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A layered membrane or membrane electrode assembly for use with a direct oxidation fuel cell provides reduced water carryover and fuel crossover while maintaining a high total protonic exchange between anode and cathode. A layer of material which is substantially impermeable to water and fuel, but wh

A layered membrane or membrane electrode assembly for use with a direct oxidation fuel cell provides reduced water carryover and fuel crossover while maintaining a high total protonic exchange between anode and cathode. A layer of material which is substantially impermeable to water and fuel, but which is foraminous to allow contact between adjacent protonically conductive layers, is used to significantly increase the system's carryover resistance while only modestly increasing the total reaction resistance.

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1. A membrane electrode assembly for use in a direct oxidation fuel cell comprising:a barrier layer of material that is substantially protonically non-conductive and which is substantially impermeable to water and carbonaceous fuel; first and second protonically conductive membranes disposed, respec

1. A membrane electrode assembly for use in a direct oxidation fuel cell comprising:a barrier layer of material that is substantially protonically non-conductive and which is substantially impermeable to water and carbonaceous fuel; first and second protonically conductive membranes disposed, respectively, on opposite surfaces of said barrier layer; selected sites comprising openings providing passages through said barrier layer enabling protonically conductive contact through said passages between said first and second membranes, said passages being large enough relative to barrier layer thickness to enable the protonically conductive contact through said barrier layer, while said passages are small enough to substantially prevent the passage of liquid therethrough; first and second catalysts disposed, respectively, on the surfaces of said membranes which are not in contact with said barrier layer; and first and second diffusion material layers disposed, respectively, on the surfaces of said catalysts which are not in contact with said membranes. 2. The assembly as in claim 1 wherein said barrier layer comprises a microporous material.3. A membrane electrode assembly for use in a direct oxidation fuel cell comprising:a barrier layer of material that is substantially protonically non-conductive and which is substantially impermeable to water and carbonaceous fuel, said barrier layer comprising a polyester microfilm with microperforations; first and second protonically conductive membranes disposed, respectively, on opposite surfaces of said barrier layer; a selected sites comprising openings providing passages through said barrier layer enabling protonically conductive contact through said passages between said first and to second membranes; first and second catalysts disposed, respectively, on the surfaces of said membranes which are not in contact with said barrier layer; and first and second diffusion material layers disposed, respectively, on the surfaces of said catalysts which are not in contact with said membranes. 4. A membrane electrode assembly for use in a direct oxidation fuel cell comprising:a barrier layer of material that is substantially protonically non-conductive and which is substantially impermeable to water and carbonaceous fuel, said barrier layer comprising a polyimide film with microperforations; first and second protonically conductive membranes disposed, respectively, on opposite surfaces of said barrier layer; selected sites comprising openings providing passages through said barrier layer enabling protonically conductive contact through said passages between said first and to second membranes; first and second catalysts disposed, respectively, on the surfaces of said membranes which are not in contact with said barrier layer; and first and second diffusion material layers disposed, respectively, on the surfaces of said catalysts which are not in contact with said membranes said barrier layer comprises a polyimide film with microperforations. 5. The assembly as in claim 1 wherein said assembly is used in a direct methanol fuel cell.6. A layered membrane for use in a direct oxidation fuel cell comprising:a barrier layer of material that is substantially protonically non-conductive and which is substantially impermeable to water and carbonaceous fuel; and first and second protonically conductive membranes disposed, respectively, on opposite surfaces of said barrier layer; and selected sites comprising openings providing passages through said barrier layer enabling protonically conductive contact through said passages between said first and second membranes, said passages being large enough relative to barrier layer thickness to enable the protonically conductive contact through said barrier layer, while said passages are small enough to substantially prevent the passage of liquid therethrough. 7. The membrane as in claim 6 wherein said barrier layer comprises a microporous material.8. A layered membrane for use in a direct oxidation fuel cell comprising:a barrier layer of material that is substantially protonically non-conductive and which is substantially impermeable to water and carbonaceous fuel, said barrier layer comprising a polyester microfilm with microperforations; first and second protonically conductive membranes disposed, respectively, on opposite surfaces of said barrier layer; and a selected sites comprising openings providing passages through said barrier layer enabling protonically conductive contact through said passages between said first and second membranes. 9. A layered membrane for use in a direct oxidation fuel cell comprising:a barrier layer of material that is substantially protonically non-conductive and which is substantially impermeable to water and carbonaceous fuel, said barrier layer comprising a polyimide film with microperforations; first and second protonically conductive membranes disposed, respectively, on opposite surfaces of said barrier layer; and selected sites comprising opening providing passages through said barrier layer enabling protonically conductive contact through said passages between said first and second membranes. 10. The membrane as in claim 6 wherein said membrane is used in a direct methanol fuel cell.11. A method of constructing a layered membrane for use in a direct oxidation fuel cell comprising the steps of:providing a layer of material that is substantially protonically non-conductive and which is substantially impermeable to water and carbonaceous fuel; and providing, on opposite sides of said layer, protonically conductive membranes; and providing sites that include passages for protons to pass through said layer which allow protonically conductive contact between said protonically conductive membranes, said passages being large enough relative to barrier layer thickness to enable the protonically conductive contact through said barrier layer, while said passages are small enough to substantially prevent the passage of liquid therethrough. 12. The method as in claim 11 wherein said layer comprises a microporous material.13. A method of constructing a layered membrane for use in a direct oxidation fuel cell comprising the steps of:providing a layer of material that is substantially protonically non-conductive and which is substantially impermeable to water and carbonaceous fuel, wherein said layer comprises a polyester microfilm with microperforations; and providing, on opposite sides of said layer, protonically conductive membranes; and providing sites that include passages for protons to pass through said layer which allow protonically conductive contact between said protonically conductive membranes. 14. A method of constructing a layered membrane for use in a direct oxidation fuel cell comprising the steps of:providing a layer of material that is substantially protonically non-conductive and which is substantially impermeable to water and carbonaceous fuel, wherein said layer comprises a polyimide film with microperforations; and providing, on opposite sides of said layer, protonically conductive membranes; and providing sites that include passages for protons to pass through said layer which allow protonically conductive contact between said protonically conductive membranes. 15. A method of constructing a membrane electrode assembly for use in a direct oxidation fuel cell comprising the steps of:providing a barrier layer of material which is substantially impermeable to water and carbonaceous fuel and which is substantially impermeable to protons; providing, on opposite sides of said barrier layer, first and second protonically conductive membranes; providing sites in said barrier layer which allow protonically conductive contact between said protonically conductive membranes, said passages being large enough relative to barrier layer thickness to enable the protonically conductive contact through said barrier layer, while said passages are small enough to substantially prevent the passage of liquid therethrough; and providing, on the surfaces of said membranes which are not in contact with said layer, first and second catalyst layers; and providing, on the surfaces of said first and second catalyst layers which are not in contact with said membranes, first and second distribution layers. 16. The method as in claim 15 wherein said barrier layer comprises a microporous material.17. A method of constructing a membrane electrode assembly for use in a direct oxidation fuel cell comprising the steps of:providing a barrier layer of material which is substantially impermeable to water and carbonaceous fuel and which is substantially impermeable to protons, said barrier layer comprising a polyester microfilm with microperforations; providing, on opposite sides of said barrier layer, first and second protonically a conductive membranes; and providing sites in said barrier layer which allow protonically conductive contact to between said protonically conductive membranes. 18. A method of constructing a membrane electrode assembly for use in a direct oxidation fuel cell comprising the steps of:providing a barrier layer of material which is substantially impermeable to water and carbonaceous fuel and which is substantially impermeable to protons, said barrier layer comprises a polyimide film with microperforations; providing, on opposite sides of said barrier layer, first and second protonically a conductive membranes; and providing sites in said barrier layer which allow protonically conductive contact to between said protonically conductive membranes. 19. A direction oxidation fuel cell comprising:an anode; a cathode; a membrane electrode assembly, said assembly including a barrier layer of material that is substantially protonically non-conductive and which is substantially impermeable to water and fuel, first and second protonically conductive membranes disposed, respectively, on opposite surfaces of said barrier layer, said barrier layer having sites in said barrier layer that allow protonically conductive contact between said membranes, said passages being large enough relative to barrier layer thickness to enable the protonically conductive contact through said barrier layer, while said passages are small enough to substantially prevent the passage of liquid therethrough first and second catalysts disposed, respectively, on the surfaces of said membranes which are not in contact with said layer, and first and second diffusion material layers disposed, respectively, on the surfaces of said catalysts which are not in contact with said membranes; and a housing in which said anode, cathode and assembly are disposed. 20. The fuel cell as in claim 19 wherein said barrier layer comprises a microporous material.21. A direction oxidation fuel cell comprising:an anode; a cathode; a membrane electrode assembly, said assembly including a barrier layer of material that is substantially protonically non-conductive and which is substantially impermeable to water and fuel, said barrier layer comprising a polyester microfilm with microperforations, first and second protonically conductive membranes disposed, respectively, on opposite surfaces of said barrier layer, said barrier layer having sites in said barrier layer that allow protonically conductive contact between said membranes, said passages being large enough relative to barrier layer thickness to enable the protonically conductive contact through said barrier layer, while said passages are small enough to substantially prevent the passage of liquid therethrough first and second catalysts disposed, respectively, on the surfaces of said membranes which are not in contact with said layer, and first and second diffusion material layers disposed, respectively, on the surfaces of said catalysts which are not in contact with said membranes; and a housing in which said anode, cathode and assembly are disposed. 22. A direction oxidation fuel cell comprising:an anode; a cathode; a membrane electrode assembly, said assembly including a barrier layer of material that is substantially protonically non-conductive and which is substantially impermeable to water and fuel, said barrier layer comprises a polyimide film with microperforations, first and second protonically conductive membranes disposed, respectively, on opposite surfaces of said barrier layer, said barrier layer having sites in said barrier layer that allow protonically conductive contact between said membranes, said passages being large enough relative to barrier layer thickness to enable the protonically conductive contact through said barrier layer, while said passages are small enough to substantially prevent the passage of liquid therethrough, first and second catalysts disposed, respectively, on the surfaces of said membranes which are not in contact with said layer, and first and second diffusion material layers disposed, respectively, on the surfaces of said catalysts which are not in contact with said membranes; and a housing in which said anode, cathode and assembly are disposed. 23. The fuel cell as in claim 22 wherein said fuel cell is a direct methanol fuel cell.