Electrochemical uses of amorphous fluoropolymers
View Patent ↗An electrochemical application that utilizes amorphous fluoropolymers providing a membrane electrode assembly that is durable, uniform and possesses a good structural integrity, produced by a method that avoids a long, complicated sintering of the fluoropolymers incorporated at undesirably high temperatures.
1. A method for forming a membrane electrode assembly comprising:
forming a layered structure including at least one substantially fluorinated solid polymer electrolyte membrane, at least one catalyst layer containing a catalyst and a substantially fluorinated ionomeric resin binder, and at least one fibrous carbon gas diffusion backing layer, wherein at least one of said layers further comprises an amorphous fluoropolymer;
heating the layered structure to a temperature of less than about 200° C.; and
applying pressure to the heated layered structure to produce a consolidated membrane electrode assembly wherein the catalyst layer is in ionically conductive contact with the solid polymer electrolyte membrane, and the gas diffusion backing layer is in electronically conductive contact with the catalyst layer.
2. The method of claim 1 wherein both the catalyst layer and the gas diffusion backing layer further comprise an amorphous fluoropolymer.
3. The method of claim 1 wherein the solid polymer electrolyte membrane comprises an ionomer comprising monomer units of tetrafluoroethylene and 2-20 mol-% of monomer units described by the formula
—(O—CF 2 CFR) a O—CF 2 (CFR′) b SO 3 —H+
where R and R′ are independently selected from F, Cl or a perfluorinated alkyl group having 1 to 10 carbon atoms, a=0, 1 or 2, b=0 to 6.
4. The method of claim 3 wherein a=1,R is trifluoromethyl, R′ is F, b=1, and the equivalent weight of the SPE membrane is in the range of 700-2000.
5. The method of claim 1 wherein the amorphous fluoropolymer is present in the gas diffusion backing layer at a concentration of less than 15% by weight.
6. A method for forming a catalyst coated membrane comprising:
combining a substantially fluorinated non-ionic polymeric ionomer-precursor resin and a catalyst to form a homogeneous mixture;
applying the mixture to the surface of a solid polymer electrolyte membrane to form a coated membrane;
contacting the coated membrane with an alkali metal base to hydrolyze the non-ionic polymeric ionomer-precursor resin forming an ionomer therefrom; and
contacting the ionomer with a mineral acid.
7. The method of claim 6 wherein the homogeneous mixture further comprises an amorphous fluoropolymer.
8. The method of claim 1 or claim 7 wherein the amorphous fluoropolymer is a copolymer comprising monomer units derived from tetrafluoroethylene (TFE) and at least 20 mol-% of monomer units derived from monomers selected from the group consisting of hexafluoropropylene (HFP), perfluoroalkyl vinyl ethers, 2,2-bistrifluoromethyl-4,5-difluoro-1,3-dioxole (PDD), and mixtures thereof.
9. The method of claim 8 wherein the amorphous fluoropolymer is a terpolymer comprising about 60 mol-% of monomer units derived from TFE, about 26 mol-% of monomer units derived from perfluoromethyl vinyl ether, and about 14 mol-% of monomer units derived from perfluoroethylvinyl ether, or a copolymer of TEE and PDD comprising 67 mol-% PDD.
10. A membrane electrode assembly comprising:
a substantially flourinated solid polymer electrolyte membrane separator;
a catalyst layer in ionic conductive contact with said separator wherein the catalyst layer comprises a catalyst and a substantially fluorinated ionomeric resin binder;
a fibrous carbon gas diffusion backing layer in electronic conductive contact with said catalyst layer; and
a fluoropolymer included in at least one of said layers, the fluoropolymer comprising an amorphous fluoropolymer.
11. The membrane electrode assembly of claim 10 wherein the solid polymer electrolyte membrane comprises an ionomer comprising monomer units of tetrafluoroethylene and 2-20 mol-% of monomer units described by the formula
—(O—CF 2 CFR) a O—CF 2 (CFR′) b SO 3 —H+
where R and R′ are independently selected from F, Cl or a perfluorinated alkyl group having 1 to 10 carbon atoms, a=0, 1 or 2, b=0 to 6.
12. The membrane electrode assembly of claim 11 wherein a=1, R is trifluoromethyl, R′ is F, b=1, and the equivalent weight of the SPE membrane is in the range of 700-2000.
13. The membrane electrode assembly of claim 10 wherein the amorphous fluoropolymer is a copolymer comprising monomer units derived from TFE and at least 20 mol-% of monomer units derived from monomers selected from the group consisting of hexafluoropropylene (HFP), perfluoroalkyl vinyl ethers, 2,2-bistrifluoromethyl-4,5-difluoro 1,3-dioxole (PDD), and mixtures thereof.
14. The membrane electrode assembly of claim 13 wherein the amorphous fluoropolymer is a terpolymer comprising about 60 mol-% of monomer units derived from TFE, about 26 mol-% of monomer units derived from perfluoromethyl vinyl ether, and about 14 mol-% of monomer units derived from perfluoroethylvinyl ether; or a copolymer of TFE and PDD comprising 67 mol-% PDD.
15. The membrane electrode assembly of claim 10 wherein the amorphous fluoropolymer is present in the gas diffusion backing layer at a concentration of less than 15% by weight.