# US 11,898,018 B2 · Liquid composition, polymer electrolyte membrane, membrane electrode assembly and polymer electrolyte fuel cell

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- Number: US 11,898,018 B2
- Document ID: US11898018B2
- Status: Granted
- Kind: B2
- Application number: 17/332,145
- Filed: 2021-05-27
- Published: 2021-09-16
- Granted: 2024-02-13
- Earliest claimed: 2018-12-07
- Assignees: AGC Inc.
- Applicants: AGC Inc.
- Inventors: Takumi Okuyama; Takeshi Hirai; Susumu Saito; Chikaya Tamitsuji; Daisuke Jomuta
- Web page: https://patentgrep.com/patent/US11898018B2

## CPC

- C08J 5/225: {containing fluorine}
- H01B 1/122: {Ionic conductors}
- C08F 8/12: Hydrolysis
- C08F 214/262: {with fluorinated vinyl ethers}
- C08L 29/10: Homopolymers or copolymers of unsaturated ethers (C08L35/08 takes precedence)
- C09D 127/18: Homopolymers or copolymers of tetrafluoroethene
- H01M 8/1004: characterised by membrane-electrode assemblies [MEA] (H01M8/12 takes precedence)
- H01M 8/1023: having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes
- H01M 8/1039: halogenated, e.g. sulfonated polyvinylidene fluorides
- H01M 8/1051: Non-ion-conducting additives, e.g. stabilisers, SiO2 or ZrO2
- H01M 8/1067: characterised by their physical properties, e.g. porosity, ionic conductivity or thickness
- C08J 2329/10: Homopolymers or copolymers of unsaturated ethers (C08J2335/08 takes precedence)
- C08K 2003/2213: {of cerium}
- H01M 2008/1095: {Fuel cells with polymeric electrolytes}
- H01M 2300/0082: Organic polymers
- Y02E 60/50: Fuel cells
- C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29)
- H01B: CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES (selection for magnetic properties H01F1/00; waveguides H01P {; printed circuits H05K})
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## 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 cm3·cm/(s·cm2·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.

## Claims

### Claim 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 RF1 and RF2 are each independently a C1-3 perfluoroalkylene group.

### Claim 2 (depends on 1)

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.

### Claim 3 (depends on 1)

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.

### Claim 4 (depends on 1)

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 cm3·cm/(s·cm2·cmHg).

### Claim 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 RF1 and RF2 are each independently a C1-3 perfluoroalkylene group.

### Claim 6 (depends on 5)

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.

### Claim 7 (depends on 5)

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.

### Claim 8 (depends on 5)

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 cm3·cm/(s·cm2·cmHg).

### Claim 9 (depends on 5)

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.

### Claim 10 (depends on 9)

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

### Claim 11 (depends on 1)

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 cm3·cm/(s·cm2·cmHg) and at most 2.5×10−9 cm3·cm/(s·cm2·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.

### Claim 12 (depends on 1)

The liquid composition according to claim 1, wherein RF1 and RF2 are each a C1 perfluoroalkylene group.

### Claim 13 (depends on 11)

The liquid composition according to claim 11, wherein RF1 and RF2 are each a C1 perfluoroalkylene group.

### Claim 14 (depends on 5)

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 cm3·cm/(s·cm2·cmHg) and at most 2.5×10−9 cm3·cm/(s·cm2·cmHg); and
the acid-type sulfonic acid group-containing fluorocarbon polymer further comprises tetrafluroethylene units.

### Claim 15 (depends on 5)

The polymer electrolyte membrane according to claim 5, wherein RF1 and RF2 are each a C1 perfluoroalkylene group.

### Claim 16 (depends on 14)

The polymer electrolyte membrane according to claim 14, wherein RF1 and RF2 are each a C1 perfluoroalkylene group.

### Claim 17 (depends on 14)

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.

### Claim 18 (depends on 17)

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