Membrane electrode assemblies and fuel cells with long lifetime
The present invention relates to improved membrane electrode assemblies and fuel cells with long lifetime, comprising two electrochemically active electrodes separated by a polymer electrolyte membrane based on polyoxazoles.
1. A proton-conducting polymer membrane based on polyoxazoles, obtained by a process comprising the steps of
(i) mixing (a) one or more aromatic diamino dihydroxy compounds with (b) one or more aromatic carboxylic acids or esters thereof comprising at least two acid groups per carboxylic acid monomer,
or
mixing one or more aromatic and/or heteroaromatic amino hydroxy carboxylic acids in polyphosphoric acid to form a solution and/or dispersion,
(ii) heating the mixture from step (i), to temperatures in the range from 120° C. up to 300° C. to form polybenzoxazole polymer,
(iii) applying a layer using the mixture from step ii) to a support or to an electrode,
(iv) at least partially hydrolyzing the polyphosphoric acid present in the layer from step (iii) by contacting with water and/or aqueous media,
(v) detaching the self-supporting membrane formed from the support and
wherein the membrane has a proton conductivity, measured at 160° C. and without additional moistening of the gases required, of at least 0.1 S/cm and
the content of polyoxazoles is between 2 and 15% by weight and the content of phosphoric acid between 40 and 70% by weight, and the remaining amount is water.
2. The membrane according to claim 1 , wherein the aromatic diamino dihydroxy compounds used are 3,3′-dihydroxy-4,4′-diaminobiphenyl, 3,3′-dihydroxy-4,4′-diaminodiphenyl sulfone, 4,6-diamino-1,3-dihydroxybenzene (DABDO) or their salts thereof, or mono- and/or dihydrochloride derivatives thereof.
3. The membrane according to claim 1 , wherein said one or more aromatic carboxylic acids used are isophthalic acid, terephthalic acid, phthalic acid, 5-hydroxyisophthalic acid, 4-hydroxyisophthalic acid, 2-hydroxyterephthalic acid, 5-aminoisophthalic acid, 5-N,N-dimethylaminoisophthalic acid, 5-N,N-diethylaminoisophthalic acid, 2,5-dihydroxyterephthalic acid, 2,5-dihydroxyisophthalic acid, 2,3-dihydroxyisophthalic acid, 2,3-dihydroxyphthalic acid, 2,4-dihydroxyphthalic acid, 3,4-dihydroxyphthalic acid, 3-fluorophthalic acid, 5-fluoroisophthalic acid, 2-fluoroterephthalic acid, tetrafluorophthalic acid, tetrafluoroisophthalic acid, tetrafluoroterephthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenic acid, 1,8-dihydroxynaphthalene-3,6-dicarboxylic acid, diphenyl ether 4,4′-dicarboxylic acid, benzophenone-4,4′-dicarboxylic acid, diphenyl sulfone 4,4′-dicarboxylic acid, biphenyl-4,4′-dicarboxylic acid, 4-trifluoromethylphthalic acid, 2,2-bis(4-carboxyphenyl)hexafluoropropane, 4,4′-stilbenedicarboxylic acid or 4-carboxycinnamic acid, or the C1-C20-alkyl esters or C5-C12-aryl esters thereof or the acid anhydrides thereof or acid chlorides thereof.
4. The membrane according to claim 1 , wherein the aromatic carboxylic acids used are tricarboxylic acids, tetracarboxylic acids or the C1-C20-alkyl esters or C5-C12-aryl esters thereof or the acid anhydrides thereof or the acid chlorides thereof.
5. The membrane according to claim 1 , wherein the aromatic carboxylic acids used are 1,3,5-benzenetricarboxylic acid (trimesic acid); 1,2,4-benzenetricarboxylic acid (trimellitic acid); (2-carboxyphenyl)iminodiacetic acid, 3,5,3′-biphenyltricarboxylic acid; 3,5,4′-biphenyltricarboxylic acid or 2,4,6-pyridinetricarboxylic acid or a mixture thereof.
6. The membrane according to claim 1 , wherein the aromatic carboxylic acids used are tetracarboxylic acids, the C1-C20-alkyl esters or C5-C12-aryl esters thereof or the acid anhydrides thereof or the acid chlorides thereof.
7. The membrane according to claim 1 , wherein the aromatic carboxylic acids used are benzene-1,2,4,5-tetracarboxylic acids; naphthalene-1,4,5,8-tetracarboxylic acids, 3,5,3′,5′-biphenyltetracarboxylic acid; benzophenonetetracarboxylic acid, 3,3′,4,4′-biphenyltetracarboxylic acid, 2,2′,3,3′-biphenyltetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid or 1,4,5,8-naphthalenetetracarboxylic acid.
8. The membrane according to claim 1 , wherein the content of tricarboxylic acid or tetracarboxylic acids (based on the dicarboxylic acid used) is between 0 and 30 mol %.
9. The membrane according to claim 4 , wherein the content of tricarboxylic acid or tetracarboxylic acids (based on the dicarboxylic acid used) is between 0.5 and 10 mol %.
10. The membrane according to claim 1 , wherein the heteroaromatic amino hydroxy carboxylic acids used are heteroaromatic dicarboxylic acids and tricarboxylic acids and tetracarboxylic acids which comprise at least one nitrogen, oxygen, sulfur or phosphorus atom in the aromatic system.
11. The membrane according to claim 1 , wherein the heteroaromatic amino hydroxy carboxylic acids used are pyridine-2,5-dicarboxylic acid, pyridine-3,5-dicarboxylic acid, pyridine-2,6-dicarboxylic acid, pyridine-2,4-dicarboxylic acid, 4-phenyl-2,5-pyridinedicarboxylic acid, 3,5-pyrazoledicarboxylic acid, 2,6-pyrimidinedicarboxylic acid, 2,5-pyrazinedicarboxylic acid, 2,4,6-pyridinetricarboxylic acid, benzimidazole-5,6-dicarboxylic acid, or the C1-C20-alkyl esters or C5-C12-aryl esters thereof, or acid anhydrides thereof or acid chlorides thereof.
12. The membrane according to claim 1 , wherein the aromatic and/or heteroaromatic amino hydroxy carboxylic acids used are 3-amino-4-hydroxybenzoic acid or 4-amino-3-hydroxybenzoic acid.
13. The membrane according to claim 1 , wherein, in step A), a polyphosphoric acid with a content, calculated as P 2 O 5 (by acidimetric means) of at least 79.8% is used, which corresponds to a concentration of min. 110% H 3 PO 4 .
14. The membrane according to claim 1 , wherein the polyoxazole polymer comprises repeat oxazole units of the general formula (I) and/or (II) and/or (III) and/or (IV) and/or (V) and/or (VI) and/or (VII)
in which
Ar is the same or different and is a tetravalent aromatic or heteroaromatic group, which is optionally mono- or polycyclic,
Ar 1 is the same or different and is a divalent aromatic or heteroaromatic group, which is optionally mono- or polycyclic,
Ar 2 the same or different and is a di- or trivalent aromatic or heteroaromatic group, which is optionally mono- or polycyclic,
Ar 3 is the same or different and is a trivalent aromatic or heteroaromatic group, which is optionally mono- or polycyclic,
Ar 4 is the same or different and is a trivalent aromatic or heteroaromatic group, which is optionally mono- or polycyclic,
Ar 5 is the same or different and is a tetravalent aromatic or heteroaromatic group, which is optionally mono- or polycyclic,
Ar 6 is the same or different and is a divalent aromatic or heteroaromatic group, which is optionally mono- or polycyclic,
Ar 7 is the same or different and is a divalent aromatic or heteroaromatic group, which is optionally mono- or polycyclic,
Ar 8 is the same or different and is a divalent aromatic or heteroaromatic group, which is optionally mono- or polycyclic,
Ar 9 is the same or different and is a divalent aromatic or heteroaromatic group, which is optionally mono- or polycyclic,
X is the same or different and is oxygen, and
n is an integer greater than or equal to 10.
15. The membrane according to claim 1 , wherein the polyoxazole, is a polybenzoxazole.
16. The membrane according to claim 1 , wherein, in step iii), a polymer comprising repeat units of the formula
where n in each case is an integer greater than or equal to 10 is formed.
17. The membrane according to claim 1 , wherein the hydrolysis in step iv) is effected at temperatures between 0° C. and 200° C., in the presence of humidity or water and/or water vapor.
18. The membrane according to claim 1 , wherein the duration of the hydrolysis in step iv) is between 10 seconds and 300 hours.
19. The membrane according to claim 1 , wherein, in step iii), a layer is obtained with a thickness of 20 and 4000 μm.
20. The membrane according to claim 1 , wherein the membrane present after step iv) has a thickness between 15 and 3000 μm.
21. The membrane according to claim 1 , wherein the hydrolysis in step iv) is effected at temperatures between room temperature (20° C.) and 90° C., in the presence of humidity or water and/or water vapor and
the duration of the hydrolysis in step iv) is between 1 minute to 200 hours and, in step iii), layer is obtained with a thickness of between 50 and 3000 μm and
the membrane present after step iv) has a thickness between 20 and 1500 μm.
22. The membrane according to claim 1 , wherein the membrane comprises at least one further polymer from the group of polyazole, polysulfone, polyether sulfone or polyether ketone, where the polymers optionally also have sulfo groups.
23. A membrane electrode assembly comprising at least one electrode and at least one membrane according to claim 1 .
24. A fuel cell comprising one or more membrane electrode assemblies according to claim 23 .
25. The membrane according to claim 1 , wherein the content of polyoxazoles is between 5 and 10% by weight and the content of phosphoric acid between 50 and 60% by weight, and the remaining amount is water.