JP2021061219A - Fluorine-containing polyelectrolyte - Google Patents
Fluorine-containing polyelectrolyte Download PDFInfo
- Publication number
- JP2021061219A JP2021061219A JP2019186340A JP2019186340A JP2021061219A JP 2021061219 A JP2021061219 A JP 2021061219A JP 2019186340 A JP2019186340 A JP 2019186340A JP 2019186340 A JP2019186340 A JP 2019186340A JP 2021061219 A JP2021061219 A JP 2021061219A
- Authority
- JP
- Japan
- Prior art keywords
- fluorine
- polymer electrolyte
- containing polymer
- catalyst layer
- electrode catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 101
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 239000011737 fluorine Substances 0.000 title claims abstract description 90
- 229920000867 polyelectrolyte Polymers 0.000 title abstract 3
- 239000003054 catalyst Substances 0.000 claims abstract description 153
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 27
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 23
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims abstract description 23
- 125000003118 aryl group Chemical group 0.000 claims abstract description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 22
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 20
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 17
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 13
- 239000005518 polymer electrolyte Substances 0.000 claims description 96
- 239000000446 fuel Substances 0.000 claims description 44
- 239000012528 membrane Substances 0.000 claims description 36
- 125000004432 carbon atom Chemical group C* 0.000 claims description 25
- 125000001424 substituent group Chemical group 0.000 claims description 18
- 239000003792 electrolyte Substances 0.000 claims description 16
- 125000005647 linker group Chemical group 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- -1 perfluoro ring Chemical group 0.000 claims description 13
- 229920002313 fluoropolymer Polymers 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 8
- 150000004292 cyclic ethers Chemical class 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 66
- 229910052760 oxygen Inorganic materials 0.000 abstract description 66
- 239000001301 oxygen Substances 0.000 abstract description 66
- 230000035699 permeability Effects 0.000 abstract description 34
- 238000010248 power generation Methods 0.000 abstract description 13
- 238000005336 cracking Methods 0.000 abstract description 9
- 239000002131 composite material Substances 0.000 abstract description 6
- 230000008878 coupling Effects 0.000 abstract 1
- 238000010168 coupling process Methods 0.000 abstract 1
- 238000005859 coupling reaction Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 35
- 239000002245 particle Substances 0.000 description 31
- 239000007789 gas Substances 0.000 description 29
- 239000000126 substance Substances 0.000 description 29
- 150000002430 hydrocarbons Chemical group 0.000 description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 20
- 238000000034 method Methods 0.000 description 18
- 239000011347 resin Substances 0.000 description 18
- 229920005989 resin Polymers 0.000 description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 16
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 16
- 229920000642 polymer Polymers 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 239000000654 additive Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- 230000000996 additive effect Effects 0.000 description 12
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 229910044991 metal oxide Inorganic materials 0.000 description 10
- 150000004706 metal oxides Chemical class 0.000 description 10
- 238000010526 radical polymerization reaction Methods 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- 239000006258 conductive agent Substances 0.000 description 9
- 229910052697 platinum Inorganic materials 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000011246 composite particle Substances 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- 238000009792 diffusion process Methods 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 125000001153 fluoro group Chemical group F* 0.000 description 7
- 239000004811 fluoropolymer Substances 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 description 7
- 239000005871 repellent Substances 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 238000005342 ion exchange Methods 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 230000002940 repellent Effects 0.000 description 6
- 125000000542 sulfonic acid group Chemical group 0.000 description 6
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 239000003505 polymerization initiator Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- KPKNTUUIEVXMOH-UHFFFAOYSA-N 1,4-dioxa-8-azaspiro[4.5]decane Chemical group O1CCOC11CCNCC1 KPKNTUUIEVXMOH-UHFFFAOYSA-N 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- 229920000557 Nafion® Polymers 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- JHRWWRDRBPCWTF-OLQVQODUSA-N captafol Chemical compound C1C=CC[C@H]2C(=O)N(SC(Cl)(Cl)C(Cl)Cl)C(=O)[C@H]21 JHRWWRDRBPCWTF-OLQVQODUSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910003437 indium oxide Inorganic materials 0.000 description 4
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 4
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000006259 organic additive Substances 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- 229910001887 tin oxide Inorganic materials 0.000 description 4
- 239000011667 zinc carbonate Substances 0.000 description 4
- 235000004416 zinc carbonate Nutrition 0.000 description 4
- 229910000010 zinc carbonate Inorganic materials 0.000 description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- YSYRISKCBOPJRG-UHFFFAOYSA-N 4,5-difluoro-2,2-bis(trifluoromethyl)-1,3-dioxole Chemical compound FC1=C(F)OC(C(F)(F)F)(C(F)(F)F)O1 YSYRISKCBOPJRG-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-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
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000011203 carbon fibre reinforced carbon Chemical group 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 description 3
- ODPUKHWKHYKMRK-UHFFFAOYSA-N cerium;nitric acid Chemical compound [Ce].O[N+]([O-])=O ODPUKHWKHYKMRK-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000001033 ether group Chemical group 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000003682 fluorination reaction Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 3
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 3
- 229910001960 metal nitrate Inorganic materials 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 150000003568 thioethers Chemical class 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229910005793 GeO 2 Inorganic materials 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 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
- JYMITAMFTJDTAE-UHFFFAOYSA-N aluminum zinc oxygen(2-) Chemical compound [O-2].[Al+3].[Zn+2] JYMITAMFTJDTAE-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 2
- 229940116318 copper carbonate Drugs 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229920000554 ionomer Polymers 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 229910000464 lead oxide Inorganic materials 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- CZDSWLXAULJYPZ-UHFFFAOYSA-J molybdenum(4+);dicarbonate Chemical compound [Mo+4].[O-]C([O-])=O.[O-]C([O-])=O CZDSWLXAULJYPZ-UHFFFAOYSA-J 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 2
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 2
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920001955 polyphenylene ether Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000012966 redox initiator Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- HNKJADCVZUBCPG-UHFFFAOYSA-N thioanisole Chemical compound CSC1=CC=CC=C1 HNKJADCVZUBCPG-UHFFFAOYSA-N 0.000 description 2
- 125000000101 thioether group Chemical group 0.000 description 2
- FOZHTJJTSSSURD-UHFFFAOYSA-J titanium(4+);dicarbonate Chemical compound [Ti+4].[O-]C([O-])=O.[O-]C([O-])=O FOZHTJJTSSSURD-UHFFFAOYSA-J 0.000 description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 description 2
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- 238000007865 diluting Methods 0.000 description 1
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- 125000004185 ester group Chemical group 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
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- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- UOYPNWSDSPYOSN-UHFFFAOYSA-N hexahelicene Chemical compound C1=CC=CC2=C(C=3C(=CC=C4C=CC=5C(C=34)=CC=CC=5)C=C3)C3=CC=C21 UOYPNWSDSPYOSN-UHFFFAOYSA-N 0.000 description 1
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- 125000000468 ketone group Chemical group 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- WXEHBUMAEPOYKP-UHFFFAOYSA-N methyl ethyl thioether Natural products CCSC WXEHBUMAEPOYKP-UHFFFAOYSA-N 0.000 description 1
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- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- NFBOHOGPQUYFRF-UHFFFAOYSA-N oxanthrene Chemical compound C1=CC=C2OC3=CC=CC=C3OC2=C1 NFBOHOGPQUYFRF-UHFFFAOYSA-N 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920002480 polybenzimidazole Polymers 0.000 description 1
- 229920002577 polybenzoxazole Polymers 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000000565 sulfonamide group Chemical group 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Fuel Cell (AREA)
- Conductive Materials (AREA)
- Inert Electrodes (AREA)
Abstract
Description
本発明は、含フッ素高分子電解質、上記含フッ素高分子電解質を含む含フッ素高分子電解質含有組成物、上記含フッ素高分子電解質含有組成物を含む電極触媒層、上記電極触媒層を備える膜電極接合体、上記膜電極接合体を備える燃料電池に関する。 The present invention comprises a fluorine-containing polymer electrolyte, a fluorine-containing polymer electrolyte-containing composition containing the fluorine-containing polymer electrolyte, an electrode catalyst layer containing the fluorine-containing polymer electrolyte-containing composition, and a membrane electrode including the electrode catalyst layer. The present invention relates to a assembly and a fuel cell including the membrane electrode assembly.
固体高分子形燃料電池は近年、家庭用燃料電池システムや燃料電池自動車に搭載、市販され、地球温暖化防止の観点から、今後も成長が期待される。
この固体高分子型燃料電池には、パーフルオロカーボンスルホン酸のような電解質膜とその両面に白金担持カーボンとバインダー樹脂(アイオノマー)からなる電極触媒層が密着した膜電極接合体(MEA)が設けられている。
このMEAの片方の電極触媒層に加湿した水素ガスを、もう一方の電極触媒層に加湿した酸素ガスを流通させると、水素ガス側(以下、アノード)の電極触媒上でプロトンが生成し、電解質膜を通して酸素ガス側(以下、カソード)に移動する。反対にカソードの電極触媒上では酸素が還元され、別回路から流れてきた電子と、アノードから流れてきたプロトンと反応し水が生成する。
In recent years, polymer electrolyte fuel cells have been installed in household fuel cell systems and fuel cell vehicles and put on the market, and growth is expected in the future from the viewpoint of preventing global warming.
This polymer electrolyte fuel cell is provided with a membrane electrode assembly (MEA) in which an electrolyte membrane such as perfluorocarbon sulfonic acid and an electrode catalyst layer made of platinum-supported carbon and a binder resin (ionomer) are adhered to both sides thereof. ing.
When the hydrogen gas humidified in one electrode catalyst layer of the MEA is passed through the oxygen gas humidified in the other electrode catalyst layer, protons are generated on the electrode catalyst on the hydrogen gas side (hereinafter referred to as the anode), and the electrolyte is generated. It moves to the oxygen gas side (hereinafter referred to as the cathode) through the membrane. On the contrary, oxygen is reduced on the electrode catalyst of the cathode, and the electrons flowing from another circuit react with the protons flowing from the anode to generate water.
固体高分子形燃料電池では、特に、カソードの電極触媒上での酸素還元反応を如何に効率よく起こすかが課題となる。
一方、今後、固体高分子形燃料電池システムの更なる市場成長のためには、システムを構成する各種部材のコスト低減が必要であるが、特に、コスト比率の高い白金触媒の使用量を削減することが必要である。
従来の固体高分子形燃料電池システムではカソードに多くの白金触媒を使用することで性能を担保していたが、白金触媒の使用量を削減すると、発電に寄与する触媒表面積の低下から発電性能が低くなる問題が生じる。
そこで、少ない触媒表面により多くの酸素を供給する為にアイオノマーの酸素透過性を向上させて、電極中に酸素を行き渡らせる試みがなされてきた。
In the polymer electrolyte fuel cell, in particular, how to efficiently cause the oxygen reduction reaction on the electrode catalyst of the cathode is an issue.
On the other hand, in order to further market growth of polymer electrolyte fuel cell systems in the future, it is necessary to reduce the cost of various components constituting the system, but in particular, the amount of platinum catalyst used, which has a high cost ratio, will be reduced. It is necessary.
In the conventional polymer electrolyte fuel cell system, the performance was guaranteed by using many platinum catalysts for the cathode, but if the amount of platinum catalyst used is reduced, the power generation performance will be improved due to the decrease in the catalyst surface area that contributes to power generation. The problem of lowering arises.
Therefore, attempts have been made to improve the oxygen permeability of ionomers in order to supply more oxygen to a smaller catalyst surface so that oxygen can be distributed throughout the electrode.
特許文献1、2には、酸素透過性が高く、カソード側触媒層含フッ素高分子電解質として好適な含フッ素高分子電解質として、ラジカル重合により主鎖に脂肪族環構造を有するポリマーを与える含フッ素モノマーに基づく繰り返し単位と、フッ素系スルホン酸含有モノマーに基づく繰り返し単位とを含む共重合体並びに当該共重合体を含有するガス拡散電極が記載されている。 Patent Documents 1 and 2 describe fluorine-containing polymers that have high oxygen permeability and are suitable as a fluorine-containing polymer electrolyte for the cathode side catalyst layer, and which provide a polymer having an aliphatic ring structure in the main chain by radical polymerization. A copolymer containing a repeating unit based on a monomer and a repeating unit based on a fluorosulfonic acid-containing monomer, and a gas diffusion electrode containing the copolymer are described.
特許文献3には、嵩高い環構造を有することで低密度化し、酸素透過性を促進する含フッ素高分子電解質として、2位にパーフルオロ環構造を有するパーフルオロ(1,3-ジオキソール)とスルホン酸を有するパーフルオロビニルエーテルの共重合体が記載されている。 Patent Document 3 describes perfluoro (1,3-dioxol) having a perfluoro ring structure at the 2-position as a fluorine-containing polymer electrolyte that has a bulky ring structure to reduce the density and promote oxygen permeability. Copolymers of perfluorovinyl ethers with sulfonic acids have been described.
特許文献4には、プロトン伝導性と酸素透過性を両立する含フッ素高分子電解質として、主鎖又は側鎖に、パーフルオロ脂肪族とスルホンイミドを有する電解質が記載されている。 Patent Document 4 describes an electrolyte having a perfluoroaliphatic compound and a sulfonimide in the main chain or side chain as a fluorine-containing polymer electrolyte having both proton conductivity and oxygen permeability.
しかしながら、上記特許文献1〜4に開示されている含フッ素高分子電解質は、嵩高い環構造の影響で、配合量を多くすると酸素透過性は上昇するものの、電極触媒層を形成させると表面に亀裂を生じ、発電性能が低下する、電池の耐久性が低下する、という問題が生じた。 However, the fluorine-containing polymer electrolytes disclosed in Patent Documents 1 to 4 have an effect of a bulky ring structure, and although the oxygen permeability increases when the blending amount is increased, when an electrode catalyst layer is formed, the surface becomes surfaced. There have been problems such as cracks, reduced power generation performance, and reduced battery durability.
そこで、本発明は、上記現状に鑑み、電極触媒層のひび割れを抑制し、酸素透過性が高く、電池での発電性能、耐久性が良好な含フッ素高分子電解質を提供することを目的とする。 Therefore, in view of the above situation, it is an object of the present invention to provide a fluorine-containing polymer electrolyte that suppresses cracking of the electrode catalyst layer, has high oxygen permeability, and has good power generation performance and durability in a battery. ..
本発明者らは、上記の課題を解決するために鋭意検討した結果、側鎖に、連結基としてスルホニル基及び/又は環構造に含まれないエーテル結合を有し、上記スルホニル基及び環構造に含まれない上記エーテル結合の少なくとも1つが、芳香族環、脂肪族環、及び芳香族環と脂肪族環とを含む複合環からなる群から選ばれる少なくとも1つの環状構造と直接結合しており、上記直接結合をしている上記環状構造が窒素原子及び/又はエーテル性の酸素原子を含む含フッ素高分子電解質により、電極触媒層の表面に亀裂を生じることなく、電池での発電性能、耐久性が高くなることを見出し、本発明を完成するに至った。 As a result of diligent studies to solve the above problems, the present inventors have a sulfonyl group as a linking group and / or an ether bond not included in the ring structure in the side chain, and the sulfonyl group and the ring structure have an ether bond. At least one of the above ether bonds not included is directly bonded to at least one cyclic structure selected from the group consisting of an aromatic ring, an aliphatic ring, and a composite ring containing an aromatic ring and an aliphatic ring. The cyclic structure having a direct bond contains a nitrogen atom and / or an ethereal oxygen atom, so that the surface of the electrode catalyst layer is not cracked due to the fluoropolymer electrolyte, and the power generation performance and durability of the battery are not generated. We have found that the value is high, and have completed the present invention.
すなわち、本発明は以下の通りである。
[1]
側鎖に、連結基としてスルホニル基及び/又は環構造に含まれないエーテル結合を有し、
上記スルホニル基及び環構造に含まれない上記エーテル結合の少なくとも1つが、芳香族環、脂肪族環、及び芳香族環と脂肪族環とを含む複合環からなる群から選ばれる少なくとも1つの環状構造と直接結合しており、
上記直接結合をしている上記環状構造が窒素原子及び/又はエーテル性の酸素原子を含むことを特徴とする、含フッ素高分子電解質。
[2]
上記スルホニル基が上記環状構造に含まれる上記窒素原子と直接結合している、[1]に記載の含フッ素高分子電解質。
[3]
上記直接結合をしている上記環状構造が、エーテル結合を含む置換基を有する、[1]又は[2]に記載の含フッ素高分子電解質。
[4]
上記エーテル結合を含む置換基が、環状エーテルである、[3]に記載の含フッ素高分子電解質。
[5]
側鎖に下記式(1)に記載の構造を有する、[1]〜[4]のいずれかに記載の含フッ素高分子電解質。
[6]
[1]〜[5]のいずれかに記載の含フッ素高分子電解質と溶媒と触媒とを含むことを特徴とする、含フッ素高分子電解質含有組成物。
[7]
[6]に記載の含フッ素高分子電解質含有組成物を含むことを特徴とする、電極触媒層。
[8]
[7]に記載の電極触媒層と電解質膜とを備えることを特徴とする、膜電極接合体。
[9]
[8]に記載の膜電極接合体を備えることを特徴とする、燃料電池。
That is, the present invention is as follows.
[1]
The side chain has a sulfonyl group as a linking group and / or an ether bond not contained in the ring structure.
At least one of the sulfonyl group and the above ether bond not included in the ring structure is selected from the group consisting of an aromatic ring, an aliphatic ring, and a complex ring containing an aromatic ring and an aliphatic ring. Is directly connected to
A fluorine-containing polymer electrolyte characterized in that the cyclic structure having a direct bond contains a nitrogen atom and / or an ethereal oxygen atom.
[2]
The fluorine-containing polymer electrolyte according to [1], wherein the sulfonyl group is directly bonded to the nitrogen atom contained in the cyclic structure.
[3]
The fluorine-containing polymer electrolyte according to [1] or [2], wherein the cyclic structure having a direct bond has a substituent containing an ether bond.
[4]
The fluorine-containing polymer electrolyte according to [3], wherein the substituent containing the ether bond is a cyclic ether.
[5]
The fluorine-containing polymer electrolyte according to any one of [1] to [4], which has the structure described in the following formula (1) in the side chain.
[6]
A fluorinated polymer electrolyte-containing composition comprising the fluorinated polymer electrolyte according to any one of [1] to [5], a solvent, and a catalyst.
[7]
An electrode catalyst layer comprising the fluorine-containing polymer electrolyte-containing composition according to [6].
[8]
A membrane electrode assembly comprising the electrode catalyst layer and an electrolyte membrane according to [7].
[9]
A fuel cell comprising the membrane electrode assembly according to [8].
本発明の含フッ素高分子電解質は、電極触媒層のひび割れを抑制し、酸素透過性が高く、電池での発電性能、耐久性が良好である。本発明の含フッ素高分子電解質含有組成物は、電極触媒層の割れを防ぐことが出来る。さらに本発明の膜電極接合体、及び燃料電池は高い発電性能、耐久性を示す。 The fluorine-containing polymer electrolyte of the present invention suppresses cracking of the electrode catalyst layer, has high oxygen permeability, and has good power generation performance and durability in a battery. The fluorine-containing polymer electrolyte-containing composition of the present invention can prevent cracking of the electrode catalyst layer. Further, the membrane electrode assembly and the fuel cell of the present invention exhibit high power generation performance and durability.
以下、本発明を具体的に説明する。 Hereinafter, the present invention will be specifically described.
[含フッ素高分子電解質]
本実施形態の含フッ素高分子電解質は、側鎖に、連結基としてスルホニル基及び/又は環構造に含まれないエーテル結合を有し、上記スルホニル基及び環構造に含まれない上記エーテル結合の少なくとも1つが、芳香族環、脂肪族環、及び芳香族環と脂肪族環とを含む複合環からなる群から選ばれる少なくとも1つの環状構造と直接結合しており、上記直接結合をしている上記環状構造が窒素原子及び/又はエーテル性の酸素原子を含む。
本実施形態の含フッ素高分子電解質によれば、高酸素透過性を発現するだけでなく、電極触媒層の表面にひび割れを少なくし、燃料電池の運転において、高性能、高化学耐久性を発現することができる。
[Fluorine-containing polymer electrolyte]
The fluorine-containing polymer electrolyte of the present embodiment has a sulfonyl group as a linking group and / or an ether bond not contained in the ring structure in the side chain, and at least the above ether bond not contained in the sulfonyl group and the ring structure. One is directly bonded to at least one cyclic structure selected from the group consisting of an aromatic ring, an aliphatic ring, and a composite ring including an aromatic ring and an aliphatic ring, and the above-mentioned direct bonding is performed. The cyclic structure contains nitrogen atoms and / or etheric oxygen atoms.
According to the fluorine-containing polymer electrolyte of the present embodiment, not only high oxygen permeability is exhibited, but also cracks are reduced on the surface of the electrode catalyst layer, and high performance and high chemical durability are exhibited in the operation of the fuel cell. can do.
本実施形態の含フッ素高分子電解質は、主鎖に上記側鎖が結合した構造単位(繰り返し単位)(本明細書において、「構造単位A」と称する場合がある)を少なくとも有する重合体であることが好ましい。上記構造単位Aは、一種であってもよいし複数種であってもよいが、生産性の観点から、一種であることが好ましい。
本実施形態の含フッ素高分子電解質は他の構造単位を有していてもよい。上記他の構造単位は、一種であってもよいし複数種であってもよい。
The fluorine-containing polymer electrolyte of the present embodiment is a polymer having at least a structural unit (repeating unit) in which the side chain is bonded to the main chain (sometimes referred to as “structural unit A” in the present specification). Is preferable. The structural unit A may be one type or a plurality of types, but is preferably one type from the viewpoint of productivity.
The fluorine-containing polymer electrolyte of the present embodiment may have other structural units. The other structural unit may be one kind or a plurality of kinds.
(構造単位A)
以下、構造単位Aについて説明する。
上記構造単位Aの側鎖には、連結基として、スルホニル基及び/又は環構造に含まれないエーテル結合を含む。
上記構造単位Aの側鎖には、連結基として、さらに、環構造に含まれない、チオエーテル基、ケトン基、エステル基、イミド基、炭素−炭素結合(例えば、部分的又は完全にフッ素化されていてもよい炭素数1〜10の炭素−炭素結合)、等を含んでいてもよい。
中でも、上記連結基は、含フッ素高分子電解質の溶液化、及び燃料電池運転での化学耐久性向上の観点から、スルホニル基及び/又は環構造に含まれないエーテル基と、炭素−炭素結合とを含むことが好ましく、合成の容易性から、スルホニル基及び/又は環構造に含まれないエーテル基のみがより好ましい。
(Structural unit A)
Hereinafter, the structural unit A will be described.
The side chain of the structural unit A contains a sulfonyl group and / or an ether bond not included in the ring structure as a linking group.
In the side chain of the structural unit A, as a linking group, a thioether group, a ketone group, an ester group, an imide group, and a carbon-carbon bond (for example, partially or completely fluorinated) which are not contained in the ring structure are further fluorinated. It may contain carbon-carbon bonds having 1 to 10 carbon atoms), and the like.
Among them, the above-mentioned linking group includes a sulfonyl group and / or an ether group not contained in the ring structure and a carbon-carbon bond from the viewpoint of solubilizing a fluorine-containing polymer electrolyte and improving chemical durability in fuel cell operation. Is preferable, and only the sulfonyl group and / or the ether group not contained in the ring structure is more preferable from the viewpoint of easiness of synthesis.
上記構造単位Aは、側鎖に、芳香族環、脂肪族環、及び芳香族環と脂肪族環とを含む複合環からなる群から選ばれる環状構造を有する。上記構造単位Aに含まれる上記環状構造は、1つであってもよいし複数であってもよい。
上記環状構造は、環構造を構成する元素として窒素原子及び/又はエーテル性の酸素原子を含むことが好ましく、電極触媒層のひび割れを一層抑制し、酸素透過性を一層向上させる観点から、窒素原子及びエーテル性の酸素原子を含むことが好ましい。
上記環状構造は、酸素透過性を一層向上させる観点から、エーテル結合を含む置換基を有することが好ましく、環状エーテルを含むことが好ましい。
The structural unit A has a cyclic structure selected from the group consisting of an aromatic ring, an aliphatic ring, and a complex ring containing an aromatic ring and an aliphatic ring in the side chain. The cyclic structure included in the structural unit A may be one or a plurality.
The cyclic structure preferably contains a nitrogen atom and / or an etheric oxygen atom as an element constituting the ring structure, and from the viewpoint of further suppressing cracking of the electrode catalyst layer and further improving oxygen permeability, the nitrogen atom. And preferably contain an ethereal oxygen atom.
From the viewpoint of further improving oxygen permeability, the cyclic structure preferably has a substituent containing an ether bond, and preferably contains a cyclic ether.
上記環状構造としては、以下に限定されないが、例えば、下記式3〜28で表される構造が挙げられる。
上記環構造の置換基(例えば、R1〜R26)としては、酸素溶解度及び酸素透過性の向上、電極のひび割れ防止による電池性能及び化学耐久性向上の観点から、フッ素原子、炭素数が1〜10のフッ素化炭化水素基が好ましい。
上記環状構造としては、式13、式14、式25で表される構造が好ましく、酸素透過性に一層優れる観点から、式13がより好ましい。
The annular structure is not limited to the following, and examples thereof include structures represented by the following formulas 3 to 28.
As the substituent of the ring structure (for example, R 1 to R 26 ), the fluorine atom and the number of carbon atoms are 1 from the viewpoint of improving oxygen solubility and oxygen permeability, and improving battery performance and chemical durability by preventing cracking of the electrode. A fluorinated hydrocarbon group of 10 to 10 is preferable.
As the annular structure, the structures represented by the formulas 13, 14 and 25 are preferable, and the formula 13 is more preferable from the viewpoint of further excellent oxygen permeability.
上記構造単位Aは、少なくとも1個の上記環状構造と、連結基としてのスルホニル基又は環構造に含まれないエーテル結合とが直接結合している構造を側鎖に含むことが好ましく、上記環状構造に含まれる窒素原子と上記スルホニル基とが直接結合している構造を側鎖に含むことがより好ましい。 The structural unit A preferably contains, in the side chain, a structure in which at least one of the cyclic structures is directly bonded to a sulfonyl group as a linking group or an ether bond not included in the ring structure, and the cyclic structure. It is more preferable that the side chain contains a structure in which the nitrogen atom contained in the above and the sulfonyl group are directly bonded.
上記構造単位Aは、下記式(1)で表される構造を有することが好ましい。
上記式(1)で表される構造としては、上記式3〜14、式23〜28を含む構造があげられ、具体的には下記式29〜34の構造が好ましい。
上記構造単位Aの側鎖に含まれる芳香族環としては、置換されていてもよい、ベンゼン、ナフタレン、アントラセン、フルオレン、ヘリセン、ピレン等の芳香族炭化水素環;置換されていてもよい、フラン、ピラン、ジオキシン、ジベンゾジオキシン、ピロール、イミダゾール、トリアゾール、ピリジン、ピリミジン、ピラジン等の芳香族複素環;等の構造が挙げられる。
上記芳香族環は、置換基を含むものが好ましい。
ここで、上記置換基とは、上記連結基以外の置換基をいう。
上記置換基とはとしては、以下に限定されないが、例えば、フッ素原子等のハロゲン原子、酸素原子、スルホン酸基、フッ素化炭化水素基、スルホンアミド基、エーテル結合を含む置換されていてもよい炭素数1以上のフッ素化炭化水素基等が挙げられるが、中でも、フッ素原子、フッ素化炭化水素基、エーテル結合を含む置換されていてもよい炭素数1以上のフッ素化炭化水素基が好ましい。
フッ素原子、フッ素化炭化水素基、エーテル結合を含む置換されていてもよい炭素数1以上のフッ素化炭化水素基が含まれることで、より一層酸素溶解度が向上し、燃料電池運転での低加湿と高加湿のいずれの条件でも高い発電性能を発現することにつながる。
The aromatic ring contained in the side chain of the structural unit A may be substituted, an aromatic hydrocarbon ring such as benzene, naphthalene, anthracene, fluorene, helicene, pyrene; or optionally substituted, furan. , Pyran, dioxine, dibenzodioxin, pyrrole, imidazole, triazole, pyridine, pyrimidine, aromatic heterocycles such as pyrazine; and the like.
The aromatic ring preferably contains a substituent.
Here, the above-mentioned substituent means a substituent other than the above-mentioned linking group.
The above-mentioned substituent is not limited to the following, and may be substituted including, for example, a halogen atom such as a fluorine atom, an oxygen atom, a sulfonic acid group, a fluorinated hydrocarbon group, a sulfonamide group, and an ether bond. Examples thereof include a fluorinated hydrocarbon group having 1 or more carbon atoms, and among them, a fluorinated hydrocarbon group having 1 or more carbon atoms which may be substituted and contains a fluorine atom, a fluorinated hydrocarbon group and an ether bond is preferable.
By containing a fluorinated hydrocarbon group having 1 or more carbon atoms which may be substituted, which contains a fluorine atom, a fluorinated hydrocarbon group, and an ether bond, oxygen solubility is further improved, and low humidification in fuel cell operation is performed. It leads to the development of high power generation performance under both conditions of high humidification and high humidification.
上記側鎖は、酸素透過性に一層優れ、電極触媒層のひび割れを一層抑制できる観点から、主鎖側に上記連結基(好ましくは、スルホニル基及び/又は環構造に含まれないエーテル結合)を有し、側鎖末端側に上記環状構造を有することが好ましい。 The side chain has the above-mentioned linking group (preferably a sulfonyl group and / or an ether bond not contained in the ring structure) on the main chain side from the viewpoint of further excellent oxygen permeability and further suppressing cracking of the electrode catalyst layer. It is preferable to have the above-mentioned cyclic structure on the terminal side of the side chain.
上記側鎖は、上記環状構造が側鎖末端に位置してもよいし、側鎖の中間に位置してもよい。例えば、環状構造よりも側鎖末端側に炭化水素基、スルホン酸基等のプロトン伝導性基が配置されてよく、主鎖側から側鎖末端に向けて、連結基、環状構造、プロトン伝導性基の順に配置される側鎖であってもよい。
上記側鎖は、酸素透過性に一層優れ、電極触媒層のひび割れを一層抑制できる観点から、主鎖に環構造に含まれないエーテル結合が結合し、該エーテル結合に炭素数1〜10(好ましくは炭素数3〜5)のフッ素化炭化水素基が結合し、該フッ素化炭化水素基にスルホニル基が結合し、該スルホニル基に上記環状構造が結合する構造が好ましい。
The side chain may have the annular structure located at the end of the side chain or in the middle of the side chain. For example, a proton conductive group such as a hydrocarbon group or a sulfonic acid group may be arranged on the side chain terminal side of the cyclic structure, and the linking group, the cyclic structure, or the proton conductive group is arranged from the main chain side to the side chain terminal. It may be a side chain arranged in the order of groups.
From the viewpoint of further excellent oxygen permeability and further suppressing cracking of the electrode catalyst layer, the side chain has an ether bond not included in the ring structure bonded to the main chain, and the ether bond has 1 to 10 carbon atoms (preferably). Is preferably a structure in which a fluorinated hydrocarbon group having 3 to 5 carbon atoms is bonded, a sulfonyl group is bonded to the fluorinated hydrocarbon group, and the cyclic structure is bonded to the sulfonyl group.
上記側鎖としては、酸素透過性に一層優れ、電極触媒層のひび割れを一層抑制できる観点から、以下の構造が好ましい。以下の構造が、例えば、後述の主鎖のAであってよい。
上記構造単位Aの主鎖としては、特に限定されないが、例えば、下記式(50)で表される構造の主鎖
(式(50)中、X1〜X3は、それぞれ独立に、水素原子、フッ素原子、塩素原子を表す。Aは上記式35〜式40を有する側鎖を表す。);下記式(51)で表される構造を含む主鎖
(式(51)中、X1〜X5のうち、少なくとも2つは、単結合、エーテル基、チオエーテル基、スルホニル基、カルボニル基から選ばれる結合基を表し、それぞれ同一でも異なっても良い。また、上記芳香族環を複数含む場合は、上記結合基を介して芳香族環が結合していてもよい。上記結合基を介して隣り合う構造単位の主鎖と結合する。上記結合基以外のX1〜X5はそれぞれ独立に、水素原子、フッ素原子、フッ素化されていてもよい炭素数1〜10のアルキル基を表す。Aは、上記側鎖を有する部位を表し、上記芳香族環が複数あるときは、少なくとも一つの芳香族環のAが上記側鎖(例えば、式41〜式46を有する部位)を有していればよい。)等の少なくとも1つの芳香族環と少なくとも1つのエーテル結合とを含む主鎖;下記式(52)で表される主鎖
(式(52)中、nは構造単位の繰り返し数を表し、Aは、上記側鎖を有する部位(例えば、式41〜式46を有する部位)を表す。);等が挙げられる。
上記主鎖としては、−(CF2−CFA)−、−(CH2−CHA)−等のエチレン系主鎖;ポリエーテルケトン(PEK)、ポリエーテルエーテルケトン(PEEK)、ポリエーテルスルホン(PES)、ポリフェニレンエーテル(PPE)等の主鎖にエーテル結合を有する主鎖;が好ましく、中でも、電池性能、化学耐久性の観点から、−(CF2−CFA)−が好ましい。
The main chain of the structural unit A is not particularly limited, but for example, the main chain of the structure represented by the following formula (50).
(In the formula (50), X 1 to X 3 independently represent a hydrogen atom, a fluorine atom, and a chlorine atom. A represents a side chain having the above formulas 35 to 40.); The following formula (51). ) Main chain containing the structure represented by
(In the formula (51) , at least two of X 1 to X 5 represent a binding group selected from a single bond, an ether group, a thioether group, a sulfonyl group, and a carbonyl group, and may be the same or different from each other. When a plurality of the aromatic rings are contained, the aromatic rings may be bonded via the bonding group. The aromatic rings are bonded to the main chains of adjacent structural units via the bonding groups. Other than the bonding groups. X 1 to X 5 independently represent a hydrogen atom, a fluorine atom, and an alkyl group having 1 to 10 carbon atoms which may be fluorinated. A represents a site having the side chain and the aromatic. When there are a plurality of rings, at least one aromatic ring such as A of at least one aromatic ring may have the above side chain (for example, a site having formulas 41 to 46) and at least one aromatic ring. Main chain containing one ether bond; main chain represented by the following formula (52)
(In formula (52), n represents the number of repetitions of the structural unit, and A represents a portion having the side chain (for example, a portion having formulas 41 to 46); and the like.
Examples of the main chain include ethylene-based main chains such as-(CF 2- CFA) -and-(CH 2- CHA)-; polyetherketone (PEK), polyetheretherketone (PEEK), and polyethersulfone (PES). ), A main chain having an ether bond in the main chain such as polyphenylene ether (PPE); among them,-(CF 2- CFA)-is preferable from the viewpoint of battery performance and chemical durability.
(他の構造単位)
上記他の構造単位としては、上記構造単位Aと同じ主鎖を有し、上記側鎖を有さない構造単位としてもよい。上記他の構造単位は、例えば、上記構造単位Aと同じ主鎖を有し、側鎖を有さない構造単位と、上記構造単位Aと同じ主鎖を有し、プロトン伝導性を促す側鎖を有する構造単位とであってもよい。
(Other structural units)
The other structural unit may be a structural unit having the same main chain as the structural unit A and not having the side chain. The other structural unit is, for example, a structural unit having the same main chain as the structural unit A and having no side chain, and a side chain having the same main chain as the structural unit A and promoting proton conductivity. It may be a structural unit having.
本実施形態の含フッ素高分子電解質は、プロトン伝導性を促す側鎖を有してもよい。
プロトン伝導性を促す側鎖としては、下記式(53)〜下記式(56)で表わされる構造であることが好ましい。
(式(53)中、Xは、F、Cl、又は置換されていてもよい炭素数1〜3のフッ素化炭化水素基を表す。kは0〜2の整数、nは0〜8の整数を表す。n個のXは、同一でも異なっていてもよい。Yは、F又はClを表す。mは1〜6の整数を表す。m個のYは、同一でも異なっていてもよい。Zは、H、アルカリ金属、又はアルカリ土類金属表す。)
上記式(53)において、特に、kが0又は2、nが0、mが2、YがF、ZがHであることが好ましい。
(式(54)中、Xは、F、Cl、又は置換されていてもよい炭素数1〜3のフッ素化炭化水素基を表す。kは0〜2の整数、nは0〜8の整数を表す。n個のXは、同一でも異なっていてもよい。Yは、F又はClを表す。mは1〜6の整数を表す。m個のYは、同一でも異なっていてもよい。Zは、NR1R2を表す。R1及びR2は、それぞれ独立に、置換されていてもよい炭素数1〜10のアルキル基、水素原子、−SO2−R3を表す。ここでR3は炭素数1〜10の炭化水素基を表す。R1、R2の一方が置換されても良いアルキル基又は水素であるとき、R2は−SO2−R3である。)
上記式(54)において、特に、kが0又は2、nが0、mが2であることが好ましい。
(式(55)中、Rfは、それぞれ独立にエーテル結合性酸素原子を含む炭素数1〜10のフッ素化炭化水素基、単結合を表す。Xは、H、アルカリ金属、又はアルカリ土類金属を表す。)
(式(56)中、Rfは、それぞれ独立にエーテル結合性酸素原子を含む炭素数1〜10のフッ素化炭化水素基、単結合を表す。XはNR1R2を表す。R1及びR2は、それぞれ独立に、置換されていてもよい炭素数1〜10のアルキル基又は水素、−SO2−R3を表す。ここでR3は炭素数1〜10の炭化水素基を表す。R1、R2の一方が置換されても良いアルキル基又は水素であるとき、R2は−SO2−R3である。)
The fluorine-containing polymer electrolyte of the present embodiment may have a side chain that promotes proton conductivity.
The side chain that promotes proton conductivity preferably has a structure represented by the following formulas (53) to (56).
(In formula (53), X represents F, Cl, or a fluorinated hydrocarbon group having 1 to 3 carbon atoms which may be substituted. K is an integer of 0 to 2, and n is an integer of 0 to 8. The n Xs may be the same or different. Y represents F or Cl. M represents an integer of 1-6. The m Ys may be the same or different. Z represents H, an alkali metal, or an alkaline earth metal.)
In the above formula (53), it is particularly preferable that k is 0 or 2, n is 0, m is 2, Y is F, and Z is H.
(In formula (54), X represents F, Cl, or a fluorinated hydrocarbon group having 1 to 3 carbon atoms which may be substituted. K is an integer of 0 to 2, and n is an integer of 0 to 8. The n Xs may be the same or different. Y represents F or Cl. M represents an integer of 1-6. The m Ys may be the same or different. Z represents NR 1 R 2. R 1 and R 2 each independently represent an alkyl group having 1 to 10 carbon atoms, a hydrogen atom, and −SO 2 −R 3 . R 3 represents a hydrocarbon group having 1 to 10 carbon atoms. When one of R 1 and R 2 is an alkyl group or hydrogen which may be substituted, R 2 is −SO 2 − R 3 ).
In the above formula (54), it is particularly preferable that k is 0 or 2, n is 0, and m is 2.
(In the formula (55), Rf independently represents a fluorinated hydrocarbon group having 1 to 10 carbon atoms containing an ether-bonding oxygen atom and a single bond. X is H, an alkali metal, or an alkaline earth metal. Represents.)
(In the formula (56), Rf independently represents a fluorinated hydrocarbon group having 1 to 10 carbon atoms containing an ether-bonding oxygen atom, and a single bond. X represents NR 1 R 2. R 1 and R 2. 2 represents an alkyl group or hydrogen having 1 to 10 carbon atoms which may be substituted independently, and −SO 2 −R 3 where R 3 represents a hydrocarbon group having 1 to 10 carbon atoms. When one of R 1 and R 2 is an alkyl group or hydrogen which may be substituted, R 2 is −SO 2 − R 3 ).
上記他の構造単位としては、下記式(57)で表される構造を有する側鎖(D)を有する構造単位を含んでいてもよく、−(CF2−CFA)−のAに上記側鎖(D)が直接結合した構造単位としてよい。上記側鎖(D)を有する構造単位を導入することで、含フッ素高分子電解質溶液を調製する際に、溶媒への溶解性を調整することが可能となる。
(式(57)中、Rfは炭素数1〜10のフッ素化炭化水素基を表す。上記フッ素化炭化水素基は構造中にエーテル性酸素原子を含んでも良い。)
上記側鎖(D)としては、−O−CF3、−O−C2F5、−O−C3F7、−O−C2F4−O−C2F5、−O−(CF2CF(CF3))−O−C3F7、等が挙げられる。
The other structural unit may include a structural unit having a side chain (D) having a structure represented by the following formula (57), and the side chain is added to A of − (CF 2-CFA) −. It may be a structural unit in which (D) is directly bonded. By introducing the structural unit having the side chain (D), it becomes possible to adjust the solubility in a solvent when preparing a fluorine-containing polymer electrolyte solution.
(In the formula (57), Rf represents a fluorinated hydrocarbon group having 1 to 10 carbon atoms. The fluorinated hydrocarbon group may contain an ethereal oxygen atom in the structure.)
The side chains (D) include -O-CF 3 , -O-C 2 F 5 , -O-C 3 F 7 , -O-C 2 F 4 -O-C 2 F 5 , -O- ( CF 2 CF (CF 3 ))-OC 3 F 7 , and the like can be mentioned.
上記他の構造単位における主鎖としては、上述の構造単位Aにおける主鎖と同様のものが挙げられる。 Examples of the main chain in the other structural unit include the same as the main chain in the structural unit A described above.
(構造単位の含有割合)
本実施形態の含フッ素高分子電解質中の上記構造単位Aの割合は、下記の導入率により求めることができる。
上記導入率は、1.0mol%以上80.0mol%以下が好ましく、10.0mol%以上70.0mol%以下がより好ましく、10.0mol%以上60.0mol%以下がさらに好ましい。上記導入率が1.0mol%以上であることにより、電極触媒層のひび割れを一層抑制し、酸素透過率が高く、耐久性に一層優れる。また、80.0mol%以下であることにより、プロトン伝導性にも優れ、電池性能に一層優れる。
なお、上記導入率は、後述の実施例に記載の方法により測定することができる。
(Content ratio of structural units)
The ratio of the structural unit A in the fluorine-containing polymer electrolyte of the present embodiment can be determined by the following introduction rate.
The introduction rate is preferably 1.0 mol% or more and 80.0 mol% or less, more preferably 10.0 mol% or more and 70.0 mol% or less, and further preferably 10.0 mol% or more and 60.0 mol% or less. When the introduction rate is 1.0 mol% or more, cracks in the electrode catalyst layer are further suppressed, the oxygen permeability is high, and the durability is further excellent. Further, when it is 80.0 mol% or less, the proton conductivity is also excellent, and the battery performance is further excellent.
The introduction rate can be measured by the method described in Examples described later.
(特性)
本実施形態の含フッ素高分子電解質は、当量重量EW(プロトン交換基1当量あたりの含フッ素高分子電解質の乾燥質量グラム数)が100〜2000g/eqであることが好ましい。即ち、上記EWの範囲内となるように共重合比やプロトン伝導性基導入率を制御することが好ましい。EWの上限は、好ましくは1000g/eqであり、より好ましくは900g/eqである。EWの下限は、好ましくは300g/eqであり、より好ましくは500g/eqである。EWが上記の範囲内にあることにより、加工性に一層優れ、電極触媒層の伝導度が低くなりすぎず、熱水への溶解性も小さい。
なお、等量重量EWは、後述の実施例に記載の方法により測定することができる。
(Characteristic)
The fluorine-containing polymer electrolyte of the present embodiment preferably has an equivalent weight EW (the number of dry mass grams of the fluorine-containing polymer electrolyte per equivalent of a proton exchange group) of 100 to 2000 g / eq. That is, it is preferable to control the copolymerization ratio and the proton conductive group introduction rate so as to be within the above EW range. The upper limit of the EW is preferably 1000 g / eq, more preferably 900 g / eq. The lower limit of the EW is preferably 300 g / eq, more preferably 500 g / eq. When the EW is within the above range, the processability is further excellent, the conductivity of the electrode catalyst layer is not too low, and the solubility in hot water is also small.
The equivalent weight EW can be measured by the method described in Examples described later.
本実施形態の含フッ素高分子電解質の数平均分子量は、加工性、電気伝導度及び機械的強度が一層優れることから、1万〜200万であることが好ましく、より好ましくは3万〜100万である。
上記数平均分子量は、GPC(ゲルパーミエーションクロマトグラフ)法により測定される値であり、例えば、以下に示す方法により、標準ポリスチレンを基準として数平均分子量を算出することができる。
TOSOH社製 HLC−8020を用い、カラムはポリスチレンゲル製MIXカラム(東ソーGMHシリーズ、30cmサイズ)を3本、40℃、NMP(5mmol/L LiBr含有)溶剤、流速0.7mL/分で行うことができる。サンプル濃度は、0.1質量%で打ち込み量は500μLで行うことができる。数平均分子量がポリスチレン換算値で10万〜80万程度のものが更に好ましく、13万〜70万程度のものが更により好ましく、16万〜60万程度のものが特に好ましい。
The number average molecular weight of the fluorine-containing polymer electrolyte of the present embodiment is preferably 10,000 to 2 million, more preferably 30,000 to 1,000,000, because the processability, electrical conductivity, and mechanical strength are further excellent. Is.
The number average molecular weight is a value measured by a GPC (gel permeation chromatography) method. For example, the number average molecular weight can be calculated with reference to standard polystyrene by the method shown below.
Using HLC-8020 manufactured by TOSOH, the column should be three polystyrene gel MIX columns (Tosoh GMH series, 30 cm size), 40 ° C., NMP (containing 5 mmol / L LiBr) solvent, and a flow rate of 0.7 mL / min. Can be done. The sample concentration can be 0.1% by mass and the driving amount can be 500 μL. Those having a number average molecular weight of about 100,000 to 800,000 in terms of polystyrene are further preferable, those of about 130,000 to 700,000 are even more preferable, and those of about 160,000 to 600,000 are particularly preferable.
本実施形態の含フッ素高分子電解質のメルトフローレート(MFR)は、加工性、電気伝導度及び機械的強度が一層優れることから、0.1〜1000g/10分であることが好ましく、0.5g/10分以上であることがより好ましく、1.0g/10分以上であることが更に好ましく、200g/10分以下であることがより好ましく、100g/10分以下であることが更に好ましい。
上記MFRは、ASTM規格D1238に従って270℃、荷重2.16kgの条件下で、MELT INDEXER TYPE C−5059D(商品名、東洋精機社製)を用いて測定することができる。
The melt flow rate (MFR) of the fluorine-containing polymer electrolyte of the present embodiment is preferably 0.1 to 1000 g / 10 minutes because it is more excellent in processability, electrical conductivity and mechanical strength. It is more preferably 5 g / 10 minutes or more, further preferably 1.0 g / 10 minutes or more, further preferably 200 g / 10 minutes or less, and further preferably 100 g / 10 minutes or less.
The MFR can be measured using MELT INDEXER TYPE C-5059D (trade name, manufactured by Toyo Seiki Co., Ltd.) under the conditions of 270 ° C. and a load of 2.16 kg according to ASTM standard D1238.
(製造方法)
上記含フッ素高分子電解質は、所定の構造単位を形成できるモノマーを重合して得てもよいし、重合後の重合体に所定の側鎖を導入してもよい。
上記含フッ素高分子電解質は、例えば、重縮合、ラジカル重合、アニオン重合等の従来公知の方法にて合成することができ、中でも、重縮合又はラジカル重合が好ましく用いられる。
上記含フッ素高分子電解質粒子が水に分散又は溶解したエマルションの形態で、上記含フッ素高分子電解質が得られる。
(Production method)
The fluorine-containing polymer electrolyte may be obtained by polymerizing a monomer capable of forming a predetermined structural unit, or a predetermined side chain may be introduced into the polymer after the polymerization.
The fluorine-containing polymer electrolyte can be synthesized by conventionally known methods such as polycondensation, radical polymerization, and anionic polymerization. Among them, polycondensation or radical polymerization is preferably used.
The fluorine-containing polymer electrolyte can be obtained in the form of an emulsion in which the fluorine-containing polymer electrolyte particles are dispersed or dissolved in water.
上記ラジカル重合は、界面活性剤の存在下に行ってもよい。界面活性剤としては、公知の含フッ素アニオン界面活性剤が好ましい。 The radical polymerization may be carried out in the presence of a surfactant. As the surfactant, a known fluorine-containing anionic surfactant is preferable.
上記ラジカル重合は、重合開始剤を添加して行うことが好ましい。上記重合開始剤としては、重合温度でラジカルを発生しうるものであれば特に限定されず、公知の油溶性及び/又は水溶性の重合開始剤を使用することができる。また、レドックス開始剤を使用してもよい。上記重合開始剤の濃度は、目的とする重合体の分子量、反応速度によって適宜決定される。
上記重合開始剤としては、過硫酸アンモニウム、過硫酸カリウム等の過硫酸塩、ジコハク酸パーオキシド、ジグルタル酸パーオキシド、tert−ブチルヒドロパーオキシド等の有機過酸化物が挙げられる。上記レドックス開始剤としては、過硫酸塩又は有機過酸化物と、亜硫酸ナトリウム等の亜硫酸塩、亜硫酸水素ナトリウム等の重亜硫酸塩、臭素酸塩、ジイミン、シュウ酸等の還元剤とを組み合わせたものが挙げられる。
The radical polymerization is preferably carried out by adding a polymerization initiator. The polymerization initiator is not particularly limited as long as it can generate radicals at the polymerization temperature, and known oil-soluble and / or water-soluble polymerization initiators can be used. You may also use a redox initiator. The concentration of the polymerization initiator is appropriately determined depending on the molecular weight and reaction rate of the target polymer.
Examples of the polymerization initiator include persulfates such as ammonium persulfate and potassium persulfate, and organic peroxides such as disuccinic acid peroxide, diglutaric acid peroxide, and tert-butyl hydroperoxide. The redox initiator is a combination of a persulfate or an organic peroxide, a sulfite such as sodium sulfite, a bisulfite such as sodium bisulfite, and a reducing agent such as bromate, diimine, and oxalic acid. Can be mentioned.
ラジカル重合は、0.05〜5.0MPaの圧力下で行うことができる。好ましい圧力の範囲は0.1〜1.5MPaである。また、ラジカル重合は、5〜100℃の温度で行うことができる。好ましい温度の範囲は10〜90℃である。ラジカル重合では、また、目的に応じて、公知の安定剤、連鎖移動剤等を添加してもよい。 Radical polymerization can be carried out under a pressure of 0.05 to 5.0 MPa. The preferred pressure range is 0.1 to 1.5 MPa. In addition, radical polymerization can be carried out at a temperature of 5 to 100 ° C. The preferred temperature range is 10 to 90 ° C. In radical polymerization, known stabilizers, chain transfer agents and the like may be added depending on the purpose.
上記含フッ素高分子電解質はフッ素化して得てもよい。フッ素化の方法としては、例えば、特開2004−143622号公報に記載があるように、フッ素ガスあるいはフッ素ガスを不活性ガス(例えば、窒素、アルゴン、ヘリウム、炭酸ガス等)で希釈した混合ガスを被処理物に接触させることにより施すことができる。 The fluorine-containing polymer electrolyte may be obtained by fluorination. As a method of fluorination, for example, as described in Japanese Patent Application Laid-Open No. 2004-143622, a mixed gas obtained by diluting fluorine gas or fluorine gas with an inert gas (for example, nitrogen, argon, helium, carbon dioxide gas, etc.) Can be applied by contacting the object to be treated.
(含フッ素高分子電解質溶液)
本実施形態の含フッ素高分子電解質溶液は、上記含フッ素高分子電解質と溶媒(例えば、水、有機溶媒等)とを含むことが好ましく、上記含フッ素高分子電解質と水及び/又は有機溶媒とを含むことがより好ましい。上記含フッ素高分子電解質溶液は、燃料電池の電極触媒層(例えば、カソード用電極触媒層)を形成する原料として好適に用いることができる。上記含フッ素高分子電解質溶液は、燃料電池の電極触媒層形成用含フッ素高分子電解質溶液であることが好ましい。
(Fluorine-containing polymer electrolyte solution)
The fluoropolymer electrolyte solution of the present embodiment preferably contains the fluoropolymer electrolyte and a solvent (for example, water, an organic solvent, etc.), and the fluoropolymer electrolyte and water and / or an organic solvent. It is more preferable to include. The fluorine-containing polymer electrolyte solution can be suitably used as a raw material for forming an electrode catalyst layer (for example, a cathode electrode catalyst layer) of a fuel cell. The fluorine-containing polymer electrolyte solution is preferably a fluorine-containing polymer electrolyte solution for forming an electrode catalyst layer of a fuel cell.
上記含フッ素高分子電解質溶液中の上記含フッ素高分子電解質の質量割合は、2〜50質量%であることが好ましく、5質量%以上であることがより好ましく、10質量%以上であることが更に好ましく、40質量%以下であることがより好ましく、30質量%以下であることが更に好ましく、25質量%以下であることが特に好ましい。 The mass ratio of the fluorine-containing polymer electrolyte in the fluorine-containing polymer electrolyte solution is preferably 2 to 50% by mass, more preferably 5% by mass or more, and preferably 10% by mass or more. It is more preferably 40% by mass or less, further preferably 30% by mass or less, and particularly preferably 25% by mass or less.
上記有機溶媒としては、メタノール、エタノール、n−プロパノール、イソプロピルアルコール、ブタノール、グリセリン等のプロトン性有機溶媒、N,N−ジメチルホルムアミド、N,N−ジメチルアセトアミド、N−メチルピロリドン等の非プロトン性溶媒、等が挙げられる。これらは1種を単独で、又は2種以上を併用することができる。 Examples of the organic solvent include protic organic solvents such as methanol, ethanol, n-propanol, isopropyl alcohol, butanol and glycerin, and aprotics such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone. Solvents, etc. may be mentioned. These can be used alone or in combination of two or more.
上記含フッ素高分子電解質溶液は、有機系添加剤を含んでもよい。また、上記含フッ素高分子電解質溶液は、無機系添加剤を含んでもよい。 The fluorine-containing polymer electrolyte solution may contain an organic additive. Further, the fluorine-containing polymer electrolyte solution may contain an inorganic additive.
上記有機系添加剤としては、原子がラジカルにより引き抜かれやすい化合物、例えば、3級炭素に結合した水素、炭素−ハロゲン結合等を構造中に有する化合物等が挙げられる。具体的には、ポリアニリンのような上記の官能基で一部置換された芳香族化合物、ポリベンゾイミダゾール、ポリベンゾオキサゾール、ポリベンゾチアゾール、ポリベンゾオキサジアゾール、フェニル化ポリキノキサリン、フェニル化ポリキノリン等の不飽和の複素環化合物を挙げることができる。
また、チオエーテル化合物も挙げられる。例えば、ジメチルチオエーテル、ジエチルチオエーテル、ジプロピルチオエーテル、メチルエチルチオエーテル、メチルブチルチオエーテルのようなジアルキルチオエーテル;テトラヒドロチオフェン、テトラヒドロアピランのような環状チオエーテル;メチルフェニルスルフィド、エチルフェニルスルフィド、ジフェニルスルフィド、ジベンジルスルフィドのような芳香族チオエーテル;等が挙げられる。
Examples of the organic additive include compounds in which atoms are easily extracted by radicals, for example, compounds having a hydrogen bonded to a tertiary carbon, a carbon-halogen bond, or the like in the structure. Specifically, aromatic compounds partially substituted with the above functional groups such as polyaniline, polybenzimidazole, polybenzoxazole, polybenzothiazole, polybenzoxadiazole, phenylated polyquinoxalin, phenylated polyquinolin, etc. An unsaturated heterocyclic compound of the above can be mentioned.
Also mentioned are thioether compounds. For example, dialkyl thioethers such as dimethyl thioether, diethyl thio ether, dipropyl thio ether, methyl ethyl thio ether, methyl butyl thio ether; cyclic thio ethers such as tetrahydrothiophene, tetrahydroapirane; methyl phenyl sulfide, ethyl phenyl sulfide, diphenyl sulfide, dibenzyl. Aromatic thioethers such as sulfide; and the like.
上記含フッ素高分子電解質溶液中の上記有機系添加剤の質量割合は、0.1質量%以上が好ましく、1質量%以上がより好ましく、3質量%以上がさらに好ましい。上記有機系添加剤を0.1質量%以上含有することで、燃料電池運転での化学耐久性を向上させることが可能となる。 The mass ratio of the organic additive in the fluorine-containing polymer electrolyte solution is preferably 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 3% by mass or more. By containing 0.1% by mass or more of the above organic additive, it is possible to improve the chemical durability in fuel cell operation.
上記無機系添加剤としては、例えば金属酸化物、金属炭酸塩、金属硝酸塩等が挙げられる。これらの無機添加剤はそれぞれ単独で用いても良いし、2種以上の混合物を用いても良い。
上記金属酸化物としては例えば、ジルコニア(ZrO2)、チタニア(TiO2)、シリカ(SiO2)、アルミナ(Al2O3)、酸化鉄(Fe2O3、FeO、Fe3O4)、酸化銅(CuO、Cu2O)、酸化亜鉛(ZnO)、酸化イットリウム(Y2O3)、酸化ニオブ(Nb2O5)、酸化モリブデン(MoO3)、酸化インジウム(In2O3、In2O)、酸化スズ(SnO2)、酸化タンタル(Ta2O5)、酸化タングステン(WO3、W2O5)、酸化鉛(PbO、PbO2)、酸化ビスマス(Bi2O3)、酸化セリウム(CeO2、Ce2O3)、酸化アンチモン(Sb2O3、Sb2O5)、酸化ゲルマニウム(GeO2、GeO)、酸化ランタン(La2O3)、酸化ルテニウム(RuO2)、酸化マンガン(MnO)、等が挙げられる。これら金属酸化物は、単独で用いても、混合物を用いてもよいし、例えば、スズ添加酸化インジウム(ITO)、アンチモン添加酸化スズ(ATO)、酸化アルミニウム亜鉛(ZnO・Al2O3)等に挙げられる複合酸化物を挙げることができる。
上記金属炭酸塩としては例えば、炭酸ジルコニウム(Zr(CO3)2)、炭酸チタニウム(Ti(CO3)2)、炭酸鉄(FeCO3)、炭酸銅(Cu2CO3)、炭酸亜鉛(ZnCO3)、炭酸モリブデン、炭酸セリウム(CeCO3)、炭酸ニッケル(NiCO3)、炭酸コバルト(CoCO3)、炭酸マンガン(MnCO3)、等が挙げられる。
上記金属硝酸塩としては例えば、硝酸ジルコニウム(Zr(NO3)4)、硝酸鉄(Fe(NO3)3)、硝酸銅(Cu(NO3)2)、硝酸チタン(Ti(NO3)4)、硝酸セリウム(Ce(NO3)3)、硝酸ニッケル(Ni(NO3)2)、硝酸コバルト(Co(NO3)2)、硝酸マンガン(Mn(NO3)2)、等が挙げられる。
Examples of the inorganic additive include metal oxides, metal carbonates, metal nitrates and the like. Each of these inorganic additives may be used alone, or a mixture of two or more kinds may be used.
Examples of the metal oxide include zirconia (ZrO 2 ), titania (TiO 2 ), silica (SiO 2 ), alumina (Al 2 O 3 ), iron oxide (Fe 2 O 3 , FeO, Fe 3 O 4 ), and the like. Copper oxide (CuO, Cu 2 O), zinc oxide (ZnO), yttrium oxide (Y 2 O 3 ), niobide oxide (Nb 2 O 5 ), molybdenum oxide (MoO 3 ), indium oxide (In 2 O 3 , In) 2 O), tin oxide (SnO 2 ), tantalum oxide (Ta 2 O 5 ), tungsten oxide (WO 3 , W 2 O 5 ), lead oxide (PbO, PbO 2 ), bismuth oxide (Bi 2 O 3 ), Celium Oxide (CeO 2 , Ce 2 O 3 ), Antimon Oxide (Sb 2 O 3 , Sb 2 O 5 ), Germanium Oxide (GeO 2 , GeO), Lantern Oxide (La 2 O 3 ), Luthenium Oxide (RuO 2 ) , Manganese oxide (MnO), and the like. These metal oxides may be used alone or as a mixture, and for example, tin-added indium oxide (ITO), antimony-added tin oxide (ATO), zinc aluminum oxide (ZnO / Al 2 O 3 ), etc. The composite oxides listed in the above can be mentioned.
Examples of the metal carbonate include zirconium carbonate (Zr (CO 3 ) 2 ), titanium carbonate (Ti (CO 3 ) 2 ), iron carbonate (FeCO 3 ), copper carbonate (Cu 2 CO 3 ), and zinc carbonate (ZnCO). 3 ), molybdenum carbonate, cerium carbonate (CeCO 3 ), nickel carbonate (NiCO 3 ), cobalt carbonate (CoCO 3 ), manganese carbonate (MnCO 3 ), and the like.
Examples of the metal nitrate include zirconium nitrate (Zr (NO 3 ) 4 ), iron nitrate (Fe (NO 3 ) 3 ), copper nitrate (Cu (NO 3 ) 2 ), and titanium nitrate (Ti (NO 3 ) 4 ). , Cerium nitrate (Ce (NO 3 ) 3 ), nickel nitrate (Ni (NO 3 ) 2 ), cobalt nitrate (Co (NO 3 ) 2 ), manganese nitrate (Mn (NO 3 ) 2 ), and the like.
上記含フッ素高分子電解質溶液中の上記無機系添加剤の質量割合は、0.1質量%以上が好ましく、1質量%以上がより好ましく、3質量%以上がさらに好ましい。上記無機系添加剤を0.1質量%以上含有することで、燃料電池運転での化学耐久性を向上させることが可能となる。 The mass ratio of the inorganic additive in the fluorine-containing polymer electrolyte solution is preferably 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 3% by mass or more. By containing 0.1% by mass or more of the above-mentioned inorganic additive, it is possible to improve the chemical durability in fuel cell operation.
上記含フッ素高分子電解質溶液は、有機溶媒を含む場合、さらに水を含むことが好ましく、有機溶媒と水との質量比は10/90〜90/10であることが好ましく、30/70以上であることがより好ましく、70/30以下であることがより好ましい。 When the fluorine-containing polymer electrolyte solution contains an organic solvent, it preferably further contains water, and the mass ratio of the organic solvent to water is preferably 10/90 to 90/10, and is 30/70 or more. It is more preferable that there is, and it is more preferable that it is 70/30 or less.
上記含フッ素高分子電解質溶液は、所望の固形分濃度にするために、濃縮することが可能である。濃縮の方法としては特に限定されない。例えば、加熱し、溶媒を蒸発させる方法や、減圧濃縮する方法等がある。その結果得られる含フッ素高分子電解質溶液の固形分率は、取り扱い性及び生産性を考慮して、最終的な含フッ素高分子電解質溶液の固形分率は0.5〜50質量%が好ましい。 The fluorine-containing polymer electrolyte solution can be concentrated to obtain a desired solid content concentration. The method of concentration is not particularly limited. For example, there are a method of heating and evaporating the solvent, a method of concentrating under reduced pressure, and the like. The solid content of the resulting fluorine-containing polymer electrolyte solution is preferably 0.5 to 50% by mass in consideration of handleability and productivity.
上記含フッ素高分子電解質溶液は、粗大粒子成分を除去する観点から、濾過されることがより好ましい。濾過方法は、特に限定されず、従来行われている一般的な方法が適用できる。例えば、通常使用されている定格濾過精度を有する濾材を加工したフィルターを用いて、加圧濾過する方法が代表的に挙げられる。フィルターについては、90%捕集粒子径が粒子の平均粒子径の10〜100倍の濾材を使用することが好ましい。この濾材は濾紙でもよいし、金属焼結フィルターのような濾材でもよい。特に濾紙の場合は、90%捕集粒子径が粒子の平均粒子径の10〜50倍であることが好ましい。金属焼結フィルターの場合は、90%捕集粒子径が粒子の平均粒子径の50〜100倍であることが好ましい。当該90%捕集粒子径を平均粒径の10倍以上に設定することは、送液するときに必要な圧力が高くなりすぎることを抑制したり、フィルターが短期間で閉塞したりすることを抑制し得る。一方、平均粒子径の100倍以下に設定することは、フィルムで異物の原因となるような粒子の凝集物や樹脂の未溶解物を良好に除去する観点から好ましい。 The fluorine-containing polymer electrolyte solution is more preferably filtered from the viewpoint of removing coarse particle components. The filtration method is not particularly limited, and a conventional general method can be applied. For example, a method of pressurizing filtration using a filter obtained by processing a filter medium having a rated filtration accuracy, which is usually used, can be typically mentioned. As for the filter, it is preferable to use a filter medium having a 90% collection particle size of 10 to 100 times the average particle size of the particles. This filter medium may be a filter paper or a filter medium such as a metal sintered filter. Especially in the case of filter paper, it is preferable that the 90% collected particle size is 10 to 50 times the average particle size of the particles. In the case of a metal sintered filter, it is preferable that the 90% collected particle size is 50 to 100 times the average particle size of the particles. Setting the 90% collected particle size to 10 times or more the average particle size prevents the pressure required for liquid transfer from becoming too high and prevents the filter from clogging in a short period of time. Can be suppressed. On the other hand, setting it to 100 times or less the average particle size is preferable from the viewpoint of satisfactorily removing agglomerates of particles and undissolved resin which may cause foreign substances in the film.
(含フッ素高分子電解質含有組成物(電極触媒インク))
上記含フッ素高分子電解質は、電極触媒インクを形成する原料として好適に用いることができる。上記電極触媒インクは、上記含フッ素高分子電解質、溶媒(例えば、水及び/又は有機溶媒)、並びに、触媒を含むことが好ましい。上記電極触媒インクは、燃料電池の電極触媒層(例えば、カソード用電極触媒層)を形成する原料として好適に用いることができる。上記電極触媒インクは、燃料電池の電極触媒層形成用電極触媒インクであることが好ましい。
(Fluorine-containing polymer electrolyte-containing composition (electrode catalyst ink))
The fluorine-containing polymer electrolyte can be suitably used as a raw material for forming the electrode catalyst ink. The electrode catalyst ink preferably contains the fluorine-containing polymer electrolyte, a solvent (for example, water and / or an organic solvent), and a catalyst. The electrode catalyst ink can be suitably used as a raw material for forming an electrode catalyst layer (for example, a cathode electrode catalyst layer) of a fuel cell. The electrode catalyst ink is preferably an electrode catalyst ink for forming an electrode catalyst layer of a fuel cell.
上記触媒としては、電極触媒層において活性を有し得るものであれば特に限定されず、上記電極触媒層が用いられる燃料電池の使用目的に応じて適宜選択される。上記触媒は、触媒金属であることが好ましい。
上記触媒としては、水素の酸化反応及び酸素の還元反応を促進する金属であることが好ましく、白金、金、銀、パラジウム、イリジウム、ロジウム、ルテニウム、鉄、コバルト、ニッケル、クロム、タングステン、マンガン、バナジウム、及びこれらの合金からなる群より選択される少なくとも一種の金属であることがより好ましい。中でも、白金が好ましい。
The catalyst is not particularly limited as long as it can have activity in the electrode catalyst layer, and is appropriately selected according to the purpose of use of the fuel cell in which the electrode catalyst layer is used. The catalyst is preferably a catalyst metal.
The catalyst is preferably a metal that promotes the oxidation reaction of hydrogen and the reduction reaction of oxygen, and is preferably platinum, gold, silver, palladium, iridium, rhodium, ruthenium, iron, cobalt, nickel, chromium, tungsten, manganese, etc. More preferably, it is at least one metal selected from the group consisting of vanadium and alloys thereof. Of these, platinum is preferable.
触媒金属の粒子径は限定されないが、10〜1000オングストロームが好ましく、より好ましくは10〜500オングストローム、最も好ましくは15〜100オングストロームである。 The particle size of the catalyst metal is not limited, but is preferably 10 to 1000 angstroms, more preferably 10 to 500 angstroms, and most preferably 15 to 100 angstroms.
上記電極触媒インク中の上記含フッ素高分子電解質の含有量は、上記電極触媒インクに対して、5〜30質量%であることが好ましく、8質量%以上であることがより好ましく、10質量%以上であることが更に好ましく、20質量%以下であることがより好ましく、15質量%以下であることが更に好ましい。
上記電極触媒インク中の上記触媒の含有量は、上記含フッ素高分子電解質に対して、50〜200質量%であることが好ましく、80質量%以上であることがより好ましく、100%質量%以上であることが更に好ましく、150質量%以下であることがより好ましく、130質量%以下であることが更に好ましい。
The content of the fluorine-containing polymer electrolyte in the electrode catalyst ink is preferably 5 to 30% by mass, more preferably 8% by mass or more, and 10% by mass with respect to the electrode catalyst ink. The above is more preferable, 20% by mass or less is more preferable, and 15% by mass or less is further preferable.
The content of the catalyst in the electrode catalyst ink is preferably 50 to 200% by mass, more preferably 80% by mass or more, and 100% by mass or more with respect to the fluorine-containing polymer electrolyte. It is more preferably 150% by mass or less, and further preferably 130% by mass or less.
上記電極触媒インクは、更に、導電剤を含むことが好ましい。上記触媒及び上記導電剤は、上記触媒の粒子を担持した導電剤からなる複合粒子(例えば、Pt担持カーボン等)であることも好ましい形態の一つである。この場合、上記含フッ素高分子電解質は、バインダーとしても機能する。 The electrode catalyst ink preferably further contains a conductive agent. It is also one of the preferable forms that the catalyst and the conductive agent are composite particles (for example, Pt-supported carbon or the like) composed of the conductive agent supporting the particles of the catalyst. In this case, the fluorine-containing polymer electrolyte also functions as a binder.
導電剤としては、導電性を有する粒子(導電性粒子)であれば限定されないが、例えば、ファーネスブラック、チャンネルブラック、アセチレンブラック等のカーボンブラック、活性炭、黒鉛及び各種金属(触媒金属を除く)からなる群より選択される少なくとも1種の導電性粒子であることが好ましい。これら導電剤の粒子径としては、好ましくは10オングストローム〜10μm、より好ましくは50オングストローム〜1μm、最も好ましくは100〜5000オングストロームである。 The conductive agent is not limited as long as it is conductive particles (conductive particles), but for example, from carbon black such as furnace black, channel black, acetylene black, activated carbon, graphite and various metals (excluding catalyst metal). It is preferable that it is at least one kind of conductive particles selected from the group. The particle size of these conductive agents is preferably 10 angstroms to 10 μm, more preferably 50 angstroms to 1 μm, and most preferably 100 to 5000 angstroms.
上記複合粒子としては、導電性粒子に対する触媒粒子の含有量が、好ましくは1〜99質量%、より好ましくは10〜90質量%、最も好ましくは30〜70質量%である。具体的には、田中貴金属工業(株)製TEC10E40E、TEC10E50E、TEC10E50HT等のPt触媒担持カーボンが好適な例として挙げられる。 As the composite particles, the content of the catalyst particles with respect to the conductive particles is preferably 1 to 99% by mass, more preferably 10 to 90% by mass, and most preferably 30 to 70% by mass. Specifically, Pt catalyst-supported carbons such as TEC10E40E, TEC10E50E, and TEC10E50HT manufactured by Tanaka Kikinzoku Kogyo Co., Ltd. are preferable examples.
複合粒子の含有量は、上記含フッ素高分子電解質に対して、1.0〜3.0質量%であることが好ましく、より好ましくは1.4〜2.9質量%、更に好ましくは1.7〜2.9質量%、特に好ましくは1.7〜2.3質量%である。 The content of the composite particles is preferably 1.0 to 3.0% by mass, more preferably 1.4 to 2.9% by mass, and further preferably 1. It is 7 to 2.9% by mass, particularly preferably 1.7 to 2.3% by mass.
上記電極触媒インクは、更に、撥水剤を含んでもよい。
上記電極触媒インクは、撥水性の向上のため、更にポリテトラフルオロエチレン(以下、PTFE)、テトラフルオロエチレンとパーフルオロ(2,2−ジメチル―1,3−ジオキソール)の共重合体を含有してもよい。この場合、撥水剤の形状としては特に限定されないが、定形性のものであればよく、粒子状、繊維状であることが好ましく、これらが単独で使用されても混合して使用されていてもよい。
The electrode catalyst ink may further contain a water repellent.
The electrode catalyst ink further contains polytetrafluoroethylene (hereinafter referred to as PTFE) and a copolymer of tetrafluoroethylene and perfluoro (2,2-dimethyl-1,3-dioxol) in order to improve water repellency. You may. In this case, the shape of the water repellent is not particularly limited, but it may be a fixed form, preferably in the form of particles or fibers, and even if these are used alone, they are mixed and used. May be good.
上記撥水剤の含有量は、上記含フッ素高分子電解質に対して、0.01〜30.0質量%であることが好ましく、より好ましくは1.0〜25.0質量%、更に好ましくは2.0〜20.0質量%、特に好ましくは5.0〜10.0質量%である。 The content of the water repellent is preferably 0.01 to 30.0% by mass, more preferably 1.0 to 25.0% by mass, still more preferably 1.0 to 25.0% by mass, based on the fluorine-containing polymer electrolyte. It is 2.0 to 20.0% by mass, particularly preferably 5.0 to 10.0% by mass.
上記電極触媒インクは、親水性向上及び化学耐久性向上のため、無機系添加剤を配合しても良い。
無機系添加剤としては、例えば金属酸化物、金属炭酸塩、金属硝酸塩等が挙げられる。
これらの無機添加剤はそれぞれ単独で用いても良いし、2種以上の混合物を用いても良い。具体的には、金属酸化物としては例えば、ジルコニア(ZrO2)、チタニア(TiO2)、シリカ(SiO2)、アルミナ(Al2O3)、酸化鉄(Fe2O3、FeO、Fe3O4)、酸化銅(CuO、Cu2O)、酸化亜鉛(ZnO)、酸化イットリウム(Y2O3)、酸化ニオブ(Nb2O5)、酸化モリブデン(MoO3)、酸化インジウム(In2O3、In2O)、酸化スズ(SnO2)、酸化タンタル(Ta2O5)、酸化タングステン(WO3、W2O5)、酸化鉛(PbO、PbO2)、酸化ビスマス(Bi2O3)、酸化セリウム(CeO2、Ce2O3)、酸化アンチモン(Sb2O3、Sb2O5)、酸化ゲルマニウム(GeO2、GeO)、酸化ランタン(La2O3)、酸化ルテニウム(RuO2)、酸化マンガン(MnO)等が挙げられる。これら金属酸化物は、単独で用いても、混合物を用いてもよいし、例えば、スズ添加酸化インジウム(ITO)、アンチモン添加酸化スズ(ATO)、酸化アルミニウム亜鉛(ZnO・Al2O3)等に挙げられる複合酸化物を挙げることができる。
金属炭酸塩としては例えば、炭酸ジルコニウム(Zr(CO3)2)、炭酸チタニウム(Ti(CO3)2)、炭酸鉄(FeCO3)、炭酸銅(Cu2CO3)、炭酸亜鉛(ZnCO3)、炭酸モリブデン、炭酸セリウム(CeCO3)、炭酸ニッケル(NiCO3)、炭酸コバルト(CoCO3)、炭酸マンガン(MnCO3)等が挙げられる。
金属硝酸塩としては例えば、硝酸ジルコニウム(Zr(NO3)4)、硝酸鉄(Fe(NO3)3)、硝酸銅(Cu(NO3)2)、硝酸チタン(Ti(NO3)4)、硝酸セリウム(Ce(NO3)3)、硝酸ニッケル(Ni(NO3)2)、硝酸コバルト(Co(NO3)2)、硝酸マンガン(Mn(NO3)2)等が挙げられる。
中でも、親水性向上の観点からシリカ(SiO2)が好ましく、化学耐久性向上の観点から酸化セリウム(CeO2、Ce2O3)、酸化マンガン(MnO)、炭酸セリウム(CeCO3)、炭酸マンガン(MnCO3)、硝酸セリウム(Ce(NO3)3)、硝酸マンガン(Mn(NO3)2)、硝酸チタン(Ti(NO3)4)が好ましい。
The electrode catalyst ink may contain an inorganic additive in order to improve hydrophilicity and chemical durability.
Examples of the inorganic additive include metal oxides, metal carbonates, metal nitrates and the like.
Each of these inorganic additives may be used alone, or a mixture of two or more kinds may be used. Specifically, examples of the metal oxide include zirconia (ZrO 2 ), titania (TiO 2 ), silica (SiO 2 ), alumina (Al 2 O 3 ), iron oxide (Fe 2 O 3 , FeO, Fe 3). O 4 ), copper oxide (CuO, Cu 2 O), zinc oxide (ZnO), yttrium oxide (Y 2 O 3 ), niobide oxide (Nb 2 O 5 ), molybdenum oxide (MoO 3 ), indium oxide (In 2) O 3 , In 2 O), tin oxide (SnO 2 ), tantalum oxide (Ta 2 O 5 ), tungsten oxide (WO 3 , W 2 O 5 ), lead oxide (PbO, PbO 2 ), bismuth oxide (Bi 2) O 3 ), cerium oxide (CeO 2 , Ce 2 O 3 ), antimony oxide (Sb 2 O 3 , Sb 2 O 5 ), germanium oxide (GeO 2 , GeO), lanthanum oxide (La 2 O 3 ), ruthenium oxide (RuO 2 ), manganese oxide (MnO) and the like can be mentioned. These metal oxides may be used alone or as a mixture, and for example, tin-added indium oxide (ITO), antimony-added tin oxide (ATO), zinc aluminum oxide (ZnO / Al 2 O 3 ), etc. The composite oxides listed in the above can be mentioned.
Examples of metal carbonates include zirconium carbonate (Zr (CO 3 ) 2 ), titanium carbonate (Ti (CO 3 ) 2 ), iron carbonate (FeCO 3 ), copper carbonate (Cu 2 CO 3 ), and zinc carbonate (ZnCO 3). ), Molybdenum carbonate, cerium carbonate (CeCO 3 ), nickel carbonate (NiCO 3 ), cobalt carbonate (CoCO 3 ), manganese carbonate (MnCO 3 ) and the like.
Examples of metallic nitrates include zirconium nitrate (Zr (NO 3 ) 4 ), iron nitrate (Fe (NO 3 ) 3 ), copper nitrate (Cu (NO 3 ) 2 ), titanium nitrate (Ti (NO 3 ) 4 ), and the like. Examples thereof include cerium nitrate (Ce (NO 3 ) 3 ), nickel nitrate (Ni (NO 3 ) 2 ), cobalt nitrate (Co (NO 3 ) 2 ), and manganese nitrate (Mn (NO 3 ) 2).
Among them, silica (SiO 2 ) is preferable from the viewpoint of improving hydrophilicity, and cerium oxide (CeO 2 , Ce 2 O 3 ), manganese oxide (MnO), cerium carbonate (CeCO 3 ), manganese carbonate from the viewpoint of improving chemical durability. (MnCO 3 ), cerium nitrate (Ce (NO 3 ) 3 ), manganese nitrate (Mn (NO 3 ) 2 ), titanium nitrate (Ti (NO 3 ) 4 ) are preferable.
無機系添加剤の形態としては、粒子状や繊維状といったものを用いても構わないが、特に非定形であることが望ましい。ここで言う非定形とは、光学顕微鏡や電子顕微鏡で観察しても、粒子状や繊維状の金属酸化物が観察されないことを言う。特に、走査型電子顕微鏡(SEM)を用いて電極触媒層を数10万倍までに拡大して観察しても、粒子状や繊維状の金属酸化物は観察されない。また、透過型電子顕微鏡(TEM)を用いて電極触媒層を数10万倍〜数100万倍に拡大して観察しても、明確に粒子状や繊維状の金属酸化物は観察することができない。このように現状の顕微鏡技術の範囲内では、金属酸化物の粒子状や繊維状を確認することができないことを指す。 As the form of the inorganic additive, particles or fibrous ones may be used, but it is particularly desirable that the inorganic additive has an atypical form. The term "atypical" as used herein means that no particle-like or fibrous metal oxide is observed even when observed with an optical microscope or an electron microscope. In particular, even when the electrode catalyst layer is magnified up to several hundred thousand times and observed using a scanning electron microscope (SEM), no particle-like or fibrous metal oxide is observed. Further, even when the electrode catalyst layer is magnified several hundred thousand times to several million times by a transmission electron microscope (TEM) and observed, the particle-like or fibrous metal oxide can be clearly observed. Can not. As described above, it means that it is not possible to confirm the particle shape or fibrous shape of the metal oxide within the scope of the current microscope technology.
上記無機系添加剤の含有量は、上記含フッ素高分子電解質に対して、0.01〜100質量%であることが好ましく、より好ましくは0.01〜45質量%、更に好ましくは0.01〜25質量%、特に好ましくは0.5〜6.0質量%である。 The content of the inorganic additive is preferably 0.01 to 100% by mass, more preferably 0.01 to 45% by mass, still more preferably 0.01, based on the fluorine-containing polymer electrolyte. It is ~ 25% by mass, particularly preferably 0.5 to 6.0% by mass.
(電極触媒層)
本実施形態の電極触媒層としては、上記含フッ素高分子電解質を含む電極触媒層であることが好ましい。上記電極触媒層は、上記電極触媒インクからなることが好ましい。上記電極触媒層は、安価に製造することができる上、酸素透過性が高い。上記電極触媒層は、カソード用電極触媒層として用いることができ、燃料電池用として好適に用いることができる。
(Electrode catalyst layer)
The electrode catalyst layer of the present embodiment is preferably an electrode catalyst layer containing the above-mentioned fluorine-containing polymer electrolyte. The electrode catalyst layer is preferably made of the electrode catalyst ink. The electrode catalyst layer can be manufactured at low cost and has high oxygen permeability. The electrode catalyst layer can be used as a cathode electrode catalyst layer, and can be suitably used for a fuel cell.
上記電極触媒層は、上記含フッ素高分子電解質及び上記触媒からなることが好ましい。上記電極触媒層は、電極面積に対する上記含フッ素高分子電解質の担持量が、好ましくは0.001〜10mg/cm2、より好ましくは0.01〜5mg/cm2、更に好ましくは0.1〜1mg/cm2である。 The electrode catalyst layer is preferably composed of the fluorine-containing polymer electrolyte and the catalyst. The electrode catalyst layer, the supported amount of the fluorine-containing polymer electrolyte to the electrode area is preferably 0.001 to 10 mg / cm 2, more preferably 0.01 to 5 mg / cm 2, more preferably 0.1 It is 1 mg / cm 2 .
本実施形態の電極触媒層は、含フッ素高分子電解質、触媒及び導電剤からなるものであることが好ましい。上記電極触媒層は、含フッ素高分子電解質と、触媒の粒子及びこれを担持した導電剤からなる複合粒子(例えば、Pt担持カーボン等)と、からなるものであることも好ましい形態の一つである。この場合、上記含フッ素高分子電解質は、バインダーとしても機能する。 The electrode catalyst layer of the present embodiment is preferably made of a fluorine-containing polymer electrolyte, a catalyst, and a conductive agent. It is also preferable that the electrode catalyst layer is composed of a fluorine-containing polymer electrolyte, composite particles composed of catalyst particles and a conductive agent supporting the catalyst particles (for example, Pt-supported carbon). is there. In this case, the fluorine-containing polymer electrolyte also functions as a binder.
上記導電剤としては、上述のものが挙げられ、上述と同様のものが好ましい。
上記複合粒子としては、導電性粒子に対して触媒粒子が、好ましくは1〜99質量%、より好ましくは10〜90質量%、最も好ましくは30〜70質量%である。具体的には、田中貴金属工業(株)製TEC10E40E等のPt触媒担持カーボンが好適な例として挙げられる。
Examples of the above-mentioned conductive agent include those mentioned above, and those similar to those described above are preferable.
As the composite particles, the catalyst particles are preferably 1 to 99% by mass, more preferably 10 to 90% by mass, and most preferably 30 to 70% by mass with respect to the conductive particles. Specifically, Pt catalyst-supported carbon such as TEC10E40E manufactured by Tanaka Kikinzoku Kogyo Co., Ltd. is a preferable example.
上記複合粒子の含有率は、電極触媒層の全質量に対し、20〜95質量%であることが好ましく、より好ましくは40〜90質量%、更に好ましくは50〜85質量%、特に好ましくは60〜80質量%である。電極触媒層が燃料電池の電極触媒層として用いられる場合、電極面積に対する触媒金属の担持量としては、電極触媒層を形成した状態で、好ましくは0.001〜10mg/cm2、より好ましくは0.01〜5mg/cm2、更に好ましくは0.1〜1mg/cm2、更により好ましくは0.2〜0.5mg/cm2である。 The content of the composite particles is preferably 20 to 95% by mass, more preferably 40 to 90% by mass, still more preferably 50 to 85% by mass, and particularly preferably 60, based on the total mass of the electrode catalyst layer. ~ 80% by mass. When the electrode catalyst layer is used as the electrode catalyst layer of the fuel cell, the amount of the catalyst metal supported with respect to the electrode area is preferably 0.001 to 10 mg / cm 2 in the state where the electrode catalyst layer is formed, more preferably 0. .01~5mg / cm 2, more preferably 0.1 to 1 mg / cm 2, even more preferably 0.2-0.5 mg / cm 2.
電極触媒層の厚みとしては、好ましくは0.01〜200μm、より好ましくは0.1〜100μm、最も好ましくは1〜50μmである。 The thickness of the electrode catalyst layer is preferably 0.01 to 200 μm, more preferably 0.1 to 100 μm, and most preferably 1 to 50 μm.
上記電極触媒層は、必要に応じて撥水剤を含んでもよい。
上記撥水剤としては、上述のものが挙げられ、上述と同様のものが好ましい。
電極触媒層が撥水剤を含有する場合、PTFE並びにテトラフルオロエチレンとパーフルオロ(2,2−ジメチル−1,3−ジオキソール)の共重合体の含有率としては、電極触媒層の全質量に対し、好ましくは0.001〜20質量%、より好ましくは0.01〜10質量%、最も好ましくは0.1〜5質量%である。
The electrode catalyst layer may contain a water repellent, if necessary.
Examples of the water repellent include those described above, and those similar to those described above are preferable.
When the electrode catalyst layer contains a water repellent, the content of PTFE and the copolymer of tetrafluoroethylene and perfluoro (2,2-dimethyl-1,3-dioxol) is the total mass of the electrode catalyst layer. On the other hand, it is preferably 0.001 to 20% by mass, more preferably 0.01 to 10% by mass, and most preferably 0.1 to 5% by mass.
上記電極触媒層は、親水性向上及び化学耐久性向上のため、無機系添加剤を配合しても良い。
上記無機系添加剤としては、上述のものが挙げられ、上述と同様のものが好ましい。
上記無機系添加剤の含有率としては、電極触媒層の全質量に対し、好ましくは0.001〜20質量%、より好ましくは0.01〜10質量%、最も好ましくは0.1〜5質量%である。
The electrode catalyst layer may contain an inorganic additive in order to improve hydrophilicity and chemical durability.
Examples of the above-mentioned inorganic additive include those mentioned above, and those similar to the above are preferable.
The content of the inorganic additive is preferably 0.001 to 20% by mass, more preferably 0.01 to 10% by mass, and most preferably 0.1 to 5% by mass with respect to the total mass of the electrode catalyst layer. %.
上記電極触媒層の空隙率としては特に限定されないが、好ましくは10〜90体積%、より好ましくは20〜80体積%、最も好ましくは30〜60体積%である。 The porosity of the electrode catalyst layer is not particularly limited, but is preferably 10 to 90% by volume, more preferably 20 to 80% by volume, and most preferably 30 to 60% by volume.
上記電極触媒層の製造方法は、得られた含フッ素高分子電解質溶液に上記触媒を分散させて上記電極触媒インクを調製する工程と、電極触媒インクを基材に塗布する工程と、基材に塗布した電極触媒インクを乾燥させて電極触媒層を得る工程と、を含む。 The method for producing the electrode catalyst layer includes a step of preparing the electrode catalyst ink by dispersing the catalyst in the obtained fluorine-containing polymer electrolyte solution, a step of applying the electrode catalyst ink to the base material, and a step of applying the electrode catalyst ink to the base material. The step of drying the applied electrode catalyst ink to obtain an electrode catalyst layer is included.
得られた含フッ素高分子電解質溶液に上記触媒を分散させて電極触媒インクを調製する工程は、得られたエマルジョン又は含フッ素高分子電解質溶液に、触媒の粒子及びこれを担持した導電剤からなる複合粒子を分散させた電極触媒インクを調製するものであることが好ましい。 The step of preparing the electrode catalyst ink by dispersing the catalyst in the obtained fluorine-containing polymer electrolyte solution comprises the catalyst particles and the conductive agent carrying the catalyst particles in the obtained emulsion or the fluorine-containing polymer electrolyte solution. It is preferable to prepare an electrode catalyst ink in which composite particles are dispersed.
上記電極触媒インクの塗布は、スクリーン印刷法、スプレー法等の一般的に知られている各種方法を用いることが可能である。 For the application of the electrode catalyst ink, various generally known methods such as a screen printing method and a spray method can be used.
(膜電極接合体)
本実施形態の膜電極接合体(membrane/electrode assembly)(以下、「MEA」ともいう。)は、上記電極触媒層を備えることが好ましい。本実施形態の膜電極接合体は、上記電極触媒層を備えるため、電池特性並びに機械的強度に優れ、安定性に優れる。上記膜電極接合体は、燃料電池用として好適に用いることができる。
(Membrane electrode assembly)
The membrane electrode assembly (membrane / ejectorode assembly) (hereinafter, also referred to as “MEA”) of the present embodiment preferably includes the electrode catalyst layer. Since the membrane electrode assembly of the present embodiment includes the electrode catalyst layer, it is excellent in battery characteristics, mechanical strength, and stability. The membrane electrode assembly can be suitably used for a fuel cell.
電解質膜の両面にアノードとカソードの2種類の電極触媒層が接合したユニットは、膜電極接合体(以下「MEA」ともいう。)と呼ばれる。電極触媒層のさらに外側に一対のガス拡散層を対向するように接合したものについても、MEAと呼ばれる場合がある。電極触媒層はプロトン伝導性を有することが必要となる。 A unit in which two types of electrode catalyst layers, an anode and a cathode, are bonded to both sides of an electrolyte membrane is called a membrane electrode assembly (hereinafter, also referred to as "MEA"). A pair of gas diffusion layers bonded to the outer side of the electrode catalyst layer so as to face each other may also be referred to as MEA. The electrode catalyst layer needs to have proton conductivity.
アノードとしての電極触媒層は、燃料(例えば水素)を酸化して容易にプロトンを生しさせる触媒を包含し、カソードとしての電極触媒層は、プロトン及び電子と酸化剤(例えば酸素や空気)を反応させて水を生成させる触媒を包含する。アノードとカソードのいずれについても、触媒としては上述した触媒金属を好適に用いることができる。 The electrode catalyst layer as an anode includes a catalyst that oxidizes a fuel (for example, hydrogen) to easily generate a proton, and the electrode catalyst layer as a cathode contains protons, electrons, and an oxidant (for example, oxygen or air). Includes catalysts that react to produce water. As the catalyst, the above-mentioned catalyst metal can be preferably used for both the anode and the cathode.
ガス拡散層としては、市販のカーボンクロス、カーボンペーパー、カーボンフェルト等を用いることができる。これらのガス拡散層にはポリテトラフルオロエチレン等により撥水処理されていることが好ましい。
具体例として、炭素繊維トレカ(東レ社製)、パイロフィル(三菱ケミカル社製)、SIGRACET GDL(MFCテクノロジー社製)等が挙げられる。
As the gas diffusion layer, commercially available carbon cloth, carbon paper, carbon felt or the like can be used. It is preferable that these gas diffusion layers are water-repellent treated with polytetrafluoroethylene or the like.
Specific examples include carbon fiber trading cards (manufactured by Toray Industries, Inc.), pyrofil (manufactured by Mitsubishi Chemical Corporation), SIGRACET GDL (manufactured by MFC Technology), and the like.
MEAは、例えば、電極触媒層の間に電解質膜を挟みこみ、熱プレスにより接合することにより作製することができる。より具体的には、上記含フッ素高分子電解質をアルコールと水の混合溶液に分散又は溶解したものに、触媒として市販の白金担持カーボン(例えば、田中貴金属(株)製TEC10E40E)を分散させてペースト状にする。これを2枚のPTFEシートのそれぞれの片面に一定量塗布して乾燥させて電極触媒層を形成する。次に、各PTFEシートの塗布面を向かい合わせにして、その間に電解質膜を挟み込み、100〜200℃で熱プレスにより転写接合してから、PTFEシートを取り除くことにより、MEAを得ることができる。当業者にはMEAの作製方法は周知である。MEAの作製方法は、例えば、JOURNAL OF APPLIED ELECTROCHEMISTRY,22(1992)p.1−7に詳しく記載されている。 The MEA can be produced, for example, by sandwiching an electrolyte membrane between the electrode catalyst layers and joining them by a hot press. More specifically, a commercially available platinum-supported carbon (for example, TEC10E40E manufactured by Tanaka Kikinzoku Co., Ltd.) is dispersed as a catalyst in a mixture of the above-mentioned fluorine-containing polymer electrolyte dispersed or dissolved in a mixed solution of alcohol and water and pasted. Make it into a shape. A certain amount of this is applied to one side of each of the two PTFE sheets and dried to form an electrode catalyst layer. Next, the coated surfaces of the PTFE sheets are made to face each other, an electrolyte membrane is sandwiched between them, transfer bonding is performed by a hot press at 100 to 200 ° C., and then the PTFE sheet is removed to obtain MEA. A method for producing MEA is well known to those skilled in the art. The method for producing MEA is described in, for example, JOURNAL OF APPLIED ELECTROCHEMISTRY, 22 (1992) p. It is described in detail in 1-7.
上記MEA(一対のガス拡散電極が対向した構造のMEAを含む。)は、更にバイポーラプレートやバッキングプレート等の一般的な燃料電池に用いられる構成成分と組み合わされて、燃料電池が構成される。 The MEA (including an MEA having a structure in which a pair of gas diffusion electrodes face each other) is further combined with components used in a general fuel cell such as a bipolar plate and a backing plate to form a fuel cell.
(燃料電池)
本実施形態の燃料電池は、上記膜電極接合体を備えることが好ましい。本実施形態の燃料電池は、固体高分子形燃料電池であることが好ましい。本実施形態の燃料電池は、上記膜電極接合体を有するものであれば特に限定されず、通常、燃料電池を構成するガス等の構成成分を含むものであってよい。本実施形態の燃料電池は、上記電極触媒層を有する膜電極接合体を備えるものであるため、電池特性並びに機械的強度に優れ、安定性に優れる。
(Fuel cell)
The fuel cell of the present embodiment preferably includes the membrane electrode assembly. The fuel cell of the present embodiment is preferably a polymer electrolyte fuel cell. The fuel cell of the present embodiment is not particularly limited as long as it has the membrane electrode assembly, and may usually include components such as gas constituting the fuel cell. Since the fuel cell of the present embodiment includes the membrane electrode assembly having the electrode catalyst layer, it is excellent in battery characteristics, mechanical strength, and stability.
バイポーラプレートとは、その表面に燃料や酸化剤等のガスを流すための溝を形成させたグラファイトと樹脂との複合材料、又は金属製のプレート等を意味する。バイポーラプレートは、電子を外部負荷回路へ伝達する機能の他、燃料や酸化剤を電極触媒近傍に供給する流路としての機能を持っている。こうしたバイポーラプレートの間にMEAを挿入して複数積み重ねることにより、燃料電池が製造される。 The bipolar plate means a composite material of graphite and resin having grooves formed on its surface for allowing gas such as fuel or an oxidizing agent to flow, or a metal plate or the like. The bipolar plate has a function of transmitting electrons to an external load circuit and also a function of a flow path for supplying fuel and an oxidizing agent in the vicinity of the electrode catalyst. A fuel cell is manufactured by inserting MEA between such bipolar plates and stacking a plurality of MEAs.
次に本発明を、実施例をあげて説明するが、本発明はかかる実施例のみに限定されるものではない。 Next, the present invention will be described with reference to examples, but the present invention is not limited to such examples.
(フッ素化)
室温の条件下、試料をフッ素ガス5vol%と窒素ガス95vol%からなる混合ガスに30分間暴露することによりフッ素化を行った。
(Fluorination)
Under room temperature conditions, the sample was fluorinated by exposing it to a mixed gas consisting of 5 vol% of fluorine gas and 95 vol% of nitrogen gas for 30 minutes.
(イオン交換容量)
イオン交換基の対イオンがプロトンの状態となっている含フッ素高分子電解質膜、およそ2〜20cm2を、25℃、飽和NaCl水溶液30mlに浸漬し、攪拌しながら30分間放置した。次いで、飽和NaCl水溶液中のプロトンを、フェノールフタレインを指示薬として0.01N水酸化ナトリウム水溶液として中和滴定した。中和後に得られた、イオン交換基の対イオンがナトリウムイオンの状態となっている含フッ素高分子電解質膜を、純水ですすぎ、更に真空乾燥して秤量した。中和に要した水酸化ナトリウムの物質量をM(mmol)、イオン交換基の対イオンがナトリウムイオンの含フッ素高分子電解質膜の重量をW(mg)とし、下記式により当量重量EW(g/eq)を求めた。
EW=(W/M)−22
更に、得られたEW値の逆数をとって1000倍とすることにより、イオン交換容量(ミリ当量/g)を算出した。
(Ion exchange capacity)
A fluorine-containing polymer electrolyte membrane in which the counter ion of the ion exchange group is in a proton state, approximately 2 to 20 cm 2, was immersed in 30 ml of a saturated NaCl aqueous solution at 25 ° C. and left for 30 minutes with stirring. Then, the protons in the saturated NaCl aqueous solution were neutralized and titrated as a 0.01N sodium hydroxide aqueous solution using phenolphthalein as an indicator. The fluorine-containing polymer electrolyte membrane obtained after neutralization in which the counter ion of the ion exchange group was in the state of sodium ion was rinsed with pure water, further vacuum-dried, and weighed. The amount of substance of sodium hydroxide required for neutralization is M (mmol), the weight of the fluoropolymer electrolyte membrane containing sodium ions as the counterion of the ion exchange group is W (mg), and the equivalent weight EW (g) is calculated by the following formula. / Eq) was calculated.
EW = (W / M) -22
Further, the ion exchange capacity (milli equivalent / g) was calculated by taking the reciprocal of the obtained EW value and multiplying it by 1000.
(導入率)
側鎖構造を導入した高分子電解質のH−NMR並びにF−NMR解析を行い、EW測定でのプロトン伝導性基導入量と併せることで、側鎖構造の導入率を算出した。また、特に環状構造を有する側鎖がプロトン伝導性基を有さない場合は下記のように導入率を測定した。
側鎖構造を導入した高分子電解質のEWを、上述のイオン交換容量測定の手法で測定した。その時の値をEW1とした。次いで、オートクレーブに側鎖構造を導入した電解質と6Nの塩酸水溶液を仕込み、N2ガスで十分に内部を置換した後、160℃、8時間の条件で加水分解を実施した。得られた高分子電解質を蒸留水で洗浄した後、120℃、1時間の条件で乾燥させた。乾燥させた樹脂のH−NMR並びにF−NMR解析から側鎖が完全に加水分解されていることを確認した。加水分解後の高分子電解質のEWを測定した。その時の値をEW2とした。以上から導入した側鎖量(C2)は1000/(EW1−EW2)と算出した。ここで加水分解前のプロトン伝導性基量をC1とした時、側鎖導入率(S)はC2/(C1+C2)×100(mol%)で表される。
また、構造をH−NMR並びにF−NMRで確認し、EWと併用することで、側鎖末端の構造にかかわらず側鎖構造の導入率を測定することができる。
(Introduction rate)
H-NMR and F-NMR analysis of the polymer electrolyte into which the side chain structure was introduced was performed, and the introduction rate of the side chain structure was calculated by combining with the amount of proton conductive groups introduced in the EW measurement. Further, especially when the side chain having a cyclic structure does not have a proton conductive group, the introduction rate was measured as follows.
The EW of the polymer electrolyte into which the side chain structure was introduced was measured by the above-mentioned ion exchange capacity measurement method. The value at that time was set to EW1. Then, charged electrolyte and 6N aqueous hydrochloric acid solution was introduced a side chain structure into the autoclave, and after sufficiently replacing the inside with N 2 gas, 160 ° C., and out the hydrolysis under the conditions of 8 hours. The obtained polymer electrolyte was washed with distilled water and then dried at 120 ° C. for 1 hour. From H-NMR and F-NMR analysis of the dried resin, it was confirmed that the side chains were completely hydrolyzed. The EW of the polymer electrolyte after hydrolysis was measured. The value at that time was set to EW2. From the above, the amount of side chain introduced (C2) was calculated to be 1000 / (EW1-EW2). Here, when the amount of proton conductive groups before hydrolysis is C1, the side chain introduction rate (S) is represented by C2 / (C1 + C2) × 100 (mol%).
Further, by confirming the structure by 1 H-NMR and F-NMR and using it in combination with EW, the introduction rate of the side chain structure can be measured regardless of the structure at the end of the side chain.
(含水率)
ポリマーの含水率を加湿可能なTG−DTA(製品名:TG−8120、リガク社製)を用いて測定した。
はじめに、120℃で1時間乾燥させ、その後、80℃まで降温し、湿度80%で1時間保持し、当該加湿条件での質量と、乾燥質量の差から、ポリマー中に含まれる水の質量割合、即ち含水率(質量%)を算出した。
(Moisture content)
The water content of the polymer was measured using a humidifiable TG-DTA (product name: TG-8120, manufactured by Rigaku Co., Ltd.).
First, it is dried at 120 ° C. for 1 hour, then cooled to 80 ° C., kept at a humidity of 80% for 1 hour, and the mass ratio of water contained in the polymer is determined from the difference between the mass under the humidifying condition and the dry mass. That is, the water content (mass%) was calculated.
(酸素溶解度)
含フッ素高分子電解質樹脂の膜の酸素溶解度を、クロノアンペロメトリー法を用いて測定した。ガラス封入した100μmφの白金微小電極を厚さ200μm程度のサンプルに押し当てて、温度、湿度を調整した。窒素又は酸素雰囲気下にて、電位を1100mV(vs.SHE)に保持した後、400mVにステップして電流値を測定した。窒素及び酸素雰囲気下で観測された電流値の差分を印加時間の−1/2乗に対してプロットし、直線性が得られた範囲において下記式を用いて酸素溶解度を算出した。
I=4πFrDc[1+r/(πDt)1/2+0.2732exp{−0.3911r/(Dt)1/2}]
ただし、Iは電流値(A)、Fはファラデー定数(96500C/mol)、rは電極半径(cm)、Dは酸素拡散係数(cm2/s)、cは酸素溶解度(mol/m3)、tは時間(s)である。
本検討では評価温度80℃、湿度80%での酸素溶解度を示した。
(Oxygen solubility)
The oxygen solubility of the film of the fluorine-containing polymer electrolyte resin was measured by using the chronoamperometry method. A glass-encapsulated 100 μmφ platinum microelectrode was pressed against a sample having a thickness of about 200 μm to adjust the temperature and humidity. After maintaining the potential at 1100 mV (vs. SHE) in a nitrogen or oxygen atmosphere, the current value was measured in steps of 400 mV. The difference between the current values observed under the atmosphere of nitrogen and oxygen was plotted against the -1 / 2th power of the application time, and the oxygen solubility was calculated using the following formula in the range where linearity was obtained.
I = 4πFrDc [1 + r / (πDt) 1/2 + 0.2732exp {-0.3911r / (Dt) 1/2 }]
However, I is the current value (A), F is the Faraday constant (96500 C / mol), r is the electrode radius (cm), D is the oxygen diffusion coefficient (cm 2 / s), and c is the oxygen solubility (mol / m 3 ). , T is the time (s).
In this study, the oxygen solubility at an evaluation temperature of 80 ° C. and a humidity of 80% was shown.
(酸素透過係数)
GTRテック(株)製フロー式ガス透過率測定装置GTR−30XFAFCを用いて膜サンプルの酸素のガス透過係数を測定した。供給ガス流量は、TESTガス(酸素)30cc/min、キャリアーガス(He)100kPaとした。ガスの加温加湿条件は、80℃、90%RHを採用した。
TESTガス側からFLOW側に膜サンプルを透過してきた酸素ガスをヤナコ分析工業(株)製ガスクロマトグラフG2700TFに導入して、ガス透過量を定量化する。
透過量をX(cc)、補正係数をk(=1.0)、膜サンプルの膜厚をT(cm)、透過面積をA(cm2)、計量管通過時間をD(sec)、酸素分圧をp(cmHg)とした時のガス透過係数P(cc・cm/(cm2・sec・cmHg))は下記式から計算される。
P=(X×k×T/(A×D×p))
(Oxygen permeability coefficient)
The gas permeability coefficient of oxygen in the membrane sample was measured using a flow-type gas permeability measuring device GTR-30XFAFC manufactured by GTR Tech Co., Ltd. The supply gas flow rate was TEST gas (oxygen) 30 cc / min and carrier gas (He) 100 kPa. As the humidifying and humidifying conditions for the gas, 80 ° C. and 90% RH were adopted.
The oxygen gas that has permeated the membrane sample from the TEST gas side to the FLOW side is introduced into a gas chromatograph G2700TF manufactured by Yanaco Analytical Industry Co., Ltd., and the amount of gas permeation is quantified.
The amount of permeation is X (cc), the correction coefficient is k (= 1.0), the film thickness of the film sample is T (cm), the permeation area is A (cm 2 ), the passage time of the measuring tube is D (sec), and oxygen. The gas permeability coefficient P (cc · cm / (cm 2 · sec · cmHg)) when the partial pressure is p (cmHg) is calculated from the following formula.
P = (X × k × T / (A × D × p))
(ひび割れの有無(SEM観察))
ダイコーターで作製した触媒層の表面を、走査型電子顕微鏡(製品名:VE8800、キーエンス社製)を用い、倍率50倍、加速電圧1kVの条件で観察した。観察の結果、触媒層表面にひび割れがなかった場合をA(良好)、ひび割れが見られた場合をB(不良)と表記した。
(Presence / absence of cracks (SEM observation))
The surface of the catalyst layer produced by the die coater was observed using a scanning electron microscope (product name: VE8800, manufactured by KEYENCE CORPORATION) under the conditions of a magnification of 50 times and an acceleration voltage of 1 kV. As a result of observation, the case where there was no crack on the surface of the catalyst layer was described as A (good), and the case where crack was observed was described as B (defective).
(触媒ペースト作製、電極作製、燃料電池評価)
高温低加湿条件下におけるMEAの性能を評価するため、以下のような手順で発電試験を実施した。
(1)電極触媒インクの調製
固形分濃度15質量%の含フッ素高分子電解質溶液、電極触媒(TEC10E40E、田中貴金属工業(株)製、白金担持量36.7wt%)を白金/パーフルオロスルホン酸ポリマーが1/1.15(質量)となるように配合し、次いで、固形分(電極触媒とパーフルオロスルホン酸ポリマーの和)が11wt%となるようにエタノールを加え、ホモジナイザー(アズワン社製)により回転数が3000rpmで10分間、撹拌することで電極触媒インクを得た。
(2)電極触媒層の作製
ダイコーター(製品名:理化ダイ、伊藤忠ファインテクノ社製)を用い、膜厚100μmのテフロン(登録商標)基材(製品名:ナフロンテープ、ニチアス社製)上に上記電極触媒インクを、白金量が0.2mg/cm2となる様に塗布し、160℃、5分の条件で乾燥・固化させることで触媒層を得た。
(3)MEAの作製
プレス機(製品名:SFA−37、神藤金属工業社製)を用い、電解質膜(製品名:NafionHP、ケマーズ社製)の両面に、アノード側に含フッ素高分子電解質としてNafionDE2020CSを用いた電極触媒層を、カソード側に本実施形態の含フッ素高分子電解質を用いた電極触媒層を、温度160℃、圧力13MPaの条件で熱プレスすることで、MEAを得た。
(4)燃料電池単セルの作製
上記MEAの両極にガス拡散層(製品名:GDL35BC、MFCテクノロジー社製)を重ね、次いでガスケット、バイポーラプレート、バッキングプレートを重ねることで燃料電池単セルを得た。
(5)発電試験
上記燃料電池単セルを評価装置(東陽テクニカ社製燃料電池評価システム890CL)にセットして、発電試験を実施した。
発電の試験条件は、セル温度65℃、アノード及びカソードの加湿ボトル60℃に設定し、アノード側に水素ガス、カソード側に空気ガスを、それぞれ900ml/minの条件で供給した。また、アノード側とカソード側の両方を無加圧(大気圧)とした。
上記評価条件において、電流密度0.2A/cm2、及び1.0A/cm2での電圧を表記した。
(6)化学耐久性試験
上記燃料電池単セルを評価装置(東陽テクニカ製燃料電池評価システム890CL)にセットして、セル温度90℃、加湿ボトル61℃(相対湿度30%RH)、アノード側に水素ガス、カソード側に空気ガスを、それぞれ300cc/minの条件で流通させることでOCV試験を実施した。
上記OCV試験の終点を判定するために、カソード側にマイクロガスクロマトグラフ(製品名:CP−4900、GLサイエンス社製)を接続し、アノード側より透過するH2ガスの濃度を測定した。上記H2ガスの濃度が1000ppmを越えた時点を終点とした。上記終点が200時間以上をA(良好)、200時間未満をB(不良)と表記した。
(Catalyst paste preparation, electrode preparation, fuel cell evaluation)
In order to evaluate the performance of MEA under high temperature and low humidification conditions, a power generation test was carried out according to the following procedure.
(1) Preparation of electrode catalyst ink A fluorine-containing polymer electrolyte solution having a solid content concentration of 15% by mass and an electrode catalyst (TEC10E40E, manufactured by Tanaka Kikinzoku Kogyo Co., Ltd., platinum carrying amount 36.7 wt%) are used as platinum / perfluorosulfonic acid. The polymer was blended to 1 / 1.15 (mass), and then ethanol was added so that the solid content (sum of the electrode catalyst and the perfluorosulfonic acid polymer) was 11 wt%, and a homogenizer (manufactured by AS ONE) was added. The electrode catalyst ink was obtained by stirring at 3000 rpm for 10 minutes.
(2) Preparation of electrode catalyst layer Using a die coater (product name: Rika Dai, manufactured by ITOCHU Fine Techno Co., Ltd.), on a Teflon (registered trademark) substrate (product name: Naflon tape, manufactured by Nichias Corporation) with a thickness of 100 μm. The electrode catalyst ink was applied so that the amount of platinum was 0.2 mg / cm 2, and dried and solidified at 160 ° C. for 5 minutes to obtain a catalyst layer.
(3) Preparation of MEA Using a press machine (product name: SFA-37, manufactured by Shinto Metal Industry Co., Ltd.), as a fluoropolymer electrolyte on both sides of the electrolyte membrane (product name: NafionHP, manufactured by Chemers) on the anode side. MEA was obtained by hot-pressing the electrode catalyst layer using NafionDE2020CS and the electrode catalyst layer using the fluoropolymer electrolyte of the present embodiment on the cathode side under the conditions of a temperature of 160 ° C. and a pressure of 13 MPa.
(4) Preparation of fuel cell single cell A fuel cell single cell was obtained by superimposing a gas diffusion layer (product name: GDL35BC, manufactured by MFC Technology) on both poles of the above MEA, and then superimposing a gasket, a bipolar plate, and a backing plate. ..
(5) Power generation test The above fuel cell single cell was set in an evaluation device (fuel cell evaluation system 890CL manufactured by Toyo Technica Co., Ltd.), and a power generation test was carried out.
The test conditions for power generation were set at a cell temperature of 65 ° C. and a humidifying bottle of the anode and cathode of 60 ° C., and hydrogen gas was supplied to the anode side and air gas was supplied to the cathode side at 900 ml / min, respectively. In addition, both the anode side and the cathode side were unpressurized (atmospheric pressure).
Under the above evaluation conditions, the voltages at current densities of 0.2 A / cm 2 and 1.0 A / cm 2 are shown.
(6) Chemical durability test Set the above fuel cell single cell in the evaluation device (fuel cell evaluation system 890CL manufactured by Toyo Technica), and set the cell temperature at 90 ° C, the humidification bottle at 61 ° C (relative humidity 30% RH), and on the anode side. The OCV test was carried out by circulating hydrogen gas and air gas on the cathode side under the conditions of 300 cc / min, respectively.
In order to determine the end point of the OCV test, a micro gas chromatograph (product name: CP-4900, manufactured by GL Science Co., Ltd.) was connected to the cathode side, and the concentration of H 2 gas transmitted from the anode side was measured. The end point was when the concentration of the H 2 gas exceeded 1000 ppm. When the end point is 200 hours or more, it is described as A (good), and when it is less than 200 hours, it is described as B (bad).
(実施例1)
100mLの三つ口フラスコに水素化ナトリウム(0.27g)を加え、系内を窒素置換後、フラスコを氷浴に付けながら、4−ピペリドンエチレンケタール(1.36g)を溶解させた1,2−ジメトキシエタン(40mL)溶液を滴下した。次にフラスコの中に、ラジカル重合法で取得した、テトラフルオロエチレンとCF2=CFOCF2CF2SO2Fとの共重合体(5.0g)を投入し、80℃で2時間反応させた。反応後、4Mの塩酸(100mL)を添加した後、フラスコから反応生成物を取り出し、80℃の熱水で十分に洗浄した。該反応生成物を、水酸化カリウム(15質量%)とメタノール(50質量%)とを溶解した水溶液中に80℃で20時間接触させ、60℃水中に5時間浸漬後、60℃の2N塩酸水溶液に1時間浸漬させる処理を5回繰り返した後、イオン交換水で水洗し、乾燥させて、含フッ素高分子電解質(A1)(4.2g)を得た。
得られた含フッ素高分子電解質(A1)とエタノール水溶液(水:エタノール=30:70(質量比))とを5Lオートクレーブ中に入れて密閉し、攪拌しながら160℃まで昇温して3時間保持した。その後、オートクレーブを自然冷却して、固形分濃度10質量%の均一なポリマー溶液を作製した。
得られた固形分濃度10質量%のポリマー溶液を80℃で減圧濃縮して、固形分濃度15質量%のポリマー溶液(AS1)を得た。
上記AS1をキャスト製膜して、厚み200μmの膜(AM1)を作製した。AM1のEWは832であり、側鎖に導入された4−ピペリドンエチレンケタールの導入率は10.3mol%であった。
AM1のEW、含水率、酸素溶解度及び酸素透過係数を表1に示す。またAS1を用いた触媒層のひび割れ有無、電池性能及び化学耐久試験の結果を表2に示す。
AM1は高い酸素溶解度、及び酸素透過係数を示す。またAS1を用いた触媒層にはひび割れがなく、電池性能及び化学耐久性が比較の材料よりも高いことが分かる。
(Example 1)
Sodium hydride (0.27 g) was added to a 100 mL three-necked flask, the inside of the system was replaced with nitrogen, and 4-piperidone ethyleneketal (1.36 g) was dissolved while the flask was placed in an ice bath. A solution of 2-dimethoxyethane (40 mL) was added dropwise. Next, a copolymer (5.0 g) of tetrafluoroethylene and CF 2 = CFOCF 2 CF 2 SO 2 F obtained by a radical polymerization method was put into a flask and reacted at 80 ° C. for 2 hours. .. After the reaction, 4M hydrochloric acid (100 mL) was added, and then the reaction product was taken out from the flask and washed thoroughly with hot water at 80 ° C. The reaction product is brought into contact with an aqueous solution of potassium hydroxide (15% by mass) and methanol (50% by mass) at 80 ° C. for 20 hours, immersed in water at 60 ° C. for 5 hours, and then 2N hydrochloric acid at 60 ° C. After repeating the treatment of immersing in an aqueous solution for 1 hour 5 times, the mixture was washed with ion-exchanged water and dried to obtain a fluorine-containing polymer electrolyte (A1) (4.2 g).
The obtained fluorine-containing polymer electrolyte (A1) and an aqueous ethanol solution (water: ethanol = 30: 70 (mass ratio)) are placed in a 5 L autoclave, sealed, and heated to 160 ° C. for 3 hours with stirring. Retained. Then, the autoclave was naturally cooled to prepare a uniform polymer solution having a solid content concentration of 10% by mass.
The obtained polymer solution having a solid content concentration of 10% by mass was concentrated under reduced pressure at 80 ° C. to obtain a polymer solution (AS1) having a solid content concentration of 15% by mass.
The AS1 was cast to produce a film (AM1) having a thickness of 200 μm. The EW of AM1 was 832, and the introduction rate of 4-piperidone ethylene ketal introduced into the side chain was 10.3 mol%.
Table 1 shows the EW, water content, oxygen solubility and oxygen permeability coefficient of AM1. Table 2 shows the presence or absence of cracks in the catalyst layer using AS1, the battery performance, and the results of the chemical durability test.
AM1 exhibits high oxygen solubility and oxygen permeability coefficient. Further, it can be seen that the catalyst layer using AS1 has no cracks, and the battery performance and chemical durability are higher than those of the comparative material.
(実施例2)
実施例1で得たA1に上記方法でフッ素化を行い、フッ素化物A2を得た。
A2を実施例1と同様な方法で溶液化しポリマー溶液(AS2)を得た。
上記AS2をキャスト製膜して、厚み200μmの膜(AM2)を作製した。AM2のEWは933であり、側鎖に導入されたパーフルオロ4−ピペリドンエチレンケタールの導入率は10.1mol%であった。
AM2のEW、含水率、酸素溶解度及び酸素透過係数を表1に示す。またAS2を用いた触媒層のひび割れ有無、電池性能及び化学耐久試験の結果を表2に示す。
AM2は高い酸素溶解度、及び酸素透過係数を示す。またAS2を用いた触媒層にはひび割れがなく、電池性能及び化学耐久性が比較の材料よりも高いことが分かる。
(Example 2)
The A1 obtained in Example 1 was fluorinated by the above method to obtain a fluorinated product A2.
A2 was solubilized in the same manner as in Example 1 to obtain a polymer solution (AS2).
The AS2 was cast to produce a film (AM2) having a thickness of 200 μm. The EW of AM2 was 933, and the introduction rate of perfluoro4-piperidone ethylene ketal introduced into the side chain was 10.1 mol%.
Table 1 shows the EW, water content, oxygen solubility and oxygen permeability coefficient of AM2. Table 2 shows the presence or absence of cracks in the catalyst layer using AS2, the battery performance, and the results of the chemical durability test.
AM2 exhibits high oxygen solubility and oxygen permeability coefficient. Further, it can be seen that the catalyst layer using AS2 has no cracks, and the battery performance and chemical durability are higher than those of the comparative material.
(実施例3)
4−ピペリドンエチレンケタールのかわりに、2,6−ジメチルモルフォリン(0.95g)を用いる以外は実施例1と同様に合成を行い、含フッ素高分子電解質(A3)を得た。
得られたA3に対して上記手法でフッ素化を行った。
フッ素化したA2を実施例1と同様な方法で溶液化しポリマー溶液(AS3)を得た。
上記AS3をキャスト製膜して、厚み200μmの膜(AM3)を作製した。AM3のEWは923であり、側鎖に導入されたパーフルオロ2,6−ジメチルモルフォリンの導入率は10.1mol%であった。
AM3のEW、含水率、酸素溶解度及び酸素透過係数を表1に示す。またAS3を用いた触媒層のひび割れ有無、電池性能及び化学耐久試験の結果を表2に示す。
AM3は高い酸素溶解度、及び酸素透過係数を示す。またAS3を用いた触媒層にはひび割れがなく、電池性能及び化学耐久性が比較の材料よりも高いことが分かる。
(Example 3)
Synthesis was carried out in the same manner as in Example 1 except that 2,6-dimethylmorpholin (0.95 g) was used instead of 4-piperidone ethylene ketal to obtain a fluorine-containing polymer electrolyte (A3).
The obtained A3 was fluorinated by the above method.
The fluorinated A2 was solubilized in the same manner as in Example 1 to obtain a polymer solution (AS3).
The AS3 was cast to produce a film (AM3) having a thickness of 200 μm. The EW of AM3 was 923, and the introduction rate of perfluoro2,6-dimethylmorpholin introduced into the side chain was 10.1 mol%.
Table 1 shows the EW, water content, oxygen solubility and oxygen permeability coefficient of AM3. Table 2 shows the presence or absence of cracks in the catalyst layer using AS3, the battery performance, and the results of the chemical durability test.
AM3 exhibits high oxygen solubility and oxygen permeability coefficient. Further, it can be seen that the catalyst layer using AS3 has no cracks, and the battery performance and chemical durability are higher than those of the comparative material.
(実施例4)
4−ピペリドンエチレンケタールのかわりに、1−アザ−15-クラウン−5−エーテル(2.28g)を用いる以外は実施例1と同様に合成を行い、含フッ素高分子電解質(A4)を得た。
得られたA4に対して実施例2と同様にフッ素化を行った。
フッ素化したA4を実施例1と同様な方法で溶液化しポリマー溶液(AS4)を得た。
上記AS4をキャスト製膜して、厚み200μmの膜(AM4)を作製した。AM4のEWは1049であり、側鎖に導入されたパーフルオロ1−アザ−15-クラウン−5−エーテルの導入率は10.0mol%であった。
AM4のEW、含水率、酸素溶解度及び酸素透過係数を表1に示す。またAS4を用いた触媒層のひび割れ有無、電池性能及び化学耐久試験の結果を表2に示す。
AM4は高い酸素溶解度、及び酸素透過係数を示す。またAS4を用いた触媒層にはひび割れがなく、電池性能及び化学耐久性が比較の材料よりも高いことが分かる。
(Example 4)
Synthesis was carried out in the same manner as in Example 1 except that 1-aza-15-crown-5-ether (2.28 g) was used instead of 4-piperidone ethylene ketal to obtain a fluorine-containing polymer electrolyte (A4). It was.
The obtained A4 was fluorinated in the same manner as in Example 2.
The fluorinated A4 was solubilized in the same manner as in Example 1 to obtain a polymer solution (AS4).
The AS4 was cast to produce a film (AM4) having a thickness of 200 μm. The EW of AM4 was 1049, and the introduction rate of perfluoro1-aza-15-crown-5-ether introduced into the side chain was 10.0 mol%.
Table 1 shows the EW, water content, oxygen solubility and oxygen permeability coefficient of AM4. Table 2 shows the presence or absence of cracks in the catalyst layer using AS4, the battery performance, and the results of the chemical durability test.
AM4 exhibits high oxygen solubility and oxygen permeability coefficient. Further, it can be seen that the catalyst layer using AS4 has no cracks, and the battery performance and chemical durability are higher than those of the comparative material.
(比較例1)
市販のナフィオン溶液(Nafion DE2020CS、SIGMA−ALDRICH社製)を用いて、実施例1と同様にして、厚さ200μmのキャスト膜を製膜し、EW、酸素溶解度及び酸素透過係数を測定した。結果を表1に示す。
また上記ナフィオン溶液を用い実施例1と同様に触媒層を作製し、ひび割れ有無、電池性能及び化学耐久性試験を行った。結果を表2に示す。
Nafion DE2020CSは、酸素溶解度が低い。また触媒層にひび割れが生じており、電池性能及び化学耐久性が低くなる。
(Comparative Example 1)
Using a commercially available Nafion solution (Nafion DE2020CS, manufactured by SIGMA-ALDRICH), a cast film having a thickness of 200 μm was formed in the same manner as in Example 1, and the EW, oxygen solubility and oxygen permeability coefficient were measured. The results are shown in Table 1.
Further, a catalyst layer was prepared using the above Nafion solution in the same manner as in Example 1, and the presence or absence of cracks, battery performance and chemical durability tests were carried out. The results are shown in Table 2.
Nafion DE2020CS has low oxygen solubility. In addition, the catalyst layer is cracked, resulting in low battery performance and chemical durability.
(比較例2)
テトラフルオロエチレン及びCF2=CFO(CF2)2−SO2Fから得られたパーフルオロスルホン酸樹脂前駆体ペレットを、水酸化カリウム(15質量%)とメチルアルコール(50質量%)を溶解した水溶液中に、80℃で20時間接触させて、加水分解処理を行った。その後、60℃水中に5時間浸漬した。次に60℃の2N塩酸水溶液に1時間浸漬させる処理を、毎回新しい塩酸水溶液を用いて5回繰り返した後、イオン交換水で水洗、乾燥した。これにより、スルホン酸基(SO3H)を有する含フッ素高分子電解質のペレットを得た。
このペレットをエタノール水溶液(水:エタノール=66.7:33.3(質量比))と共に5Lオートクレーブ中に入れて密閉し、撹拌翼で攪拌しながら160℃まで昇温して5時間保持した。その後、オートクレーブを自然冷却して、5質量%の均一なパーフルオロスルホン酸樹脂溶液を調製した。
次に、この溶液1200gを2Lのナスフラスコに移し、湯浴を80℃に設定したロータリーエバポレータ―(BUCHI社製 Rotavapor R−200)に設置し、固形分濃度が20質量%になるように減圧濃縮し、パーフルオロスルホン酸樹脂溶液−1を調製した。
ポリマー溶液(AS1)のかわりにパーフルオロスルホン酸樹脂溶液−1を用いたこと以外は実施例1と同様にして、厚さ200μmのキャスト膜を製膜し、EW、酸素溶解度及び酸素透過係数を測定した。結果を表1に示す。
また上記パーフルオロスルホン酸樹脂溶液−1を用い実施例1と同様に触媒層を作製し、ひび割れ有無、電池性能及び化学耐久性試験を行った。結果を表2に示す。
パーフルオロスルホン酸樹脂溶液−1を用いたキャスト膜は、酸素溶解度が低い。また触媒層にひび割れが生じており、電池性能及び化学耐久性が低くなる。
(Comparative Example 2)
Tetrafluoroethylene and CF 2 = CFO (CF 2) 2 perfluorosulfonic acid resin precursor pellets obtained from -SO 2 F, and dissolved potassium hydroxide (15 wt%) of methyl alcohol (50 wt%) It was hydrolyzed by contacting it in an aqueous solution at 80 ° C. for 20 hours. Then, it was immersed in water at 60 ° C. for 5 hours. Next, the treatment of immersing in a 2N hydrochloric acid aqueous solution at 60 ° C. for 1 hour was repeated 5 times with a new hydrochloric acid aqueous solution, washed with ion-exchanged water, and dried. As a result, pellets of a fluorine-containing polymer electrolyte having a sulfonic acid group (SO 3 H) were obtained.
The pellets were placed in a 5 L autoclave together with an aqueous ethanol solution (water: ethanol = 66.7: 33.3 (mass ratio)), sealed, heated to 160 ° C. while stirring with a stirring blade, and held for 5 hours. Then, the autoclave was naturally cooled to prepare a uniform perfluorosulfonic acid resin solution of 5% by mass.
Next, 1200 g of this solution was transferred to a 2 L eggplant flask and placed in a rotary evaporator (BUCHI Rotavapor R-200) in which the hot water bath was set to 80 ° C., and the pressure was reduced so that the solid content concentration became 20% by mass. The mixture was concentrated to prepare a perfluorosulfonic acid resin solution-1.
A cast film having a thickness of 200 μm was formed in the same manner as in Example 1 except that the perfluorosulfonic acid resin solution-1 was used instead of the polymer solution (AS1), and the EW, oxygen solubility and oxygen permeability coefficient were determined. It was measured. The results are shown in Table 1.
Further, a catalyst layer was prepared in the same manner as in Example 1 using the above-mentioned perfluorosulfonic acid resin solution-1, and the presence or absence of cracks, battery performance and chemical durability were tested. The results are shown in Table 2.
The cast membrane using the perfluorosulfonic acid resin solution-1 has low oxygen solubility. In addition, the catalyst layer is cracked, resulting in low battery performance and chemical durability.
(比較例3)
テトラフルオロエチレン及びCF2=CFO(CF2)2−SO2Fから得られたパーフルオロスルホン酸樹脂前駆体ペレットを用いる以外は比較例2と同様にキャスト膜、パーフルオロスルホン酸樹脂溶液−2を得た。キャスト膜を用い、EW、酸素溶解度及び酸素透過係数を測定した。結果を表1に示す。
また上記パーフルオロスルホン酸樹脂溶液−2を用い実施例1と同様に触媒層を作製し、ひび割れ有無、電池性能及び化学耐久性試験を行った。結果を表2に示す。
パーフルオロスルホン酸樹脂溶液−2を用いたキャスト膜は、酸素溶解度が低い。また触媒層にひび割れが生じており、電池性能及び化学耐久性が低くなる。
(Comparative Example 3)
Cast membrane and perfluorosulfonic acid resin solution-2 as in Comparative Example 2 except that perfluorosulfonic acid resin precursor pellets obtained from tetrafluoroethylene and CF 2 = CFO (CF 2 ) 2- SO 2 F are used. Got EW, oxygen solubility and oxygen permeability coefficient were measured using cast membranes. The results are shown in Table 1.
Further, a catalyst layer was prepared in the same manner as in Example 1 using the above-mentioned perfluorosulfonic acid resin solution-2, and the presence or absence of cracks, battery performance and chemical durability were tested. The results are shown in Table 2.
The cast membrane using the perfluorosulfonic acid resin solution-2 has low oxygen solubility. In addition, the catalyst layer is cracked, resulting in low battery performance and chemical durability.
(比較例4)
ラジカル重合法で得られた、パーフルオロ(2,2−ジメチル−1,3−ジオキソール)とCF2=CFOCF2CF(CF3)OCF2CF2SO2Fとの共重合体(69.8mol%/30.2mol%)を用いる以外は比較例2と同様にキャスト膜、パーフルオロスルホン酸樹脂溶液−3を得た。キャスト膜を用い、EW、酸素溶解度及び酸素透過係数を測定した。結果を表1に示す。
また上記パーフルオロスルホン酸樹脂溶液−3を用い実施例1と同様に触媒層を作製し、ひび割れ有無、電池性能及び化学耐久性試験を行った。結果を表2に示す。
パーフルオロスルホン酸樹脂溶液−3を用いたキャスト膜は、実施例1と比較して酸素溶解度は高いものの、触媒層にひび割れが生じており、電池性能及び化学耐久性が低くなる。
(Comparative Example 4)
Copolymer (69.8 mol) of perfluoro (2,2-dimethyl-1,3-dioxol) obtained by radical polymerization method and CF 2 = CFOCF 2 CF (CF 3 ) OCF 2 CF 2 SO 2 F % / 30.2 mol%) was used, and a cast film and a perfluorosulfonic acid resin solution-3 were obtained in the same manner as in Comparative Example 2. EW, oxygen solubility and oxygen permeability coefficient were measured using cast membranes. The results are shown in Table 1.
Further, a catalyst layer was prepared in the same manner as in Example 1 using the above-mentioned perfluorosulfonic acid resin solution-3, and the presence or absence of cracks, battery performance and chemical durability were tested. The results are shown in Table 2.
The cast membrane using the perfluorosulfonic acid resin solution-3 has higher oxygen solubility as compared with Example 1, but the catalyst layer is cracked, and the battery performance and chemical durability are lowered.
Claims (9)
前記スルホニル基及び環構造に含まれない前記エーテル結合の少なくとも1つが、芳香族環、脂肪族環、及び芳香族環と脂肪族環とを含む複合環からなる群から選ばれる少なくとも1つの環状構造と直接結合しており、
前記直接結合をしている前記環状構造が窒素原子及び/又はエーテル性の酸素原子を含むことを特徴とする、含フッ素高分子電解質。 The side chain has a sulfonyl group as a linking group and / or an ether bond not contained in the ring structure.
At least one of the ether bonds not contained in the sulfonyl group and the ring structure is selected from the group consisting of an aromatic ring, an aliphatic ring, and a complex ring containing an aromatic ring and an aliphatic ring. Is directly connected to
A fluorine-containing polymer electrolyte, wherein the directly bonded cyclic structure contains nitrogen atoms and / or etheric oxygen atoms.
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