アニオン交換型燃料電池用電解質膜の研究開発（第2報） …

1 67 2 1 1 2 2 3 3 1 2 3 ( ) Research and development of anion exchange electrolyte membrane for fuel cells 2nd report Takefumi MIKAMI1, Takahiro SATO1, Michiyoshi NISHIMURA2, Osamu ABE2, Naoki YOKOTA3 and Manai Shimada3 1 Yamanashi Prefectural Industrial Technology Center, 2 Yamanashi Prefectural Fuji Industrial Technology Center, 3 TAKAHATA Precision Japan Co., Ltd. QPE QPE QPE TMA QPP QPE QPP 40 C 1M KOH QPE 300 ,QPP 1000.

2 Abstract The polymer electrolyte fuel cell which used the anion exchange membrane instead of the proton exchange membrane has attracted attention in recent years. Although this system has a subject in durability of electrolyte membranes, there is an advantage such as the availability of an inexpensive metallic catalyst and constituent material, and the suitability for use of liquid fuel. In this research, the anion exchange membrane which is this important material was studied. Previously the polyether electrolyte membrane was synthesized by chloromethylation and quaternization with amine Menschutkin reaction . The chloromethylation reaction was difficult to control and has used harmful reagents, therefore an alternative method was investigated.

3 In particular, original bisphenol monomers having various amine groups were synthesized, and electrolyte membranes were synthesized from those monomers by easier method. The synthesized aromatic polyether electrolyte membranes with various ammonium groups such as cyclic or long-chain alkyl ammonium groups were evaluated. Those electrolyte membranes were shown better stability in an alkaline environment then the membrane having typical trimethyl ammonium TMA group. The decomposition of the polyether main chain was also suggested. Therefore, the renewed electrolyte membrane having polyphenylene structure without ether bond at hydrophilic segments were synthesized. The membranes having polyphenylene structure was shown excellent alkaline stability as compared to conventional polyether membranes.

4 It was suggested that the stability of the polymer main chain in an alkaline environment were PEFC 10 SOFC 2014 MIRAI PEFC 68 PEFC 1 1 2. 2-1 Decafluorobipheyl DFBP hexafluorobisphenol A HFBPA 4,4 -dihydroxydiphenylether DHDPE CMME 1,1,2,2- TCE Ni cod 2 2.

5 2 -bipyridine DMAc DMAc THF Aldrich 2-2 DHDPE Mannich DHDPE 2 24 48 DADPE 64% 2-3 QPE-1 DHDPE DFBP DADPE DFPB DMAc 60 C DMAc 60 C DMAc 6 50 C 50 m 10 10cm 1M KOH 48 OH- 2-4 DHDPE DFBP DMAc DMAc 6 DMAc 50 C 50 m 10 10cm 69 1M KOH 48 OH- 2-5 QPP HFBPA DFBP DMAc 60 C 2h DFBP p.

6 P- m- Ni cod 2, 2,2 -bipyridine DMAc 80 C IEC p- m- TCE CMME THF 80 C 120 TCE 48h 1M KOH 48 OH- 2-6 NMR JEOL JNM-ECA500 GPC Shodex KF-805 IEC 1H NMR Solartolon 1255B/1287 HIOKI 3532-80 4 300 mV 10-100000 Hz 1mm 80 C 48 1M KOH 3.

7 3-1 DHDPE Mannich 2 2 DADPE DHDPE THF 1H NMR 3 GCMS 3 DADPE 1H NMR 3-2 QPE-1 QPE-1 4 DHDPE DFBP DMAc 60 C DHDPE HFBPA DFBP DHDPE DFBP 70 DFPB DABPA DMAc DFBP 1H, 19F NMR GPC = x = y 1.

8 1 NMR DMAc 1H, 19F NMR GPC Mn> 50kDa DMAc 6 1H NMR X 1M KOH 48 OH- 5 QPE-2 4 QPE-1, TMA 713-3 IEC QPE-2, 5 1 QPE-1 x6y8 IEC meq/g 1H NMR KOH OH- OH- QPE-2 QPE-1 IEC QPE-2 60 C QPE-1 IEC = meq/g 45 mS/cm QPE-2 IEC = meq/g 53 mS/cm 80 C 120 1 Polymer block length x.

9 Y IECa meq/g conductivityb mS/cm Water uptake % QPE-1 x6y8 x6y8 x6y6 x6y6 x5y11 x5y4 calculated from 1H NMR spectra. b measured in water 60 C . c quaternized with CH3I, d quaternized with CH3O TMA 6 DHDPE DFBP DMAc K2CO3 Mn> 50kDa 1H 6 1M KOH 48 OH- 3-5 1.

10 1 x= y= , 6 2 72 TMA C4 C10 C10 Pyr C10 Pip C4 Pip C10 Mor C10 IEC= 3 80 C 24 1M KOH 48 OH- 1M HCO3- 1M KOH OH- OH- Pip C4 Pip C10 2 ion- exchange groupIECa meq/g conductivityb mS/cm Water uptake % C1 C4 C10 C1 C4 C10 C1 C4 C10 from 1H NMR spectra. bmeasured in water 60 C.