SOLID ELECTROLYTE MULTILAYER MEMBRANE, METHOD AND APPARATUS FOR PRODUCING THE SAME, MEMBRANE ELECTRODE ASSEMBLY, AND FUEL CELL

• US 20090130525A1
• Filed: 07/05/2006
• Published: 05/21/2009
• Est. Priority Date: 07/07/2005
• Status: Active Grant

• Current Assignee: Fujifilm Corporation (Fujifilm Holdings Corporation)
• Original Assignee: Fujifilm Corporation (Fujifilm Holdings Corporation)
• Inventors: Miyachi, Hiroshi, Takeda, Ryo
• Granted Patent: US 8,586,266 B2
• Time in Patent Office: Days
• US Class Current: 429/490
• CPC Class Codes: B01D 2323/081 Heating
• CPC Class Codes: B01D 2323/082 Cooling
• CPC Class Codes: B01D 2325/04 Characteristic thickness
• CPC Class Codes: B01D 2325/22 Thermal or heat-resistance properties
• CPC Class Codes: B01D 2325/24 Mechanical properties, e.g. strength
• CPC Class Codes: B01D 2325/26 Electrical properties
• CPC Class Codes: B01D 67/00091 by evaporation
• CPC Class Codes: B01D 67/0011 Casting solutions therefor
• CPC Class Codes: B01D 67/0013 Casting processes
• CPC Class Codes: B01D 67/0088 Physical treatment with compounds, e.g. swelling, coating or impregnation
• CPC Class Codes: B01D 67/0095 Drying
• CPC Class Codes: B01D 69/06 Flat membranes
• CPC Class Codes: B01D 69/1216 Three or more layers
• CPC Class Codes: B01D 71/421 Polyacrylonitrile
• CPC Class Codes: B01D 71/68 Polysulfones; Polyethersulfones
• CPC Class Codes: B01D 71/82 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
• CPC Class Codes: B29C 41/28 by depositing flowable material on an endless belt
• CPC Class Codes: B29C 41/32 Making multilayered or multicoloured articles
• CPC Class Codes: B29K 2081/06 PSU, i.e. polysulfones; PES, i.e. polyethersulfones or derivatives thereof
• CPC Class Codes: C08J 2371/12 Polyphenylene oxides
• CPC Class Codes: C08J 5/2243 : obtained by introduction of active groups capable of ion-exchange into compounds of the type C08J5/2231
• CPC Class Codes: C08J 5/2256 : based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
• CPC Class Codes: H01B 1/122 : Ionic conductors
• CPC Class Codes: H01M 2300/0082 : Organic polymers
• CPC Class Codes: H01M 2300/0094 : in the form of layered products, e.g. coatings
• CPC Class Codes: H01M 8/1004 : characterised by membrane-electrode assemblies [MEA] H01M8/12 takes precedence
• CPC Class Codes: H01M 8/1032 : having sulfur, e.g. sulfonated-polyethersulfones [S-PES]
• CPC Class Codes: H01M 8/1081 : starting from solutions, dispersions or slurries exclusively of polymers
• CPC Class Codes: Y02E 60/50 : Fuel cells
• CPC Class Codes: Y02P 70/50 : Manufacturing or production processes characterised by the final manufactured product

Abstract

First, second and third dopes 114, 115 and 116 each of which contains a solid electrolyte and an organic solvent are cast from a casting die 81 provided with a feed block 119 to a moving belt 82. A three-layer casting membrane 112 is peeled off from the belt 82 as a three-layer membrane 62 containing the organic solvent. After being dried in a tenter device 64, the membrane 62 still containing the organic solvent is contacted with a liquid which is a poor solvent of the solid electrolyte and having lower boiling point than the organic solvent. Thereafter, the membrane 62 is transported to a drying chamber 69 and dried while being supported by the plural rollers.

Claims

1. A producing method for a solid electrolyte multilayer membrane comprising the steps of:

(A) forming a layered casting membrane by casting plural dopes from at least one casting die onto a moving support, each of said dopes containing a solid electrolyte and an organic solvent and having different composition;

(B) peeling said casting membrane from said support as a layered membrane containing said organic solvent;

(C) contacting at least one of said casting membrane and said membrane with a liquid which is a poor solvent of said solid electrolyte and having a lower boiling point than said organic solvent; and

(D) drying said membrane to form a solid electrolyte multilayer membrane.

2. A producing method according to claim 1, wherein said dopes are a first dope and a second dope each of which having a different combination ratio of said solid electrolyte and said organic solvent.

3. A producing method according to claim 2, wherein a second casting die for casting said second dope is disposed downstream from a first casting die for casting said first dope.

4. A producing method according to claim 1, wherein a thickness of said solid electrolyte multilayer membrane is in a range of 10 μ

m to 200 μ

m.

5. A producing method according to claim 1, wherein said organic solvent is a mixture of a first component which is a compound of a poor solvent of said solid electrolyte and a second component which is a compound of a good solvent of said solid electrolyte.

6. A producing method according to claim 5, wherein a weight ratio of said first component with respect to a sum of weights of said first component and said second component is not less than 10% and less than 100%.

7. A producing method according to claim 5, wherein said first component contains alcohol having one to five carbons, and said second component contains dimethylsulfoxide.

8. A producing method according to claim 1, wherein said solid electrolyte is a hydrocarbon polymer.

9. A producing method according to claim 8, wherein said hydrocarbon polymer is an aromatic polymer having a sulfonic acid group.

10. A producing method according to claim 9, wherein said aromatic polymer is a copolymer formed of structural units represented by general formulae (I), (II) and (III) shown in chemical formula 1.

(X is H, Y is SO₂, Z has a structure represented in (I) or (II) in a chemical formula 2, n and m satisfy 0.1≦

n/(m+n)≦

0.5)

12. A solid electrolyte multilayer membrane produced by a method described in claim 1.

13. A membrane Electrode Assembly comprising:

a solid electrolyte multilayer membrane according to claim 12;

an anode electrode being adhered to one side of said solid electrolyte multilayer membrane for generating protons from hydrogen-containing substance supplied from outside; and

a cathode electrode being adhered to the other side of said solid electrolyte multilayer membrane for synthesizing water from said protons passed through said solid electrolyte multilayer membrane and a gas supplied from said outside.

14. A fuel cell comprising:

a membrane electrode assembly according to claim 13; and

current collectors attached to said electrodes of said membrane electrode assembly for transmitting electrons between said anode electrode and outside and between said cathode electrode and said outside.

11. A producing apparatus of a solid electrolyte multilayer membrane comprising:

a casting device for casting plural dopes each of which containing a solid electrolyte and an organic solvent of different composition from each other from at least one casting die onto a moving support to form a layered casting membrane;

a peeling device for peeling said casting membrane from said support as a layered membrane containing said organic solvent;

a drying device for drying said membrane to form a solid electrolyte multilayer membrane; and

a membrane wetting section for contacting a liquid which is a poor solvent of said solid electrolyte and having a lower boiling point than said organic solvent with at least one of said casting membrane and said membrane.