Polymer membrane, method for the production and use thereof
View Patent ↗The present invention relates to an acid-doped polymer membrane based on polyazoles. The acid-doped polymer membrane can be used in a variety of applications because of its excellent mechanical properties and is useful as polymer electrolyte membrane (PEM) in PEM fuel cells. A doped polymer membrane based on polyazoles is obtained by a process comprising the steps of: A) casting a film using a solution of polymers based on polyazoles in a polar, aprotic organic solvent; B) drying the film formed in step A) until it is self-supporting; C) treating the film obtained in step B) with a treatment liquid at a temperature in the range from room temperature to the boiling point of the treatment liquid; D) drying and/or dabbing the film treated according to step C) to remove the treatment liquid from step C); and E) doping the film treated according to step D) with a doping agent.
1. A process for producing a doped polymer polyazole membrane comprising the steps of:
A) casting a film using a solution of polyazole polymers in a polar, aprotic organic solvent;
B) partially drying the film formed in step A) with heat or under reduced pressure or both until it is self-supporting and forms a partially dried film, said partially dried film having a residual content of said polar, aprotic organic solvent in a range of 10 to 23%;
C) treating the film obtained in step B) with a treatment liquid at a temperature in the range from 20° C. to the boiling point of the treatment liquid;
D) removing the treatment liquid from step C) by drying and/or dabbing the film; and
E) doping the film treated according to step D) with a concentrated doping agent, said concentrated doping agent has a concentration of at least 85 wt % and is selected from the group consisting of: Lewis acids and BrØnsted acids; and
where doping is to a degree from 3 to 15 mol of acid per mol of recurring unit of polymer to obtain a polymer electrolyte membrane.
2. The process of claim 1 where the doping is to a degree from 6 to 12 mols of acid per mol of recurring units of said polymer.
3. The process of claim 1 , wherein the polyazole polymer comprises recurring azole units of the formula (I) and/or (II)
where
Ar are identical or different and are each a tetravalent aromatic or heteroaromatic group which may have one or more rings,
Ar1 are identical or different and are each a divalent aromatic or heteroaromatic group which may have one or more rings,
Ar2 are identical or different and are each a trivalent aromatic or heteroaromatic group which may have one or more rings,
X are identical or different and are each oxygen, sulfur or an amino group which bears a hydrogen atom and a group having 1-20 carbon atoms, preferably a branched or unbranched alkyl or alkoxy group, or an aryl group as other radical.
4. The process of claim 3 , wherein the polymer comprising recurring azole units is a copolymer comprising at least two units of the formula (I) and/or (II) which differ from one another.
5. The process of claim 4 , wherein the polyazole consists only of units of the formula (I) and/or (II).
6. The process of claim 1 , wherein the polyazole is a polymer comprising recurring benzimidazole units of the formula (III)
where n is an integer greater than or equal to 10.
7. The process of claim 6 wherein n is an integer greater than or equal to 100.
8. The process of claim 1 , wherein doping is performed for 1 to 96 hours at a temperature ranging from 20° C. to 100° C.
9. The process of claim 1 where said doping agent is selected from the group consisting of: inorganic Lewis acids and inorganic BrØnsted acids.
10. The process of claim 9 where said doping agent is selected from the group consisting of: sulfuric acid and phosphoric acid.
11. The process of claim 9 where said doping agent phosphoric acid.
12. The process of claim 11 where said phosphoric acid has a concentration of 85%.
13. The process of claim 1 wherein said treatment liquids being selected from the group consisting of: alcohols, ketones, alkanes, ethers, esters, carboxylic acids, halogenated alcohols, halogenated ketones, halogenated alkanes, halogenated ethers, halogenated esters, halogenated carboxylic acids, water, inorganic acids, and mixtures thereof.
14. The process of claim 1 wherein the treated doped membrane having at least a 10% improvement in proton conductivity and/or a 5.5% improvement in elongation at break when compared to an equivalent untreated membrane.