Proton-conductive composite electrolyte membrane and producing method thereof

• US 20060083962A1
• Filed: 10/19/2005
• Published: 04/20/2006
• Est. Priority Date: 10/20/2004
• Status: Abandoned Application

• Current Assignee: kiyoshi Kanamura, Nissan Motor Co., Ltd.
• Original Assignee: kiyoshi Kanamura, Nissan Motor Co., Ltd.
• Inventors: Kanamura, Kiyoshi, Takekawa, Toshihiro, Kanesaka, Hiroyuki
• Application Number:
  US11/252,542
• Publication Number:
  US 20060083962A1
• Time in Patent Office: Days
• US Class Current: 428/304.400
• CPC Class Codes: B01D 67/00793 Dispersing a component, e.g. as particles or powder, in another component
• CPC Class Codes: B01D 67/0088 Physical treatment with compounds, e.g. swelling, coating or impregnation
• CPC Class Codes: B01D 67/00931 by introduction of specific groups after membrane formation, e.g. by grafting
• CPC Class Codes: B01D 69/02 characterised by their properties
• CPC Class Codes: B01D 69/106 Membranes in the pores of a support, e.g. polymerized in the pores or voids
• CPC Class Codes: B01D 69/108 Inorganic support material
• CPC Class Codes: B29C 67/20 for porous or cellular articles, e.g. of foam plastics, coarse-pored chemical aspects of working up macro-molecular substances to porous or cellular articles C08J9/00
• CPC Class Codes: H01M 2300/0082 Organic polymers
• CPC Class Codes: H01M 2300/0091 in the form of mixtures
• CPC Class Codes: H01M 8/1023 having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes
• CPC Class Codes: H01M 8/106 characterised by the chemical composition of the porous support
• CPC Class Codes: H01M 8/1067 characterised by their physical properties, e.g. porosity, ionic conductivity or thickness
• 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
• CPC Class Codes: Y10T 428/249953 Composite having voids in a component [e.g., porous, cellular, etc.]

Abstract

A composite electrolyte membrane of the present invention includes a porous body composed of an inorganic substance and an electrolyte material. The porous body includes therein plural spherical pores in which a diameter is substantially equal, and communicating ports each allowing the spherical pores adjacent to each other to communicate with each other. The electrolyte material is provided on the spherical pores and the communicating ports, has proton conductivity, and is composed of a hydrocarbon polymer. The proton-conductive composite electrolyte membrane has excellent ion conductivity, high heat resistance, and restricted swelling when being hydrous, and is capable of being produced at low cost.

Claims

1. A composite electrolyte membrane, comprising:

a porous body composed of an inorganic substance, the porous body including therein plural spherical pores in which a diameter is substantially equal, and communicating ports each allowing the spherical pores adjacent to each other to communicate with each other; and

an electrolyte material provided on the spherical pores and the communicating ports, having proton conductivity, and composed of a hydrocarbon polymer.

2. The composite electrolyte membrane of claim 1,

wherein the porous body is composed of a material that forms a sol composed of the inorganic substance.

3. The composite electrolyte membrane of claim 2,

wherein the material that forms the sol is colloid composed of the inorganic substance.

4. The composite electrolyte membrane of claim 1,

wherein the porous body comprises at least one selected from the group consisting of silica, titania, zirconia, and tantalum oxide.

5. The composite electrolyte membrane of claim 1,

wherein the electrolyte material comprises a first functional group expressing the proton conductivity to an aromatic hydrocarbon polymer.

6. The composite electrolyte membrane of claim 1,

wherein the electrolyte material has an ion-exchange capacity of at least 1 to 6 meq/g.

7. The composite electrolyte membrane of claim 1,

wherein the electrolyte material comprises polyether.

8. The composite electrolyte membrane of claim 7,

wherein the electrolyte material comprises polyether ether sulfone.

9. The composite electrolyte membrane of claim 1, further comprising:

a second proton-conductive functional group formed on surfaces of the spherical pores of the porous body.

10. The composite electrolyte membrane of claim 9,

wherein a diameter of the spherical pore is within a range from 20 to 200 nm.

11. The composite electrolyte membrane of claim 10,

wherein the diameter is within a range from 50 to 150 nm.

12. The composite electrolyte membrane of claim 9,

wherein the second functional group comprises a functional group having a function as a Brø

nsted acid.

13. The composite electrolyte membrane of claim 12,

wherein the second functional group comprises at least one selected from the group consisting of a sulfonic acid group, a phosphoric acid group, and a carboxylic acid group.

14. The composite electrolyte membrane of claim 9,

wherein the second functional group is contained in a ratio of 0.2 to 2.8 mmol/g per unit weight of the porous body.

15. The composite electrolyte membrane of claim 14,

wherein the second functional group is contained in a ratio of 0.3 to 1.2 mmol/g per unit weight of the porous body.

16. The composite electrolyte membrane of claim 9,

wherein weight of the dried porous body per equivalent weight of the second functional group is within a range from 350 to 3600 g/eq.

17. The composite electrolyte membrane of claim 16,

wherein the weight of the dried porous body per equivalent weight of the second functional group is within a range from 890 to 2700 g/eq.

18. A method of producing a composite electrolyte membrane, comprising:

mixing and agitating a sol composed of an inorganic substance, a spherical organic resin and a solvent;

filtering a mixed liquid comprising the sol, the organic resin and the solvent to fabricate a membrane comprising the sol and the organic resin;

removing an extra solvent contained in the membrane;

drying the membrane from which the extra solvent is removed;

firing the dried membrane to form a porous body;

impregnating the porous body with an electrolyte material comprising a hydrocarbon polymer; and

drying the porous body impregnated with the electrolyte material.

19. The method of producing a composite electrolyte membrane of claim 18,

wherein, in the agitating, a suspension comprising the sol, the organic resin and the solvent is prepared.

20. The method of producing a composite electrolyte membrane of claim 18, further comprising:

introducing a proton-conductive functional group on surfaces of spherical pores of the porous body after the firing and before the impregnating.

21. The method of producing a composite electrolyte membrane of claim 20,

wherein the introducing comprises:

forming a mercapto group on the spherical pore surfaces; and

oxidizing the mercapto group to form a sulfonic acid group.

22. The method of producing a composite electrolyte membrane of claim 20,

wherein the introducing comprises:

reacting sultone with a hydroxyl group of the porous body.

23. The method of producing a composite electrolyte membrane of claim 20,

wherein the introducing comprises:

increasing a hydroxyl group on the spherical pore surfaces.