Polymer electrolyte membrane, membrane-electrode assembly comprising the same and fuel cell comprising the same

Patent metadata

Field	Value
Publication number	US-10003096-B2
Application number	US-201515127825-A
Country	US
Kind code	B2
Filing date	Mar 25, 2015
Priority date	Mar 28, 2014
Publication date	Jun 19, 2018
Grant date	Jun 19, 2018

Abstract

The present invention relates to a polymer electrolyte membrane, and a membrane-electrode assembly and a fuel cell containing the same, and the polymer electrolyte membrane comprises a polymer comprising repeating units represented by the following chemical formulas 1-3. Chemical formulas 1-3 are as defined in the specification. The polymer electrolyte membrane has excellent resistance to radical attack and has improved acid-base interaction, thereby maximizing the function of an ion conductive group, and thus can improve the operation performance of a fuel cell in a low humidification state.

First claim

The invention claimed is:

1. A polymer electrolyte membrane comprising a polymer including repeat units represented by Formulae 1 to 3 below:

wherein A is an ion conducting group selected from the group consisting of a sulfonic acid group, a carboxylic acid group and a phosphoric acid group;
X is any one selected from the group consisting of a single bond, —CO—, —SO 2 —, —CONH—, —COO—, —CR′ 2 —, a cyclohexylidene group, a fluorenylidene group, —O— and —S— in which R′ is any one selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, a halogenated alkyl group, an allyl group, an aryl group, a nitro group and a nitrile group;
Y is a bivalent nitrogen-containing aromatic ring;
Z is —O— or —S—;
R 1 to R 14 are each independently any one selected from the group consisting of a sulfonic acid group, a carboxylic acid group, a phosphoric acid group, a hydrogen atom, a halogen atom, an alkyl group, a halogenated alkyl group, an allyl group, an aryl group, a nitro group and a nitrile group; and
n is an integer of 0 to 4.

2. The polymer electrolyte membrane according to claim 1 , wherein the polymer comprises 100 parts by mole of the repeat unit represented by Formula 3, 1 to 200 parts by mole of the repeat unit represented by Formula 1 and 1 to 200 parts by mole of the repeat unit represented by Formula 2.

3. The polymer electrolyte membrane according to claim 1 , wherein the bivalent nitrogen-containing aromatic ring comprises any one selected from the group consisting of pyrrole, thiazole, isothiazole, oxazole, iso-oxazole, imidazole, imidazoline, imidazolidine, pyrazole, triazine, pyridine, pyrimidine, pyridazine, pyrazine, indole, quinoline, isoquinoline, tetrazole, tetrazine, triazole, carbazole, quinoxaline, quinazoline, indolizine, isoindole, indazole, phthalazine, naphthyridine, bipyridine, benzimidazole, imidazole, pyrrolidine, pyrroline, pyrazoline, pyrazolidine, piperidine, piperazine and indoline.

4. The polymer electrolyte membrane according to claim 1 , wherein the polymer further comprises a repeat unit represented by Formula 4 below:

wherein Z is —O— or —S—; and
R 15 to R 22 are each independently any one selected from the group consisting of a sulfonic acid group, a carboxylic acid group, a phosphoric acid group, a hydrogen atom, a halogen atom, an alkyl group, a halogenated alkyl group, an allyl group, an aryl group, a nitro group and a nitrile group.

5. The polymer electrolyte membrane according to claim 4 , wherein the polymer comprises 100 parts by moles of the repeat unit represented by Formula 3, 1 to 200 parts by mole of the repeat unit represented by Formula 1, 1 to 200 parts by mole of the repeat unit represented by Formula 2, and 1 to 200 parts by mole of the repeat unit represented by Formula 4.

6. The polymer electrolyte membrane according to claim 1 , wherein the polymer further comprises repeat units represented by Formulae 5 and 6 below:

wherein A is an ion conducting group selected from the group consisting of a sulfonic acid group, a carboxylic acid group and a phosphoric acid group;
Y is a bivalent nitrogen-containing aromatic ring;
Z is —O— or —S—; and
R 1 to R 6 and R 15 to R 22 are each independently any one selected from the group consisting of a sulfonic acid group, a carboxylic acid group, a phosphoric acid group, a hydrogen atom, a halogen atom, an alkyl group, a halogenated alkyl group, an allyl group, an aryl group, a nitro group and a nitrile group.

7. The polymer electrolyte membrane according to claim 6 , wherein the polymer further comprises repeat units represented by Formulae 7 and 8 below:

wherein A is an ion conducting group selected from the group consisting of a sulfonic acid group, a carboxylic acid group and a phosphoric acid group;
X is any one selected from the group consisting of a single bond, —CO—, —SO 2 —, —CONH—, —COO—, —CR′ 2 —, a cyclohexylidene group, a fluorenylidene group, —O— and —S— in which R′ is any one selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, a halogenated alkyl group, an allyl group, an aryl group, a nitro group and a nitrile group;
Z is —O— or —S—;
R 1 to R 22 are each independently any one selected from the group consisting of a sulfonic acid group, a carboxylic acid group, a phosphoric acid group, a hydrogen atom, a halogen atom, an alkyl group, a halogenated alkyl group, an allyl group, an aryl group, a nitro group and a nitrile group; and
n is an integer of 0 to 4.

8. The polymer electrolyte membrane according to claim 1 , wherein the polymer electrolyte membrane comprises:
a porous support comprising nanofibers integrated in the form of a non-woven fabric including a plurality of pores; and
the polymer filling pores of the porous support.

9. A membrane-electrode assembly comprising:
an anode and a cathode which face each other; and
the polymer electrolyte membrane according to claim 1 disposed between the anode and the cathode.

10. A fuel cell comprising the membrane-electrode assembly according to claim 9 .

11. A membrane-electrode assembly comprising:
an anode and a cathode which face each other; and
the polymer electrolyte membrane according to claim 8 disposed between the anode and the cathode.

12. A fuel cell comprising the membrane-electrode assembly according to claim 11 .

Assignees

• Kolon Inc

Inventors

• Kim Na Young
• Lee Moo Seok
• Lee Dong Hoon
• Shin Yong Cheol

Classifications

• H01M2008/1095

  Fuel cells with polymeric electrolytes · CPC title

• H01M2300/0082

  Organic polymers · CPC title

• H01M8/1025

  having only carbon and oxygen, e.g. polyethers, sulfonated polyetheretherketones [S-PEEK], sulfonated polysaccharides, sulfonated celluloses or sulfonated polyesters · CPC title

• H01M8/1032 Primary

  having sulfur, e.g. sulfonated-polyethersulfones [S-PES] · CPC title

• C08L79/04

  Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors · CPC title