Proton-conducting membrane and use thereof
The present invention relates to a novel proton-conducting polymer membrane based on polyazoles which can, owing to its excellent chemical and thermal properties, be used for a variety of purposes and is particularly suitable as a polymer-electrolyte membrane (PEM) for the production of membrane electrode units for so-called PEM fuel cells.
1. A proton-conducting polymer membrane based on polyazoles and further containing organic phosphonic anhydride, and partial hydrolysis products of the organic phosphonic anhydride which can be obtained by a process comprising the steps of:
A) dissolving the polyazole polymer in organic phosphonic anhydrides with formation of a solution and/or dispersion,
B) heating the solution obtainable in accordance with step A) under inert gas to temperatures of up to 400° C.,
C) forming a membrane using the solution of the polyazole polymer in accordance with step B) on a support and
D) treating the membrane formed in step C) in the presence of moisture at temperatures and for a period of time until the membrane is self-supporting and can be detached from the support without any damage and
wherein in step A), said organic phosphonic anhydrides are of the formula (1), (2) or (3) and said partial hydrolysis products of the organic phosphonic anhydride are the partial hydrolysis products of the organic phosphonic anhydride of the formulas (1), (2) or (3), wherein:
formula (1) is of the formula
formula (2) is a linear compound of the formula
and
formula (3) is an anhydride of the multiple organic phosphonic acids of the formula
wherein the radicals R and R′ are identical or different and represent a C 1 -C 20 carbon-containing group selected from the group consisting of:
C 1 -C 20 alkyl,
C 6 -C 20 aryl, C 1 -C 20 fluoroalkyl, C 6 -C 20 fluoroaryl, C 1 -C 20 alkoxy, C 6 -C 20 aryloxy, C 7 -C 20 arylalkyl, C 7 -C 20 alkylaryl, C 7 -C 20 aryloxyalkyl, C 12 -C 20 aryloxyaryl, C 7 -C 20 heteroaryl, C 4 -C 20 heterocycloalkyl and C 2 -C 20 heteroatom-containing group; and
where one or more of the C 1 -C 20 carbon-containing groups can form a cyclic system.
2. The membrane according to claim 1 , wherein in step B) said heating is up to 300° C.
3. The membrane according to claim 1 , which further comprises in step A), a polyphosphoric acid having a content of at least 83%, calculated as P 2 O 5 by acidimetry.
4. The membrane according to claim 1 , which further comprises in step A), P 2 O 5 .
5. The membrane according to claim 1 , wherein in step A), B) or step C), a solution or a dispersion/suspension is produced.
6. The membrane according to claim 1 , wherein the polyazole polymer used in step A) contains recurring azole units of the general formula (I) and/or (II) wherein
Ar are identical or different and represent a tetracovalent aromatic or heteroaromatic group which can be mononuclear or polynuclear,
Ar″ are identical or different and represent a bicovalent aromatic or heteroaromatic group which can be mononuclear or polynuclear,
Ar 2 are identical or different and represent a bicovalent or bicovalent aromatic or heteroaromatic group which can be mononuclear or polynuclear, and
X are identical or different and represent oxygen, sulphur or an amino group which carries a hydrogen atom, or a group having 1-20 carbon atoms.
7. The membrane according to claim 6 , wherein X are identical or different and represent oxygen, sulphur or an amino group which carries a hydrogen atom, a branched or -unbranched alkyl or alkoxy group, or an aryl group as a further radical.
8. The membrane according to claim 1 , wherein, in step A), the polyazole polymer is selected from the group consisting of polybenzimidazole, poly(pyridines), poly(pyrimidines), polyimidazoles, polybenzothiazoles, polybenzoxazoles, polyoxadiazoles, polyquinoxalines, polythiadiazoles and poly(tetrazapyrenes) is used.
9. The membrane according to claim 1 , wherein, before, during or after step A) and/or step B) or before step C), a further polymer is added as blend material.
10. The membrane according to claim 1 , wherein, before step D), the viscosity is adjusted by addition of phosphoric acid and/or organophosphonic acids.
11. The membrane according to claim 1 , wherein the treating of the membrane in step D) is performed at temperatures of more than 0° C. and less than 150° C., in the presence of moisture or water and/or steam.
12. The membrane according to claim 1 , wherein the treating of the membrane in step D) is performed at temperatures of more than 20° C. and less than 90° C., in the presence of moisture or water and/or steam.
13. The membrane according to claim 1 , wherein the treating of the membrane in step D) is for 10 seconds to 300 hours.
14. The membrane according to claim 1 , wherein, in step C), an electrode is chosen as the support and the treatment in accordance with step C) is such that the membrane formed is no longer self-supporting.
15. The membrane according to claim 1 , wherein, in step C), a layer having a thickness of 20 to 4,000 μm, is produced.
16. The membrane according to claim 1 , wherein the membrane formed in step D) has a thickness between 15 and 3,000 μm.
17. A membrane electrode unit containing at least one electrode and at least one membrane according to claim 16 .
18. The membrane according to claim 1 , wherein in step A), the polyazole polymer used contains one or more recurring benzimidazole units of the formula
where n is an integer greater than or equal to 10.
19. The membrane according to claim 1 , wherein the treating of the membrane in step D) is performed at temperatures of more than 20° C. and less than 90° C., in the presence of moisture or water and/or steam for 1 minute to 200 hours and the membrane formed in step D) has a thickness between 20 and 1,500 μm.
20. The membrane according to claim 1 , wherein the radicals R and R′ are identical or different and represent methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, s-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-octyl, cyclooctyl, phenyl, biphenyl, naphthyl, anthracenyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, triphenylenyl, [1,1′;3′,1]-terphenyl-2′-yl, binaphthyl, phenanthrenyl, tetrafluorophenyl, heptafluoronaphthyl, methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, phenoxy, naphthoxy, biphenyloxy, anthracenyloxy, phenanthrenyloxy, o-tolyl, m-tolyl, p-tolyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, 2,6-di-i-propylphenyl, 2,6-di-t-butylphenyl, o-t-butylphenyl, m-t-butylphenyl, p-t-butylphenyl, benzyl, ethylphenyl, propylphenyl, diphenylmethyl, triphenylmethyl, naphthalenyl methyl, o-methoxyphenyl, m-phenoxymethyl, p-phenoxymethyl, p-phenoxyphenyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, quinolinyl, isoquinolinyl, acridinyl, benzoquinolinyl, benzo-isoquinolinyl, furyl, benzofutyl, 2-pyrrolidinyl, 2-indolyl, 3-indolyl, 2,3-dihydroindolyl, carbonyl, benzoyl, oxybenzoyl, benzoyloxy, acetyl, acetoxy or nitril.
21. An electrode having a proton-conducting polymer coating based on polyazoles and further containing organic phosphonic anhydride, and partial hydrolysis products of the organic phosphonic anhydride which can be obtained by a process comprising the steps of:
A) dissolving the polyazole polymer in organic phosphonic anhydrides with formation of a solution and/or dispersion,
B) heating the solution obtainable in accordance with step A) under inert gas to temperatures of up to 400° C.,
C) forming a membrane using the solution of the polyazole polymer in accordance with step B) on an electrode and
D) treating the layer formed in step C) in the presence of moisture and
wherein in step A), said organic phosphonic anhydrides are of the formula (1), (2) or (3) and said partial hydrolysis products of the organic phosphonic anhydride are the partial hydrolysis products of the organic phosphonic anhydride of the formulas (1), (2) or (3), wherein:
formula (1) is of the formula
formula (2) is a linear compound of the formula
and
formula (3) is an anhydride of the multiple organic phosphonic acids of the formula
wherein the radicals R and R′ are identical or different and represent a C 1 -C 20 carbon-containing group selected from the group consisting of:
C 1 -C 20 alkyl,
C 6 -C 20 aryl, C 1 -C 20 fluoroalkyl, C 6 -C 20 fluoroaryl, C 1 -C 20 alkoxy, C 6 -C 20 aryloxy, C 7 -C 20 arylalkyl, C 7 -C 20 alkylaryl, C 7 -C 20 aryloxyalkyl, C 12 -C 70 aryloxyaryl, C 7 -C 20 heteroaryl, C 4 -C 20 heterocycloalkyl and C 2 -C 20 heteroatom-containing group; and
where one or more of the C 1 -C 20 carbon-containing groups can form a cyclic system.
22. The electrode according to claim 21 , where the coating has a thickness between 2 and 3,000 μm.
23. A membrane electrode unit containing at least one electrode according to claim 21 .
24. A fuel cell containing one or more membrane electrode units according to claim 23 .