode assembly (MEA), wherein the polymer solid electrolyte membrane is the above composite electrolyte membrane.
- a gas diffusion electrode comprising a polymer solid electrolyte membrane (a) and an electrocatalyst composed of a conductive carrier carrying a catalytic metal and a proton conducting material, which are joined to the electrolyte membrane, as main constituent materials
- MEA membrane electrode assembly
- Immediate network polymer has high proton conductivity, but its skeletal structure is hard and its flexibility is low, so it is difficult to keep it alone.
- An imid network polymer that is difficult to form by itself can be formed into a film thickness of, for example, several tens of meters / m or less.
- a polycondensation electrolyte material which has been difficult to form a composite film, can be formed into a composite film.
- the pore surface of the porous material can be functionalized by using an imid network polymer crosslinked with strongly acidic groups. Brief description of the drawings ''
- FIG. 1 shows the I-V characteristic evaluation and cell resistance of ME A using the composite films obtained in Example 25 and Comparative Example 3.
- a polymer porous membrane is desirable.
- methacrylate resins such as polymethyl methacrylate (PMMA); polystyrene, acrylonitrile monostyrene copolymer (AS resin), acrylonitrile monobutadiene-styrene copolymer (AB) Polystyrene; Polyimide; Polyester imide; Polyacetal; Polyarylate; Polyaryl; Polysulfone Polyurethanes; Polyether ketones; Polybutyl esters such as polybutyl butyl acrylate and polyethyl acrylate; Polybutyl esters such as polybutoxymethylene; Polysiloxanes; Polysiloxanes; Polyphosphazenes; Poly Polycarbones; Polynorbornene; Epoxy resin; Polyvinyl alcohol; Polyvinyl chloride; Polyenes such as polyisoprene and polybutadiene; Polyalkenes such as polyisobutylene; Vinylidene fluoride tree Fluorine resins such as
- functional groups may be introduced into the pore surface for the purpose of improving the adhesion with the electrolyte.
- the functional group those corresponding to ⁇ 2 and ⁇ 3 in the monomer (5) represented by the above chemical formula are preferable.
- Preferred examples of the inorganic porous film include silica and alumina.
- the technique for opening pores in the above-described polymer material is not particularly limited, and various methods such as a stretching method, a solution casting method, an etching method by chemical treatment, and a laser beam irradiation method can be used.
- porous membrane which is the main component of the composite electrolyte membrane of the present invention is used in a fuel battery.
- the pore size of the porous membrane is 0.0 1 ⁇ ! -3 m is preferable, and 0.05 m to 1 m is more preferable.
- the pore size is small, it is difficult to impregnate the monomer, and the filling rate of the network polymer in the composite membrane tends to be small.
- the pore size is large, there is a tendency that the effect of reinforcing the mechanical strength of the composite membrane and the effect of suppressing the dimensional change when containing water are not obtained.
- the porosity of the porous membrane is preferably 20% to 95%, more preferably 40% to 95%, and even more preferably 40% to 80%.
- the porosity is small, the ratio of the electrolyte in the composite membrane decreases, and sufficient conductivity cannot be obtained.
- the porosity is large, the proportion of the base material in the composite membrane is reduced, and sufficient mechanical strength reinforcement effect and suppression effect of dimensional change when containing water cannot be obtained.
- the thickness of the porous membrane is 5 ⁇ ⁇ ! ⁇ 500 m, preferably 10 ⁇ m to 2,000 ⁇ m, more preferably 15 m to 100 ⁇ m.
- the film thickness is too thin, the mechanical strength of the composite film is not sufficient, and the durability tends to decrease.
- the film thickness is too thick, the proton conduction in the film thickness direction of the composite film decreases, and when used in a fuel cell, the power generation characteristics tend to deteriorate.
- the “imido network polymer crosslinked with a strong acid group” constituting the electrolyte portion in the composite electrolyte membrane of the present invention will be specifically described.
- the “imido network polymer crosslinked with a strongly acidic group” as used in the present invention is a solid polymer electrolyte having both a high crosslinking density and a high electrical conductivity.
- the “imido network polymer bridged by a strongly acidic group”, which is a polymer electrolyte according to the first embodiment of the present invention, includes one or more first monomers satisfying a predetermined condition, and 1 It is obtained by reacting a seed or two or more second monomers.
- the “first monomer” means that the molecular weight is not more than 100 00, and n (n ⁇ 2) reactive functional groups A and B-reactive functional groups B are included in one molecule. Say something to include.
- the “second monomer” means that the molecular weight is not more than 100 000 and m (m ⁇ 3, m ⁇ n) reactive functional groups A and Z or reactive functionalities in one molecule. Say something containing group B.
- reactive functional group A and “reactive functional group B” refer to bissulfonimide group (one S 0 2 NH S 0 2 —), sulfone carbonimido group (_ SO 2 NH CO-), or a functional group capable of forming a biscarbonimide group (_CONHCO_) (hereinafter collectively referred to as “strongly acidic imide group”).
- the molecular weights of the first monomer and the second monomer are not particularly limited, and optimal values are selected according to the characteristics and applications required for the polymer electrolyte.
- the smaller the molecular weight of the first monomer and Z or second monomer A solid polymer electrolyte having a high crosslink density and high electrical conductivity can be obtained.
- the higher the molecular weight of the first monomer and Z or the second monomer the more flexible the polymer electrolyte can be obtained.
- the molecular weight of the monomer is too high, it will be difficult to achieve both high crosslink density and high electrical conductivity at the same time. For this reason, it is preferable to use the first monomer and the second monomer having a molecular weight of 1 000 or less, respectively.
- the molecular weights of the first monomer and the second monomer are preferably 1 30 or more and 100 0 or less, respectively.
- the reactive functional group A and the reactive functional group B contained in the first monomer and the second monomer can be reacted by directly reacting them or after adding an appropriate functional group conversion.
- Any material capable of forming a strongly acidic imido group may be used.
- the reactive functional group A is — S ⁇ 2 X, or one COX (where X is F, C 1, Br, I, or OH) (hereinafter referred to as “halide functional group”)
- the reactive functional group B is one of S OsNZ i Z 2 , or —CONZ i Z s (where Z Z 2 is H, M, or S i Me 3 , respectively.
- M is a metal Ions.) (Hereinafter referred to as “imido functional group”) or vice versa.
- the metal ion M is preferably a monovalent metal ion such as Li, K, or Na.
- halide functional group and imide functional group is often easy to react directly without adding functional group conversion, so the combination of reactive functional group A and reactive functional group B Is particularly suitable.
- these functional groups can be converted into sulfonic acid groups or carboxylic acid groups by appropriate treatment, so that a solid having high electrical conductivity can be obtained.
- a polymer electrolyte is obtained.
- halide functional groups those in which X consists of F, C 1, Br or I have high reactivity, so they are designated as reactive functional group A or reactive functional group B. Is preferred.
- the combination of (Z ⁇ Z 2 ) is (H, H), (H, M), (S i Me e 3 , M), or (H, S i Me Since those having 3 ) have high reactivity, they are suitable as the reactive functional group A or the reactive functional group B.
- the total number n of reactive functional groups A and reactive functional groups B contained in one molecule of the first monomer may be two or more.
- the total number m of reactive functional groups A and reactive functional groups B contained in one molecule of the second monomer is 3 or more, and is different from the total number n of functional groups in the first monomer. If it is a thing (m ⁇ n).
- the first monomer may include only one of the reactive functional group A and the reactive functional group B, or may include both.
- these reactive functional groups A (or reactive functional groups B) are the same type. (For example, only one S 0 2 X) or a different type of functional group (for example, one so 2 x and —COX combination). The same applies to the second monomer.
- first and second monomers There are various types of such first and second monomers. Among these, the monomer (1) to monomer (8). And the monomer (9) to monomer (18) shown in the following formula are suitable as the first monomer.
- Pi, P2, P3, 4 S0 2 NZ 1 Z 2.
- X is G and Br, or 0H.
- l Z 2 is H, M, or SiMe 3 , respectively.
- M is a metal ion.
- Z 3 is H or F. ⁇ 22 ⁇ 28 (CF 2 ) M S0 2 X (10) Z 1 Z 2 N0C (CF2) M SO2X
- the monomer (5) to monomer (8), and the monomer (5) force and the monomer (18) shown in the following formula are suitable as the second monomer.
- these monomers those that do not contain a C-H bond in the molecule are particularly suitable because the polymer chain becomes a perfluoro skeleton, and a solid polymer electrolyte excellent in heat resistance and oxidation resistance is obtained. is there. .
- X is F, G and Br, or 0H.
- ZZ 2 is H, M, or Si Me 3 and M are metal ions, respectively.
- Z 3 is H or F.
- Pi, P2, P3, 4 S0 2 NZ 1 Z 2.
- l Z 2 is H, M, or SiMe 3 , respectively.
- M is a metal ion.
- Z 3 is H or F.
- Examples of the first monomer and the second monomer other than the above include, for example, an oligomer having a molecular weight of not more than 100 0 0 selected from naphthion monomers and monomers (A) to (F) represented by the following formulas, or derivatives thereof: A suitable example is given.
- Z and Z 2 are H, M, or Si Me 3 respectively.
- M is a metal ion
- one or two or more first monomers and one or two or more second monomers are used to synthesize a “imide network polymer crosslinked with a strongly acidic group”
- one or two One or more species of the first monomer and one or more species of the second monomer are any of these, and at least one reactive functional group A And at least one reactive functional group B.
- one or more of the first monomers and one or more of the second monomers must be at least one of these. Those containing at least two reactive functional groups A and at least two reactive functional groups B are preferred.
- a bifunctional monomer having two imide functional groups (A) for example, the monomer (1) or (2) shown in the above formula.
- AA the monomer (1) or (2) shown in the above formula.
- AA the monomer represented by the above formula (15)
- AAB the trifunctional monomer having two imide functional groups
- AAB the monomer represented by the above formula (15)
- AAB the trifunctional monomer AAB
- the trifunctional monomer AAB is bonded to both ends of the bifunctional monomer AA, and the oligomer having the structure “AAB_AA_BAA” is obtained.
- a total of two strongly acidic imide groups (“; B—A” and “A—B”) are formed at the point of attachment of the bifunctional monomer AA and the trifunctional monomer AAB.
- the halide functional group (B) of the trifunctional monomer AAB binds to one of the imide functional groups (A) at the end of the oligomer.
- a new strongly acidic imide group (AB) is formed.
- a so-called “dendrimer” in which polymer chains grow radially with the bifunctional monomer AA as the center can be formed.
- a bifunctional monomer having one imide functional group (A) and one halide functional group (B) for example, the monomer (9) shown in the above formula, (1 0), (1 2), or (1 4).
- this is abbreviated as “AB”.
- AB halide functional groups
- B 3 halide functional groups
- the imide functional group (A) of the bifunctional monomer AB is bonded to one of the halide functional groups (B) at the end of the oligo.
- a strongly acidic imido group (AB) is formed.
- a so-called “dendrimer” in which polymer chains grow radially centering on the trifunctional monomer BBB can be formed.
- a bifunctional monomer AA having two imido functional groups (A) is used as the first monomer, and three halide functional groups (B) are used as the second monomer.
- the trifunctional monomer BBB is used, an oligomer having the structure “AA—BB ′ (AA) B—AA” can be obtained by reacting them.
- the trifunctional monomer BBB and the bifunctional monomer AA are bonded in this order to one of the imide functional groups (A) at the end of the oligomer.
- a new strongly acidic imidazole group (AB) is formed.
- an “imido network polymer crosslinked with a strongly acidic group” in which the grown polymer chains are crosslinked with each other via the bifunctional monomer AA can be obtained.
- a bifunctional monomer AA having two imido functional groups (A) is used as the first monomer, and one imido functional group (A) and two are used as the second monomer.
- a trifunctional monomer BAB having a halide functional group (B) for example, the monomer (15) shown in the above formula
- the structure “AA— BAB— AA” is obtained.
- the oligomer having is obtained.
- the halide functional group (B) of the trifunctional monomer BAB is newly bonded to any imide functional group (A) at the end or center of the oligomer. In this, a strongly acidic imide group (A_B) is newly formed.
- the halide functional group (B) remaining at the end of the oligomer further binds to the new trifunctional monomer BAB or imide functional group (A) of the bifunctional monomer AA.
- a new strongly acidic imide group (AB) is formed.
- a “imido network polymer cross-linked with a strong acid group” in which the grown polymer chains are cross-linked with each other via a bifunctional monomer AA is obtained.
- a bifunctional monomer AB having one imide functional group (A) and one halide functional group (B) is used as the first monomer, and one monomer is used as the second monomer.
- a trifunctional monomer BAB having an imide functional group (A) and two halide functional groups (B) is used, reaction of these results in an oligomer having the structure “BA- BAB-AB”. can get.
- the imide functional group (A) of the bifunctional monomer AB or the trifunctional monomer BAB is bonded to one of the halide functional groups' (B) at the end of the oligomer.
- a new strongly acidic imide group (A 1 B) is formed.
- the halide functional group (B) of the bifunctional monomer AB or the trifunctional monomer BAB is bonded to one of the imide functional groups (A) at the end of the oligomer.
- a strongly acidic imide group (AB) is formed in the following, such a reaction is sequentially repeated to obtain a “imido network polymer cross-linked with a strong acid group” in which the grown polymer chains are cross-linked with each other by a bifunctional monomer AB.
- a bifunctional monomer AB having one imide functional group (A) and one halide functional group (B) is used as the first monomer, and three monomers are used as the second monomer.
- a trifunctional monomer AAA having an imide functional group (A) for example, a monomer (5) shown in the formula 5
- a trifunctional monomer BBB having three halide functional groups these are used.
- the trifunctional monomer AAA reacts with the bifunctional monomer AB to obtain an oligomer having the structure “AB—AA (BA) A—BA”. .
- the trifunctional monomer BBB or the bifunctional monomer BA is first bonded to one of the imide-based functional groups (A) at the end of the oligomer.
- a strongly acidic imide group (AB) is formed in
- the trifunctional monomer AAA or the bifunctional monomer AB is further bonded to the halide functional group (B) at the end, and the trifunctional monomer (A) is further bonded to the trifunctional monomer (A).
- BBB or bifunctional monomer BA Bonding occurs, and a strong acid imide group (AB) is newly formed at each bonding point.
- an “imido network polymer crosslinked with strongly acidic groups” in which the grown polymer chains are mutually crosslinked is obtained.
- a bifunctional monomer AA having two imide functional groups (A) and a bifunctional monomer BB having two halide functional groups (B) are used as the first monomer.
- a trifunctional monomer BBB having three halide functional groups (B) is used as the two monomer, when these are reacted, the trifunctional quinoma BBB reacts with the bifunctional monomer AA, and “AA”
- An oligomer having the structure _BB (AA) B—AA is obtained.
- the trifunctional monomer BBB or the bifunctional monomer BB is first bonded to one of the imide functional groups (A) at the end of the oligomer, and each of the bonding points is newly added.
- a strongly acidic imide group (AB) is formed in
- the bifunctional monomer AA is further bonded to the halide functional group (B) at the end, and a new strongly acidic imide group (A-B) is formed at each bonding point. Is done.
- a “imid network polymer crosslinked with strongly acidic groups” in which the grown polymer chains are mutually crosslinked is obtained. ⁇
- At least one reactive functional group A and at least one reactive functional group A are added to any of a plurality of different types of monomers.
- the reactive functional group B is included, a dendrimer in which polymer chains are grown radially can be obtained.
- any of a plurality of different types of monomers contains at least two reactive functional groups A and at least two reactive functional groups B, the polymer chains are mutually connected. Cross-linked “imido network polymer cross-linked with strongly acidic group” is obtained.
- the combination ratio of one or more types of first monomer and one or more types of second monomer depends on the required properties of the synthesized ⁇ imido network polymer cross-linked with strongly acidic groups ''. Select the optimal ratio accordingly.
- dendrima When synthesizing the polymer, it is preferable to relatively increase the ratio of the monomer constituting the polymer chain to the monomer serving as the core of the dendrimer.
- the ratio of the monomer constituting the polymer chain is preferably 10 mol or more and 70 mol or less, more preferably 30 mol or more, with respect to 1 mol of the monomer serving as the core of the dendrimer. T is 300 mol or more.
- these dendrimers may be made to be “imido network polymers cross-linked with strongly acidic groups” by further reacting one having a reactive functional group A and one having a reactive functional group B with each other. it can.
- the number of moles of the reactive functional group A and the number of moles of the reactive functional group B contained in the first monomer and the second monomer are determined.
- a strongly acidic imide group can be generated from all the reactive functional groups A and B.
- the number of moles of the reactive functional group A and the reactive functional group B contained in the first monomer and the second monomer is not necessarily the same, and either one may be excessive or insufficient. This is because even if either one is excessive or deficient, unreacted reactive functional group A or reactive functional group B remains in the polymer chain, or a polymer crosslinked in a network form. This is because it is thought that linear or branched polymer chains only grow radially around the periphery. However, if the ratio of the reactive functional group A and the reactive functional group B deviates greatly from the theoretical value, unreacted monomers or low molecular weight oligomers remain in the solid polymer electrolyte, and these monomers are used during use. Or, the oligomer may be eluted, which is not preferable. Therefore, it is better to follow the so-called gelation theory when synthesizing “imido network polymer crosslinked with strongly acidic groups”.
- a branching unit connects to the next branched monomer via a bifunctional monomer If the probability is ⁇ , (1 ⁇ 1) is the probability that a chain from a branch does not extend further through the branch. So if the branching point is trifunctional> 1 ⁇ 2 and if the branching point is f-functional, ⁇ > 1 Z (f-1), the molecule will go on infinitely. Let ⁇ be the gel point where the infinite mesh has just begun. Then,.
- the ratio of the reactive functional group B to 1 mole of the reactive functional group A is 0.5. It is preferable to blend the first monomer and the second monomer so that the amount is from 2 to 2 moles.
- the ratio of the reactive functional group B to 1 mol of the reactive functional group A is more preferably 0.8 mol or more and 1.2 mol or less.
- the ratio of the reactive functional group B to 1 mole of the reactive functional group A is 0.3 mol or more.
- the first monomer and the second monomer are preferably blended so as to be less than or equal to a mole.
- the ratio of the reactive functional group B to 1 mol of the reactive functional group A is more preferably 0.6 mol or more and 1.5 mol or less.
- the porous film is made of polytetrafluoroethylene, polyimide, polyethylene, polyethylene. From Tetrafluoroethylene, pFA (Tetrafluoroethylene perfluoroethylene port vinylol ether copolymer), FEP (Tetrafluoroethylene hexafluoropropylene copolymer), porous silica, porous ceramics, etc. It is preferable to use In this case, select the optimum values for the porosity, average pore diameter, thickness, etc. of the porous membrane in accordance with the application of the composite electrolyte membrane and the required characteristics.
- the “imido network polymer crosslinked with a strongly acidic group” may be uniformly dispersed in the porous film, or may be unevenly distributed on the surface or inside of the porous film.
- crosslinking means “physical crosslinking” formed by physical entanglement of polymer chains, and the polymer chains are molecularly crosslinked by the first monomer or the second monomer. “Chemical cross-linking” means both.
- Crosslink density can be prepared by optimizing the synthesis conditions.
- the higher the crosslink density the less the swelling / shrinkage with respect to water, and the solid polymer electrolyte with excellent heat resistance and durability can be obtained.
- the crosslinking density is preferably 0.1 mm o 1 Zg or more, more preferably 0.5 mm o 1 / g or more.
- the electrical conductivity of the solid polymer electrolyte is preferably 0. Ol SZ cm or more, more preferably 0.05 S / cm. More than cm.
- the solvent used may be any solvent that can dissolve additives such as monomers and bases used in the reaction.
- amide solvents such as highly polar acetonitrile, dimethylacetamide, and dimethylformamide
- ether solvents such as jetyl ether and tetrahydrofuran
- halogen solvents such as chloroform and dichloromethan
- hydrocarbon solvents such as hexane
- the polymer solid part and the solvent may be separated during gelation, but it may be advantageous for high loading of the polymer in the porous membrane. May be used.
- the concentration of the solvent used tends to increase the filling rate into the porous membrane as the monomer concentration increases. If the monomer is liquid and can be impregnated into the porous material alone, it is not necessary to use a solvent.
- the solid part after polymerization is preferably 10% to 90% by weight. More preferably, it is 30 to 80% by weight.
- the solvent can be distilled off in the middle of the polymerization step, and the solid content concentration can be increased to improve the filling rate. It is preferable that the solvent is retained immediately before the gel point. If the timing of solvent retention is too fast, some of the monomer may be distilled off and the crosslinking density of the network polymer may be reduced. If the timing of solvent retention is too late, the polymer component will become more viscous than gelation and lose its fluidity, and may not be able to enter the porous material effectively.
- the “imido network polymer cross-linked with a strongly acidic group” is a mixed liquid containing one or more first monomers and one or more second monomers. Can be synthesized by reacting the first monomer and the second monomer.
- the first monomer and the second monomer may be reacted as they are, or may be reacted after appropriate functional group conversion.
- the first monomer and the second monomer are preferably dissolved in a solvent capable of dissolving both.
- the solvent may be selected according to the type of the first monomer and the second monomer, and is not particularly limited. Also in solution The concentration of the first monomer and the second monomer to be contained is not particularly limited, and an optimal one may be selected according to the type of the first monomer and the second monomer.
- a reagent that increases the reaction rate of the reactive functional group A and the reactive functional group B may be added thereto.
- a reagent specifically, basic compounds such as triethylamine, trimethylamine, tripropylamine, tributylamine, DBU (diazabicycloundecene) and the like are suitable.
- the amount of the reagent having a catalytic action is selected in accordance with the use of the solid polymer electrolyte and the required characteristics. By optimizing the amount of reagent, the viscosity of the mixture can be adjusted.
- a porous membrane may be disposed on the bottom of a shallow container, a small amount of the mixed solution may be poured from above, and the thus prepared mixed solution may be impregnated inside the porous membrane.
- the mixed solution contains a reagent having a catalytic action
- the reaction has already progressed to some extent inside the mixed solution, and the viscosity of the mixed solution may increase.
- a small amount of the mixed solution is poured from above the porous membrane and then pressure is applied to press the mixed solution into the porous membrane. .
- pressure is applied to press the mixed solution into the porous membrane.
- the reaction of the first monomer and the second monomer is preferably carried out in an inert atmosphere such as Ar or N 2 in order to prevent alteration such as hydrolysis of the first monomer and the second monomer.
- the reaction temperature, reaction time, and pressure during the reaction are not particularly limited, and the types of the first monomer and the second monomer, the concentration of the mixed solution, and the type and amount of the reagent having a catalytic action. The optimum value is selected according to the above.
- a method in which a synthesized polymer is treated with an acid such as nitric acid to produce a proton and a method in which a synthesized polymer is saponified with an alkaline solution and then treated with an acid to produce a proton. Etc. are suitable.
- the polymer network according to the second embodiment of the present invention “imido network polymer crosslinked with a strongly acidic group” contains one or more third monomers satisfying a predetermined condition. It is obtained by reacting.
- the “third monomer” means a molecular weight of 1 000 000 or less, and p (p ⁇ 3) reactive functional groups A and / or reactive functional groups B in one molecule.
- the present embodiment is characterized in that one or two or more third monomers having the same number of functional groups per molecule are used as starting materials.
- the molecular weight of the third monomer and the types and combinations of the reactive functional group A and reactive functional group B contained in the third monomer are the same as those of the first monomer and the second monomer described above. Therefore, explanation is omitted.
- the total number of reactive functional group A and reactive functional group B contained in one molecule of the third monomer may be p (p ⁇ 3). Further, the third monomer may include only one of the reactive functional group A and the reactive functional group B, or may include both. Further, when the third monomer contains two or more reactive functional groups A (or reactive functional groups B), these reactive functional groups A (or reactive functional groups B) are of the same type. It may be a functional group (for example, only 1 S 2 X), or may be a different type of functional group (for example, a combination of 1 SO 2 X and 1 COX).
- a third monomer there are various monomers.
- the monomer (5) to monomer (8) and the monomer (15) to monomer (18) shown in the following formula are suitable as the third monomer.
- those that do not contain a C—H bond in the molecule have a polymer chain with a perfluoro skeleton, resulting in a solid polymer electrolyte with excellent heat resistance and oxidation resistance. Is particularly suitable.
- Suitable third monomers include, for example, Nafion monomers and oligomers having a molecular weight selected from the following formulas (A) to (F) of 1 000 or less, or derivatives thereof. Can be mentioned.
- third monomers When one or two or more types of third monomers are used to synthesize an “imid network polymer bridged with a strongly acidic group”, one or more types of third monomers are used. Must contain at least one reactive functional group A and at least one reactive functional group B. The '
- the third monomer when chemical crosslinking is introduced into the “imido network polymer crosslinked with a strong acidic group”, when a compound having three reactive functional groups in one molecule is used as the third monomer, It is preferable to use two or more kinds of third monomers, each of which contains at least two reactive functional groups A and at least two reactive functional groups B. In addition, when the third monomer having four or more reactive functional groups in one molecule is used, it is one or two or more third monomers, and at least 2 It is preferable to use those containing one reactive functional group A and at least two reactive functional groups B.
- the halide functional group (B) of the new trifunctional monomer AAB binds to the imide functional group (A) at the end of the oligomer.
- the amide functional group (A) of the new trifunctional monomer AAB is bonded to the halide functional group (B) at the end, and a new strongly acidic imide group (A) is attached to each bonding point.
- — B) is formed.
- a trifunctional monomer AAA having three imide functional groups (A) and a trifunctional monomer BBB having three halide functional groups (B) were used as the third monomer.
- an oligomer having a structure of “A AA—BB (AAA) B—AAA) is obtained by reacting them.
- the trifunctional monomer BBB binds to one of the imide functional groups (A) at the end of the oligo, and a new strongly acidic imide is attached to each of the bonding points.
- the group (A-B) is formed.
- a “imid network polymer crosslinked with strongly acidic groups” in which the grown polymer chains are crosslinked with each other can be obtained.
- a tetrafunctional monomer AA AB having three imide functional groups (A) and one halide functional group (B) is used as the third monomer
- One tetrafunctional monomer AAAB's halide functional group (B) and another trifunctional monomer AAA B's imide functional group (A) bind to yield an oligomer with the structure “AAAB—AAAB”. It is done.
- one imide group (BA) is formed at the point of attachment.
- a new tetrafunctional monomer AAAB has a halide functional group (B) bound to (A), and a new tetrafunctional monomer (B) at the end of the oligomer has a new tetrafunctional monomer.
- AAAB's imide functional group (A) is bonded, and a strongly acidic imide group (A-B) is newly formed at the bonding point.
- A-B strongly acidic imide group
- one of the imide functional groups (A) at the end of the oligomer has a new tetrafunctional monomer AAB B /, a rigid functional group.
- the “imido network polymer crosslinked with a strongly acidic group” according to the present embodiment is synthesized by preparing a mixed solution containing one or more third monomers and reacting the third monomers. be able to.
- the manufacturing method according to the present embodiment is the same as that of the first embodiment except that one or two or more third monomers are used as a starting material, and thus the description thereof is omitted.
- the action of the “imido network polymer crosslinked with a strongly acidic group” according to the present invention will be described.
- the two monomers react with the reactive functional group A.
- an imide group that functions as a strong acid group is formed at the bonding point. Therefore, as the polymerization proceeds, acidic groups increase, and a solid polymer electrolyte having high electrical conductivity can be obtained.
- physical or chemical crosslinks are also formed between the polymer chains.
- the composite electrolyte according to the present invention when used as an electrolyte membrane for a fuel cell, since a physical or chemical crosslink is formed in the membrane, the outflow of high molecules is suppressed. In addition, since the swelling / shrinkage of the film is suppressed by the cross-linking, it is possible to suppress performance degradation due to film tearing or electrode peeling. In addition, fuel hydrogen leaks due to membrane tearing are also suppressed, improving fuel economy. In particular, in a crosslinked network type solid polymer electrolyte, the polymer chains are chemically cross-linked, so even if the amount of acidic groups is increased, there is no risk of the polymer flowing out. High resistance.
- the first to third monomers are synthesized by using a commercially available monomer having a similar molecular structure as a starting material, and performing a predetermined functional group conversion using a known method. can do.
- the trifunctional monomer “F 0 2 S—CF 2 _C (F) (SO 2 F) and CF 2 — SO 2 F” with three sulfonyl fluoride groups (halide functional groups) is It can be synthesized by the procedure shown in the following formula.
- the monomer is immersed in a 30% aqueous hydrogen peroxide solution at room temperature for 72 hours. Next, it is treated with 1N sulfuric acid at 100 ° C for 1 hour and washed with ion-exchanged water. As a result, the terminal thio (s x )
- this monomer is mixed with phosphorus pentachloride (PC 1 5 ) 10 0 g, oxychloride Li down (POC l 3) dissolved in a solution containing the 2 5 0 g, reacted for 12 hours at 9 0 ° C. After the reaction, the solvent was removed, in the wash with carbon tetrachloride (CC 1 4) (6 0 ° C, 3 hours, agitation).
- PC 1 5 phosphorus pentachloride
- POC l 3 oxychloride Li down
- a trifunctional monomer “1, 3, 5_benzenetris / lephonyl chloride” with three sulfo-urek lide groups (halide functional groups) can be synthesized by the procedure shown in the following formula. it can.
- reaction formula (2) charge 5 L reaction vessel with sodium 1,5,5-benzenetrisulfonate 55.5 g (1.43 mo 1) and thionyl chloride (SOC 1 2 ) 2.5 L, DMF 3 30 m 1 is added dropwise at room temperature over 30 minutes. After dropping, heat to reflux for 12 hours. Cool the reaction mixture, pour it into 36 kg of ice, filter the precipitated crystals, wash with water and dry. The obtained crude crystals were recrystallized with ethyl acetate to obtain the target monomer “1, 3, 5-benzenetrisulfuryl chloride (yield 20 8 g, yield 37.8%)”. (Reaction formula (2)).
- a monomer having an imide functional group is first synthesized by a monomer having a halide functional group by the same or similar procedure as described above, and then synthesized with ammonia, hexamethyldisilazane (HMD S), It can be obtained by reacting with hexamethyldisilazane lithium (Li HMD S) or the like to convert all or part of halide functional groups to imide functional groups.
- HMD S hexamethyldisilazane
- Li HMD S hexamethyldisilazane lithium
- the content of the “imido network polymer crosslinked with strongly acidic groups” in the composite electrolyte membrane of the present invention is not particularly limited as long as it does not impair its excellent ionic conductivity, but is preferably based on the total amount of the composite electrolyte membrane. As 40 to 98% by weight.
- the content of the “imido network polymer bridged by strongly acidic groups” in the composite electrolyte membrane is less than the lower limit. When the relative humidity in the atmosphere is less than 1.0, a sufficiently high ion conductivity tends not to be obtained. On the other hand, when the upper limit is exceeded, it is difficult to form a film, The strength tends to decrease.
- the composite electrolyte membrane of the present invention having the above configuration can obtain sufficiently high ionic conductivity at a lower humidity than conventional solid electrolytes even when the relative humidity in the atmosphere is less than 1.0. Therefore, it can be suitably used for applications such as an electrolyte membrane for a solid polymer fuel cell, an electrolyte for an all-solid battery, and a sensor.
- Example 1 An electrolyte membrane for a solid polymer fuel cell, an electrolyte for an all-solid battery, and a sensor.
- a porous membrane of ⁇ 50 m is impregnated with a solution in which a monomer, which is a starting compound of "imido network polymer crosslinked with strongly acidic groups", is dissolved in a solvent with high wettability and low molecular weight. After superimposing with, a composite film is formed by protonation. If necessary, the polymerization process may be performed multiple times.
- an HD PE ultra high molecular weight polyethylene Z made by Teijin Solfil / porosity 85%, average pore size 0.3 Aim, film thickness 50 ⁇ m
- the electrolyte was used as the electrolyte.
- “Imid network polymer cross-linked with strong acid group” whose typical molecular structure is represented by the following chemical formula was used.
- R f include one CF 2 CF 2 —, one CF 2 CH 2 — or one C FHCH 2 —.
- R f include one CF 2 CF 2 —, one CF 2 CH 2 — or one C FHCH 2 —.
- -SO 2- (sulfol group) may be contained.
- the specific number of repetitions is: ⁇ 10 0 0, preferably 3 to 50, more preferably 3 to 10.
- the specific value of the molecular weight is that the molecular weight after synthesis is 1 0 0 0 0 0 or more, preferably 1 0 0 0 0 or more, more preferably 5 0 0 0 0 0 0 or more.
- the crosslinking agent one having a sulfonyl fluoride (F—SO 2 —R f —) structure at the end of the molecular structure is most preferable. However, a carbon fluoride (F—C O_R f _) structure may be used.
- the degree of cross-linking it is preferable to have 1 to 3 cross-linking structures per benzene structure, and 1 or 2 is more preferable from the viewpoint of mechanical brittleness.
- the acid density of the “imido network polymer cross-linked with a strongly acidic group” is preferably an EW value of 2500 to 7500, more preferably 2500 to 600.
- the Young's modulus is 0.1 NZ.mm 2 to 20 1 NZmm 2 and the yield elongation at that time is 5% to 200%.
- BT SA is represented by the following chemical formula. It is a trifunctional monomer represented (molecular weight: 3 1 5, white powder)
- P PD SF is difunctional monomer "F 0 2 S (CF 2) 3 S_ ⁇ 2 F” (molecular weight: 3 1 6, density 1. 7 7 6 g / cm 3 , transparent liquid).
- the obtained monomer solution was impregnated into an HDPE membrane in a vial, irradiated with ultrasonic waves for 3 minutes, reacted at 50 ° C. for 24 hours, and further heated at 90 ° C. for 24 hours.
- 1 5 V o 1% nitric acid + 85 V o 1% Stir with EtOH solution for 12 hr (room temperature), then stir in 1 5 percent nitric acid solution (50 ° C) for 24 hr.
- the membrane was completed.
- the filling rate of the obtained composite membrane was 77% by volume ratio to the pores.
- the conductivity (RH 20%) of the composite membrane was 0.0 0 25 S / cm.
- the dimensional change rate in the plane direction was 0.5%.
- this gel-like insoluble matter was acid-treated in 15 V o 1% HNO 3 + 85 V o 1% EtOH (both manufactured by Wako Pure Chemical Industries, Ltd.) for 24 hr, and further dried for 12 hr.
- the obtained material was pulverized in a mortar and dispersed in 9 9% EtOH to attempt impregnation into Teijin Solfil HD PE porous membrane (Product name: 7 P 0 3 A) 20 mmXmm.
- the increase in weight was 0.2 mg, which was about 2% in terms of filling rate.
- Example 1 The composite membrane obtained in Example 1 was again filled in the same procedure as in Example 1 to obtain a double-filled composite membrane.
- the resulting composite membrane has a filling rate of 100%, conductivity (RH 20%): 0.06 S / cm, dimensional change rate in the plane direction (dry ⁇ underwater): 4% Met.
- Example 2 In the same manner as in Example 1, heating was started at 50 ° C. Four hours later, nitrogen was flowed into the vial, and the solvent was distilled off over about 30 minutes to reduce the weight of the solution by about 1 g. The mixture was reacted at 50 ° C for a total of 24 hours, and then heated at 90 ° C for 24 hours. In the same manner as in Example 1, acid treatment was performed to obtain a composite membrane.
- the obtained composite membrane had a filling rate of 94%, a conductivity (RH 20%): 0.004 S / cm, and a dimensional change rate in the plane direction (dry * to ⁇ water): 3%.
- Example 2 In the same manner as in Example 1, heating was started at 50 ° C. Four hours later, nitrogen was flowed into the vial, and the solvent was distilled off over about 30 minutes to reduce the weight of the solution by about 1 lg. After reacting at 50 ° C. for a total of 24 hours, the mixture was heated at 90 ° C. for 24 hours. In the same manner as in Example 1, acid treatment was performed to obtain a composite membrane. Further, this membrane was refilled by the procedure of Example 3 to produce a membrane. The resulting composite membrane has a filling rate of 100%, conductivity (RH 20%): 0.07 S / cm, in the plane direction Dimensional change rate (dry ⁇ underwater): 6%.
- Example 4 The membrane obtained in Example 4 was dried at 50.degree. C. for 5 hours, then immersed in a solution consisting of 30 ml of tetrahydrofuran, 3 ml of triethylamine, 1.5 g of PPD SF, and at 60.degree. C. under nitrogen. Allowed to stand for 50 hours.
- the treated membrane was immersed for 3 hours at 70 ° C in a solvent of 3 g of hydroxide power, 7 g of dimethyl sulfoxide, 10 g of ion-exchanged water, and the like.
- the obtained composite membrane had a filling rate of 100%, a conductivity (RH 20%): 0.014 SZcm, and a dimensional change rate in the plane direction (dry ⁇ ⁇ ⁇ water): 8%.
- the composite membrane was taken out and post-treated in the same manner as in Example 1.
- the obtained composite membrane has a filling rate of 100%, a conductivity (RH 20%): 0.010 S / cm, a dimensional change rate in the plane direction (dry ⁇ underwater): 6 ° /. Met.
- Nafion 1 1 2 (trade name). Conductivity (RH 20%): 0. O 0 15 S / cm, dimensional change rate in the plane direction (dry * ⁇ > underwater): 20%. Nafion 1 1 2 (trade name) has low conductivity, water content, and large dimensional change during drying.
- composition of the I NP electrolyte differs between the first and second filling (different composition) Composite membrane
- Table 1 shows the composition of the three monomer mixtures and solvents used in Examples 7 to 33. Indicates the weight ratio (molar ratio)
- Example 7 1 2: 5 7% solution used
- a solvent was mixed with the three monomer mixtures (compositions 1 to 6) and stirred to obtain a monomer solution.
- the obtained monomer solution was impregnated in an HD PE membrane in a container, irradiated with ultrasonic waves for 1 minute, reacted at 50 ° C. for a predetermined time (Table 2), and further heated at 90 ° C. for 24 hours.
- Example 2 3 to 2 6 Filling 2 times of Example 2 0 to 2 2 (using 6 7% solution) partially different composition]
- Example 2 7 HD ⁇ ⁇ : Ultra high molecular weight polyethylene / manufactured by Teijin Solfil / porosity 88%, average pore size 0.7 Aim, film thickness 60 / m
- Example 2 8 HD PE: ultra high molecular weight polyethylene / Teijin Solufill Ltd. / porosity: 8 4%, an average pore diameter of 0. 7 ⁇ ⁇ , thickness 5 0 m
- Example 3 2 Filling in Example 3 1 twice]
- Example 3 3 Bifunctionalization
- the composite membrane obtained in Example 25 was dried at 60 ° C for 3 hours, then immersed in a solution consisting of 90 ml of tetrahydrofuran, 90 ml of triethylamine, 4.6 g force of PPDSF, and nitrogen. The mixture was allowed to stand at 50 ° C. for 72 hours. The treated membrane was shaken with tetrahydrofuran for 3 hours (room temperature), shaken with 3 V o 1% sulfuric acid aqueous solution for 12 hours (room temperature), and immersed for 12 hours (room temperature). Shake with ultrapure water for 12 hours (room temperature), wash with water, and dry to obtain a composite membrane.
- Table 2 shows the production conditions and physical properties of Examples 7 to 33.
- Example 25 The composite film obtained in 5 was spray-coated on both sides with a solution containing Pt-supported carbon, Nafion (trade name) solution, and ethanol, and 1 30 ° C, 50 kg / cm. Hot-pressed with 2 for 6 minutes to obtain MEA. The gas diffusion layer was placed on both sides, and the IV characteristics were evaluated under the conditions of 80 ° C, 20 ° CZ, 20 ° C and 20 ° C force sword / anode bubbler humidification.
- the present invention provides a composite electrolyte membrane having self-supporting properties. I was able to.
- the composite electrolyte membrane of the present invention can be used in various fields as a functional membrane.
- the composite electrolyte membrane of the present invention is suitable as an electrolyte membrane for fuel cells, and has high strength, high proton conductivity, excellent chemical stability, and flexibility (strong against deformation). Is obtained. As a result, a high-performance fuel cell can be realized, which contributes to the practical application and spread of fuel cells.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Polymers & Plastics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Chemistry (AREA)
- Conductive Materials (AREA)
- Fuel Cell (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2008508692A JP5040911B2 (ja) | 2006-03-27 | 2007-03-27 | 強酸性基で架橋されたイミドネットワークポリマを有する複合電解質膜、その製造方法、及び燃料電池 |
EP07740779A EP2009723A1 (en) | 2006-03-27 | 2007-03-27 | Composite electrolyte membrane comprising imide network polymer crosslinked with strongly acidic group, method for manufacturing the composite electrolyte membrane, and fuel cell |
CA002646797A CA2646797A1 (en) | 2006-03-27 | 2007-03-27 | Composite electrolyte membrane having imido-network polymer cross-linked with strongly-acidic groups, method for manufacturing the same, and fuel cell |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2006086261 | 2006-03-27 | ||
JP2006-086261 | 2006-03-27 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2007114406A1 true WO2007114406A1 (ja) | 2007-10-11 |
Family
ID=38563670
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2007/057343 WO2007114406A1 (ja) | 2006-03-27 | 2007-03-27 | 強酸性基で架橋されたイミドネットワークポリマを有する複合電解質膜、その製造方法、及び燃料電池 |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP2009723A1 (ja) |
JP (1) | JP5040911B2 (ja) |
CN (1) | CN101411018A (ja) |
CA (1) | CA2646797A1 (ja) |
WO (1) | WO2007114406A1 (ja) |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008243511A (ja) * | 2007-03-27 | 2008-10-09 | Toyota Central R&D Labs Inc | 複合電解質及びその製造方法 |
JP2009231162A (ja) * | 2008-03-25 | 2009-10-08 | Toyota Central R&D Labs Inc | 膜電極接合体 |
JP2009238738A (ja) * | 2008-03-07 | 2009-10-15 | Toyota Central R&D Labs Inc | 固体高分子電解質 |
JP2009259793A (ja) * | 2008-03-24 | 2009-11-05 | Toyota Central R&D Labs Inc | 強酸性基架橋型複合電解質 |
CN101407592B (zh) * | 2008-11-20 | 2011-06-08 | 上海交通大学 | 含咪唑基磺化聚酰亚胺共价-离子交联膜的制备方法 |
JP2012158725A (ja) * | 2011-02-02 | 2012-08-23 | Toyota Central R&D Labs Inc | プレポリマ及びプレポリマ溶液、並びに、触媒層 |
JP2013129694A (ja) * | 2011-12-20 | 2013-07-04 | Nitto Denko Corp | プロトン伝導性の高分子電解質およびその製造方法、電解質膜およびその製造方法、ならびにそれを用いた膜・電極接合体および燃料電池 |
JP2014067605A (ja) * | 2012-09-26 | 2014-04-17 | Nitto Denko Corp | 高分子電解質膜およびそれを用いた燃料電池 |
JP2014067607A (ja) * | 2012-09-26 | 2014-04-17 | Nitto Denko Corp | プロトン伝導性を有する高分子電解質および高分子電解質膜、それらの製造方法、ならびに、それらを用いた膜・電極接合体および燃料電池 |
JP2014067609A (ja) * | 2012-09-26 | 2014-04-17 | Nitto Denko Corp | プロトン伝導性の電解質膜およびその製造方法、ならびにそれを用いた膜・電極接合体および燃料電池 |
JP2014067606A (ja) * | 2012-09-26 | 2014-04-17 | Nitto Denko Corp | 高分子電解質膜およびそれを用いた燃料電池 |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008269900A (ja) * | 2007-04-18 | 2008-11-06 | National Univ Corp Shizuoka Univ | 高分子電解質材料及びこれを用いた燃料電池用膜・電極接合体 |
WO2011087459A1 (en) * | 2010-01-14 | 2011-07-21 | Agency For Science, Technology And Research | Method of forming a polymer electrolyte membrane |
JP5764956B2 (ja) * | 2010-02-16 | 2015-08-19 | セントラル硝子株式会社 | 固体電解質膜およびその製造方法 |
US9120898B2 (en) | 2011-07-08 | 2015-09-01 | Baker Hughes Incorporated | Method of curing thermoplastic polymer for shape memory material |
US8939222B2 (en) | 2011-09-12 | 2015-01-27 | Baker Hughes Incorporated | Shaped memory polyphenylene sulfide (PPS) for downhole packer applications |
US8829119B2 (en) | 2011-09-27 | 2014-09-09 | Baker Hughes Incorporated | Polyarylene compositions for downhole applications, methods of manufacture, and uses thereof |
US8604157B2 (en) * | 2011-11-23 | 2013-12-10 | Baker Hughes Incorporated | Crosslinked blends of polyphenylene sulfide and polyphenylsulfone for downhole applications, methods of manufacture, and uses thereof |
CN102522574B (zh) * | 2011-12-24 | 2014-10-01 | 山东东岳高分子材料有限公司 | 一种液流电池用隔膜及其制备方法 |
US9144925B2 (en) | 2012-01-04 | 2015-09-29 | Baker Hughes Incorporated | Shape memory polyphenylene sulfide manufacturing, process, and composition |
US9707642B2 (en) | 2012-12-07 | 2017-07-18 | Baker Hughes Incorporated | Toughened solder for downhole applications, methods of manufacture thereof and articles comprising the same |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999010165A1 (en) * | 1997-08-29 | 1999-03-04 | Foster-Miller, Inc. | Composite solid polymer electrolyte membranes |
JP2000188013A (ja) | 1998-12-22 | 2000-07-04 | Toyota Central Res & Dev Lab Inc | 高耐熱性高分子電解質 |
JP2002083612A (ja) * | 2000-09-07 | 2002-03-22 | Takehisa Yamaguchi | 電解質膜及びその製造方法、並びに燃料電池及びその製造方法 |
JP2002516348A (ja) | 1998-05-22 | 2002-06-04 | ミネソタ マイニング アンド マニュファクチャリング カンパニー | 架橋イオン伝導性膜 |
JP2002246041A (ja) | 2001-02-21 | 2002-08-30 | Matsushita Electric Ind Co Ltd | 固体高分子電解質型燃料電池用膜・電極接合体 |
JP2005174800A (ja) | 2003-12-12 | 2005-06-30 | Toyota Central Res & Dev Lab Inc | 固体高分子電解質及びその製造方法、並びに燃料電池 |
-
2007
- 2007-03-27 CN CNA2007800106697A patent/CN101411018A/zh active Pending
- 2007-03-27 CA CA002646797A patent/CA2646797A1/en not_active Abandoned
- 2007-03-27 WO PCT/JP2007/057343 patent/WO2007114406A1/ja active Application Filing
- 2007-03-27 EP EP07740779A patent/EP2009723A1/en not_active Withdrawn
- 2007-03-27 JP JP2008508692A patent/JP5040911B2/ja not_active Expired - Fee Related
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999010165A1 (en) * | 1997-08-29 | 1999-03-04 | Foster-Miller, Inc. | Composite solid polymer electrolyte membranes |
JP2002516348A (ja) | 1998-05-22 | 2002-06-04 | ミネソタ マイニング アンド マニュファクチャリング カンパニー | 架橋イオン伝導性膜 |
JP2000188013A (ja) | 1998-12-22 | 2000-07-04 | Toyota Central Res & Dev Lab Inc | 高耐熱性高分子電解質 |
JP2002083612A (ja) * | 2000-09-07 | 2002-03-22 | Takehisa Yamaguchi | 電解質膜及びその製造方法、並びに燃料電池及びその製造方法 |
JP2002246041A (ja) | 2001-02-21 | 2002-08-30 | Matsushita Electric Ind Co Ltd | 固体高分子電解質型燃料電池用膜・電極接合体 |
JP2005174800A (ja) | 2003-12-12 | 2005-06-30 | Toyota Central Res & Dev Lab Inc | 固体高分子電解質及びその製造方法、並びに燃料電池 |
Non-Patent Citations (1)
Title |
---|
"Tokyo Kagaku Dojin", 1978, SOCIETY OF POLYMER SCIENCE, article "Kobunshi Kagaku no Kiso", pages: 250 - 251 |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008243511A (ja) * | 2007-03-27 | 2008-10-09 | Toyota Central R&D Labs Inc | 複合電解質及びその製造方法 |
JP2009238738A (ja) * | 2008-03-07 | 2009-10-15 | Toyota Central R&D Labs Inc | 固体高分子電解質 |
JP2009259793A (ja) * | 2008-03-24 | 2009-11-05 | Toyota Central R&D Labs Inc | 強酸性基架橋型複合電解質 |
JP2009231162A (ja) * | 2008-03-25 | 2009-10-08 | Toyota Central R&D Labs Inc | 膜電極接合体 |
CN101407592B (zh) * | 2008-11-20 | 2011-06-08 | 上海交通大学 | 含咪唑基磺化聚酰亚胺共价-离子交联膜的制备方法 |
JP2012158725A (ja) * | 2011-02-02 | 2012-08-23 | Toyota Central R&D Labs Inc | プレポリマ及びプレポリマ溶液、並びに、触媒層 |
JP2013129694A (ja) * | 2011-12-20 | 2013-07-04 | Nitto Denko Corp | プロトン伝導性の高分子電解質およびその製造方法、電解質膜およびその製造方法、ならびにそれを用いた膜・電極接合体および燃料電池 |
JP2014067605A (ja) * | 2012-09-26 | 2014-04-17 | Nitto Denko Corp | 高分子電解質膜およびそれを用いた燃料電池 |
JP2014067607A (ja) * | 2012-09-26 | 2014-04-17 | Nitto Denko Corp | プロトン伝導性を有する高分子電解質および高分子電解質膜、それらの製造方法、ならびに、それらを用いた膜・電極接合体および燃料電池 |
JP2014067609A (ja) * | 2012-09-26 | 2014-04-17 | Nitto Denko Corp | プロトン伝導性の電解質膜およびその製造方法、ならびにそれを用いた膜・電極接合体および燃料電池 |
JP2014067606A (ja) * | 2012-09-26 | 2014-04-17 | Nitto Denko Corp | 高分子電解質膜およびそれを用いた燃料電池 |
Also Published As
Publication number | Publication date |
---|---|
EP2009723A1 (en) | 2008-12-31 |
JP5040911B2 (ja) | 2012-10-03 |
CN101411018A (zh) | 2009-04-15 |
CA2646797A1 (en) | 2007-10-11 |
JPWO2007114406A1 (ja) | 2009-08-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2007114406A1 (ja) | 強酸性基で架橋されたイミドネットワークポリマを有する複合電解質膜、その製造方法、及び燃料電池 | |
Machado et al. | Redox flow battery membranes: improving battery performance by leveraging structure–property relationships | |
Ye et al. | Ionic liquid polymer electrolytes | |
Long et al. | A novel double branched sulfonated polyimide membrane with ultra-high proton selectivity for vanadium redox flow battery | |
US8114550B2 (en) | Reinforced electrolyte membrane for fuel cell, production method thereof, membrane electrode assembly for fuel cell, and solid polymer fuel cell comprising the same | |
WO2005001969A1 (ja) | 高分子電解質ならびにそれを用いた高分子電解質膜、膜電極複合体および高分子電解質型燃料電池 | |
JP4930690B2 (ja) | イオン伝導性ポリマ及びイミドモノマ | |
KR102486446B1 (ko) | 과불화술폰산 이오노머가 그래프트된 그래핀 옥사이드를 포함하는 양이온 교환막 및 이를 이용한 용도 | |
CN105378994A (zh) | 电解质膜、分散体及其方法 | |
Das et al. | Nanoporous covalent organic framework and polybenzimidazole composites for proton exchange membranes | |
WO2014157389A1 (ja) | 電解質膜用組成物、固体高分子電解質膜、該電解質膜の製造方法、膜-電極接合体、固体高分子型燃料電池、水電解セルおよび水電解装置 | |
JP2009259793A (ja) | 強酸性基架橋型複合電解質 | |
Rao et al. | Construction of Surface Sulfonic and Amino Acid–Base Pair Modified Graphene Oxide for Effectively Promoting the Selectivity of the Proton Exchange Membrane | |
Ying et al. | Perspectives on Membrane Development for High Temperature Proton Exchange Membrane Fuel Cells | |
JP4576830B2 (ja) | 固体高分子電解質及びその製造方法、並びに燃料電池 | |
JP2009270078A (ja) | 高分子電解質膜 | |
JP2009185250A (ja) | 単離ポリマーの製造方法 | |
JP5627491B2 (ja) | 固体高分子電解質膜及びその製造方法 | |
JP4431939B2 (ja) | 高分子電解質の製造方法及び燃料電池 | |
JP2005216525A (ja) | 直接メタノール型燃料電池用プロトン伝導膜およびその製造方法 | |
JP5194509B2 (ja) | 複合電解質及びその製造方法 | |
JP4857523B2 (ja) | 高分子電解質及び高分子電解質膜 | |
JP4665396B2 (ja) | ミクロ相分離構造によりメタノール透過抑制が改良されたプロトン伝導膜 | |
CN108070097B (zh) | 嵌段共聚物、离子交换膜及其制造方法 | |
JP5537457B2 (ja) | プレポリマ及びプレポリマ溶液、並びに、触媒層 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 07740779 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2646797 Country of ref document: CA |
|
WWE | Wipo information: entry into national phase |
Ref document number: 200780010669.7 Country of ref document: CN |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2008508692 Country of ref document: JP Ref document number: 2007740779 Country of ref document: EP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |