Liquid composition, polymer electrolyte membrane, membrane electrode assembly and polymer electrolyte fuel cell

Patent metadata

Field	Value
Publication number	US-11898018-B2
Application number	US-202117332145-A
Country	US
Kind code	B2
Filing date	May 27, 2021
Priority date	Dec 7, 2018
Publication date	Feb 13, 2024
Grant date	Feb 13, 2024

Abstract

To provide a liquid composition capable of forming a membrane excellent in durability against hydrogen peroxide or peroxide radicals and excellent in hydrogen gas barrier property; a polymer electrolyte membrane; a membrane electrode assembly; and a polymer electrolyte fuel cell.
Liquid composition comprising a liquid medium, an acid-type sulfonic acid group-containing fluorocarbon polymer of which the hydrogen gas permeation coefficient under the conditions of a temperature of 80° C. and a relative humidity of 10% is at most 2.5×10 −9 cm 3 ·cm/(s·cm 2 ·cmHg), and cerium atoms; a polymer electrolyte membrane 15 comprising the acid-type sulfonic acid group-containing fluorocarbon polymer, and cerium atoms; and a membrane electrode assembly 10 comprising an anode 13 having a catalyst layer, a cathode 14 having a catalyst layer, and the polymer electrolyte membrane 15 disposed between the anode 13 and the cathode 14.

First claim

What is claimed is:

1. A liquid composition comprising a liquid medium, an acid-type sulfonic acid group-containing fluorocarbon polymer comprising units represented by the following formula u1, and
cerium atoms:

where R F1 and R F2 are each independently a C 1-3 perfluoroalkylene group.

2. The liquid composition according to claim 1 , wherein a ratio of a total number of moles of the cerium atoms to a total number of moles of the sulfonic acid groups contained in the acid-type sulfonic acid group-containing fluorocarbon polymer, is from 0.001 to 0.13.

3. The liquid composition according to claim 1 , wherein an ion exchange capacity of the acid-type sulfonic acid group-containing fluorocarbon polymer is from 0.5 to 2.5 meq/g dry resin.

4. The liquid composition according to claim 1 , wherein a hydrogen gas permeation coefficient under conditions of a temperature of 80° C. and a relative humidity of 10% of the acid-type sulfonic acid group-containing fluorocarbon polymer comprising units represented by formula u1 is at most 2.5×10 −9 cm 3 ·cm/(s·cm 2 ·cmHg).

5. A polymer electrolyte membrane comprising an acid-type sulfonic acid group-containing fluorocarbon polymer comprising units represented by the following formula u1, and cerium atoms:

where R F1 and R F2 are each independently a C 1-3 perfluoroalkylene group.

6. The polymer electrolyte membrane according to claim 5 , wherein a ratio of the total number of moles of the cerium atoms to a total number of moles of the sulfonic acid groups contained in the acid-type sulfonic acid group-containing fluorocarbon polymer is from 0.001 to 0.13.

7. The polymer electrolyte membrane according to claim 5 , wherein an ion exchange capacity of the acid-type sulfonic acid group-containing fluorocarbon polymer is from 0.5 to 2.5 meq/g dry resin.

8. The polymer electrolyte membrane according to claim 5 , wherein a hydrogen gas permeation coefficient under conditions of a temperature of 80° C. and a relative humidity of 10% of the acid-type sulfonic acid group-containing fluorocarbon polymer comprising units represented by formula u1 is at most 2.5×10 −9 cm 3 ·cm/(s·cm 2 ·cmHg).

9. A membrane electrode assembly comprising an anode comprising a catalyst layer, a cathode comprising a catalyst layer, and the polymer electrolyte membrane as defined in claim 5 disposed between the anode and the cathode.

10. A polymer electrolyte fuel cell comprising the membrane electrode assembly as defined in claim 9 .

11. The liquid composition according to claim 1 , wherein:
a ratio of a total number of moles of the cerium atoms to a total number of moles of the sulfonic acid groups contained in the acid-type sulfonic acid group-containing fluorocarbon polymer, is from 0.001 to 0.13;
an ion exchange capacity of the acid-type sulfonic acid group-containing fluorocarbon polymer is from 0.5 to 2.5 meq/g dry resin;
a hydrogen gas permeation coefficient under conditions of a temperature of 80° C. and a relative humidity of 10% of the acid-type sulfonic acid group-containing fluorocarbon polymer comprising units represented by formula u1 is at least 1.0×10 −12 cm 3 ·cm/(s·cm 2 ·cmHg) and at most 2.5×10 −9 cm 3 ·cm/(s·cm 2 ·cmHg);
the liquid medium comprises an organic solvent and water wherein a proportion of the organic solvent is from 1 to 80 mass % and a proportion of the water is from 20 to 99 mass % based on a total of water and organic solvent; and
the acid-type sulfonic acid group-containing fluorocarbon polymer further comprises tetrafluroethylene units.

12. The liquid composition according to claim 1 , wherein R F1 and R F2 are each a C 1 perfluoroalkylene group.

13. The liquid composition according to claim 11 , wherein R F1 and R F2 are each a C 1 perfluoroalkylene group.

14. The polymer electrolyte membrane according to claim 5 , wherein:
a ratio of a total number of moles of the cerium atoms to a total number of moles of the sulfonic acid groups contained in the acid-type sulfonic acid group-containing fluorocarbon polymer, is from 0.001 to 0.13;
an on exchange capacity of the acid-type sulfonic acid group-containing fluorocarbon polymer is from 0.5 to 2.5 meq/g dry resin;
a hydrogen gas permeation coefficient under conditions of a temperature of 80° C. and a relative humidity of 10% of the acid-type sulfonic acid group-containing fluorocarbon polymer comprising units represented by formula u1 is at least 1.0×10 −12 cm 3 ·cm/(s·cm 2 ·cmHg) and at most 2.5×10 −9 cm 3 ·cm/(s·cm 2 ·cmHg); and
the acid-type sulfonic acid group-containing fluorocarbon polymer further comprises tetrafluroethylene units.

15. The polymer electrolyte membrane according to claim 5 , wherein R F1 and R F2 are each a C 1 perfluoroalkylene group.

16. The polymer electrolyte membrane according to claim 14 , wherein R F1 and R F2 are each a C 1 perfluoroalkylene group.

17. A membrane electrode assembly comprising an anode comprising a catalyst layer, a cathode comprising a catalyst layer, and the polymer electrolyte membrane as defined in claim 14 disposed between the anode and the cathode.

18. A polymer electrolyte fuel cell comprising the membrane electrode assembly as defined in claim 17 .

Assignees

• Agc Inc

Inventors

• Okuyama Takumi
• Hirai Takeshi
• Saito Susumu
• Tamitsuji Chikaya
• Jomuta Daisuke

Classifications

• C08J5/225 Primary

  containing fluorine · CPC title

• C08L29/10

  Homopolymers or copolymers of unsaturated ethers (C08L35/08 takes precedence) · CPC title

• H01M8/1004

  characterised by membrane-electrode assemblies [MEA] (H01M8/12 takes precedence) · CPC title

• H01M8/1039

  halogenated, e.g. sulfonated polyvinylidene fluorides · CPC title

• H01M8/1051

  Non-ion-conducting additives, e.g. stabilisers, SiO2 or ZrO2 · CPC title