Membrane-electrode assembly for polymer electrolyte fuel cells, and polymer electrolyte fuel cell
View Patent ↗The present invention provides a membrane-electrode assembly for polymer electrolyte fuel cells and a polymer electrolyte fuel cell having excellent dimensional stability and mechanical strength, and having high durability at the time of a power generation. Each of polymer electrolyte membranes ( 111, 211, 311 ) have a region 1 having proton conductivity over the entirety in the thickness direction of the membrane and a region 2 located at the outer peripheral portion of the region 1 and having a non-porous sheet disposed so that the region 2 has no proton conductivity over the entirety in the thickness direction of the membrane, and outer edges of the catalyst layers ( 127, 128 ) are disposed so as to be located in the area 2.
1. A membrane-electrode assembly for polymer electrolyte fuel cells which comprises:
a polymer electrolyte membrane; and
electrodes disposed on both sides of the polymer electrolyte membrane;
wherein
the electrodes comprise:
catalyst layers containing a catalyst; and
gas diffusion layers, at least equal in size to the catalyst layers, disposed on the surfaces of the catalyst layers not in contact with the polymer electrolyte membrane;
the polymer electrolyte membrane comprises:
a filled layer, and
resin layers consisting of an ion exchange resin, coated on both surfaces of the filled layer
a first central region having proton conductivity in the thickness direction of the polymer electrolyte membrane, wherein the filled layer comprises a reinforcing material comprising void portions and the void portions are filled with the ion exchange resin; and
a second region peripheral to the first central region wherein the filled layer comprises a non-perforated sheet coated on both surfaces with the resin layers and having no proton conductivity in the thickness direction of the polymer electrolyte membrane;
the electrodes have an outer edge located on the second region of the polymer electrolyte membrane; and
the gas diffusion layer support the catalyst layers.
2. The membrane-electrode assembly according to claim 1 wherein both the outer edges of the catalyst layers and the peripheral edges of the gas diffusion layers disposed on the surfaces of the catalyst layers not in contact with the polymer electrolyte membrane are located on the second region of the polymer electrolyte membrane.
3. The membrane-electrode assembly according to claim 2 further comprising gaskets contacting both surfaces of the polymer electrolyte membrane in the second region of the polymer electrolyte membrane, wherein an inner portion of the gaskets is located peripheral to an outer edge of each electrode.
4. The membrane-electrode assembly according to claim 1 further comprising a third region of the polymer electrolyte membrane having proton conductivity in the thickness direction of the polymer electrolyte membrane wherein the third region is located peripheral to an outer edge of the second region of the polymer electrolyte membrane.
5. The membrane-electrode assembly according to claim 4 wherein the first central region having proton conductivity in the thickness direction of the polymer electrolyte membrane and the third region of the polymer electrolyte membrane having proton conductivity in the thickness direction of the polymer electrolyte membrane comprise a filled layer comprising:
at least one reinforcing material, having void portions selected from the group consisting of a fibrous reinforcing material, a fibrillated reinforcing material, a porous membrane, a woven fabric, a non-woven fabric and a perforated sheet having a plurality of through-holes; and
an ion exchange resin packed in the void portions of the reinforcing material.
6. The membrane-electrode assembly according to claim 5 wherein the at least one reinforcing material having void portions is a perforated sheet having a plurality of through-holes
7. The membrane-electrode assembly according to claim 6 wherein:
the through-holes have an average area per through-hole of from 1×10 −3 to 20 mm 2 ;
the through-holes are substantially parallel to the thickness direction of the perforated sheet; and
an open area ratio of through-hole area to total area of the third region having proton conductivity is from 30 to 80%.
8. The membrane-electrode assembly according to claim 7 wherein the open area ratio is smaller in a portion of the third region having proton conductivity near the second region peripheral to the first central region than in a portion of the third region having proton conductivity at a greater distance from the second region peripheral to the first central region.
9. The membrane-electrode assembly according to claim 6 wherein the perforated sheet having a plurality of through-holes and the non-perforated sheet of the second region peripheral to the first central region is at least one member selected from the group consisting of a polytetrafluoroethylene, a tetrafluoroethylene/hexafluoropropylene copolymer, a tetrafluoroethylene/perfluoroalkoxyethylene copolymer, a tetrafluoroethylene/ethylene copolymer, a polyethylene, a polypropylene, a polyetheramide, a polyetherimide, a polyether ketone, a polysulfone, a polyphenylene sulfide, a polyphenylene oxide, a polyphosphazene, a polyarylate, a polyimide, a polyamide-imide and a polybenzimidazole.
10. A polymer electrolyte fuel cell comprising the membrane electrode assembly according to claim 9 .
11. The membrane-electrode assembly according to claim 5 wherein the perforated sheet having a plurality of through-holes is a material having a water content of at most 5% after completion of immersion in hot water at 90° C.
12. The membrane-electrode assembly according to claim 1 wherein the first central region having proton conductivity in the thickness direction of the polymer electrolyte membrane comprises a filled layer comprising:
at least one reinforcing material having void portions selected from the group consisting of a fibrous reinforcing material, a fibrillated reinforcing material, a porous membrane, a woven fabric, a non-woven fabric and a perforated sheet having a plurality of through-holes; and
an ion exchange resin packed in the void portions of the reinforcing material.
13. The membrane-electrode assembly according to claim 12 wherein the at least one reinforcing material having void portions is a perforated sheet having a plurality of through-holes.
14. The membrane-electrode assembly according to claim 13 wherein:
the through-holes have an average area per through-hole of from 1×10 −3 to 20 mm 2 ;
the through-holes are substantially parallel to the thickness direction of the perforated sheet; and
an open area ratio of through-hole area to total area of the first central region having proton conductivity is from 30 to 80% .
15. The membrane-electrode assembly according to claim 14 wherein the open area ratio is smaller in a portion of the first central region having proton conductivity near the second region peripheral to the first central region than in a central portion of the first central region having proton conductivity.
16. The membrane-electrode assembly according to claim 13 wherein the perforated sheet having a plurality of through-holes is a material having a water content of at most 5% after completion of immersion in hot water at 90° C.
17. The membrane-electrode assembly according to claim 13 wherein the perforated sheet having a plurality of through-holes and the non-perforated sheet of the second region peripheral to the first central region is at least one member selected from the group consisting of a polytetrafluoroethylene, a tetrafluoroethylene/hexafluoropropylene copolymer, a tetrafluoroethylene/perfluoroalkoxyethylene copolymer, a tetrafluoroethylene/ethylene copolymer, a polyethylene, a polypropylene, a polyetheramide, a polyetherimide, a polyether ketone, a polysulfone, a polyphenylene sulfide, a polyphenylene oxide, a polyphosphazene, a polyarylate, a polyimide, a polyamide-imide and a polybenzimidazole.
18. A polymer electrolyte fuel cell comprising the membrane electrode assembly according to claim 17 .
19. A polymer electrolyte fuel cell comprising the membrane electrode assembly according to claim 1 .