Electrolyte material, liquid composition and membrane/electrode assembly for polymer electrolyte fuel cell

Patent metadata

Field	Value
Publication number	US-9508463-B2
Application number	US-79039110-A
Country	US
Kind code	B2
Filing date	May 28, 2010
Priority date	May 29, 2009
Publication date	Nov 29, 2016
Grant date	Nov 29, 2016

Abstract

It is to provide an electrolyte material with which an increase in the water content can be suppressed even when the ion exchange capacity of a polymer having repeating units based on a monomer having a dioxolane ring is high; and a membrane/electrode assembly excellent in the power generation characteristics under low or no humidity conditions and under high humidity conditions.
It is to use an electrolyte material, which comprises a polymer (H) having ion exchange groups converted from precursor groups in a polymer (F), and having an ion exchange capacity of at least 1.35 meq/g dry resin, the polymer (F) having repeating units (A) based on a perfluoromonomer having a precursor group of an ion exchange group and a dioxolane ring and repeating units (B) based on a perfluoromonomer having no precursor group and having a dioxolane ring, and having a TQ of at least 200° C., which is a temperature at which the melt volume rate becomes 100 mm 3 /sec when the polymer (F) is subjected to melt-extrusion under an extrusion pressure condition of 2.94 MPa from a nozzle having a length of 1 mm and an inner diameter of 1 mm.

First claim

What is claimed is:

1. An electrolyte material, which comprises a polymer (H) having ion exchange groups converted from precursor groups in the following polymer (F), and having an ion exchange capacity of at least 1.35 meq/g dry resin:
polymer (F): a polymer which has repeating units (A) based on a perfluoromonomer having a precursor group of an ion exchange group and a dioxolane ring and repeating units (B) based on a perfluoromonomer having no ion exchange group nor its precursor group and having a dioxolane ring, and which has a TQ as defined below of at least 200° C.:
TQ: a temperature at which the melt volume rate becomes 100 mm 3 /sec, when the polymer (F) is subjected to melt extrusion under an extrusion pressure condition of 2.94 MPa from a nozzle having a length of 1 mm and an inner diameter of 1 mm.

2. The electrolyte material according to claim 1 , wherein the ion exchange groups in the polymer (H) are groups represented by the following formula (g1):
—(SO 2 X(SO 2 R f ) a ) 31 M +   (g1)

wherein M + is H + , a monovalent metal cation or an ammonium ion in which at least one hydrogen atom may be substituted by a hydrocarbon group, R f is a linear or branched perfluoroalkyl group which optionally has an etheric oxygen atom, and X is an oxygen atom, a nitrogen atom or a carbon atom, provided that when X is an oxygen atom, a=0, when X is a nitrogen atom, a=1, and when X is a carbon atom, a=2.

3. The electrolyte material according to claim 2 , wherein at least one type of repeating units having ion exchange groups converted from the precursor groups in the repeating units (A) are repeating units represented by the following formula (u1):

wherein R 1 is a bivalent perfluoroorganic group which optionally has an etheric oxygen atom, and each of R 2 to R 6 which are independent of one another, is a monovalent perfluoroorganic group which optionally has an etheric oxygen atom, or a fluorine atom.

4. The electrolyte material according to claim 3 , wherein R 5 and R 6 are a fluorine atom.

5. The electrolyte material according to any one of claims 2 to 4 , wherein M + is H + .

6. The electrolyte material according to claim 3 , wherein at least one type of the repeating units represented by the formula (u1) are repeating units represented by the following formula (u1-1):

7. The electrolyte material according to claim 1 , wherein at least one type of the repeating units (B) are repeating units represented by the following formula (u2):

wherein each of R 7 to R 12 which are independent of one another, is a monovalent perfluoroorganic group which optionally has an etheric oxygen atom, or a fluorine atom.

8. The electrolyte material according to claim 7 , wherein at least one type of the repeating units represented by the formula (u2) are repeating units represented by the following formula (u2-1):

9. A liquid composition comprising a dispersion medium and the electrolyte material as defined in claim 1 dispersed in the dispersion medium, wherein the dispersion medium contains an organic solvent having a hydroxy group.

10. A membrane/electrode assembly for a polymer electrolyte fuel cell, which comprises an anode having a catalyst layer containing a proton conductive polymer, a cathode having a catalyst layer containing a proton conductive polymer, and a polymer electrolyte membrane disposed between the anode and the cathode, wherein the proton conductive polymer contained in the catalyst layer of at least one of the cathode and the anode is the electrolyte material as defined in claim 1 .

11. The electrolyte material according to claim 1 , wherein the ion exchange capacity is from 1.5 to 3.8 meq/g dry resin.

12. The electrolyte material according to claim 1 , wherein TQ is at least 230° C.

13. The electrolyte material according to claim 1 , wherein TQ is at least 250° C.

Assignees

• Hommura Satoru
• Saito Susumu
• Shimohira Tetsuji
• Watakabe Atsushi
• Asahi Glass Co Ltd

Inventors

• Hommura Satoru
• Saito Susumu
• Shimohira Tetsuji
• Watakabe Atsushi

Classifications

• C08F216/1408

  Monomers containing halogen · CPC title

• H01M8/1081

  starting from solutions, dispersions or slurries exclusively of polymers · CPC title

• H01M8/1023

  having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes · CPC title

• C08F8/44

  Preparation of metal salts or ammonium salts · CPC title

• H01M8/1039

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