Polymer membrane for a fuel cell, a method of preparing the same, and a membrane-electrode assembly fuel cell system comprising the same

• US 8,313,873 B2
• Filed: 07/14/2009
• Issued: 11/20/2012
• Est. Priority Date: 06/24/2005
• Status: Expired due to Fees

• Current Assignee: Samsung SDI Company Limited
• Original Assignee: Samsung SDI Company Limited
• Inventors: Song, Min-Kyu, Yoon, Hae-Kwon, Park, Young-Mi
• Primary Examiner(s): Ruddock, Ula C.
• Assistant Examiner(s): Parsons, Thomas H.
• Application Number:
  US12/502,898
• Publication Number:
  US 20090273123A1
• Time in Patent Office: 1,225 Days
• Field of Search: 429/491, 429/494, 264/614, 264/623, 264/634, 521/27
• US Class Current: 429/494
• CPC Class Codes: C08J 5/22 Films, membranes or diaphragms
• CPC Class Codes: C08J 5/2275 Heterogeneous membranes
• CPC Class Codes: H01M 2008/1095 Fuel cells with polymeric electrolytes
• CPC Class Codes: H01M 2300/0082 Organic polymers
• CPC Class Codes: H01M 8/1025 having only carbon and oxygen, e.g. polyethers, sulfonated polyetheretherketones [S-PEEK], sulfonated polysaccharides, sulfonated celluloses or sulfonated polyesters
• CPC Class Codes: H01M 8/1027 having carbon, oxygen and other atoms, e.g. sulfonated polyethersulfones [S-PES]
• CPC Class Codes: H01M 8/103 having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
• CPC Class Codes: H01M 8/1032 having sulfur, e.g. sulfonated-polyethersulfones [S-PES]
• CPC Class Codes: H01M 8/1048 Ion-conducting additives, e.g. ion-conducting particles, heteropolyacids, metal phosphate or polybenzimidazole with phosphoric acid
• 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

A polymer electrolyte membrane for a fuel cell, a method of preparing the same, and a fuel cell system comprising the same. The polymer electrolyte membrane includes a metal-bound inorganic ion-conductive salt and an ion-conductive cation exchange resin.

Claims

1. A method of preparing a polymer electrolyte membrane for a fuel cell, comprising:

preparing a metal-bound inorganic ion-conductive salt by reacting a metal compound and an inorganic ion conductor in a solvent;

mixing 1 to 20 parts by weight of the inorganic ion-conductive salt with an ion-conductive cation polymer resin solution to form a mixture, wherein the cation polymer resin solution contains 100 parts by weight of an ion-conductive cation polymer resin; and

casting or electrospinning the mixture to produce a polymer electrolyte membrane comprising the metal-bound inorganic ion-conductive salt.

2. The method of claim 1, wherein the inorganic ion conductor is at least one selected from the group consisting of phosphotungstic acid, silicotungstic acid, zirconium hydrogen phosphate, α

-Zr(O_a1PCH_a2OH)_a(O_b1PC_b2H_b4SO_b5H)_b.nH₂O, wherein a1, a2, a, b1, b2, b4, b5, and b are the same or different from each other and are integers of 0 to 14 , and n is an integer of 0 to 50, v-Zr(PO_a1) (H_a2PO_a3)_a(HO_b1PC_b2H_b3SO_b4H)_b.nH₂O, wherein a1, a2, a3, a, b1, b2, b3, b4, and b are the same or different from each other and are integers of 0 to 14 , and n is an integer of 0to 50, Zr(O_a1PC_a2H_a3)_aY_b, wherein a1, a2, a3, a, and b are the same or different from each other and are integers of 0 to 14 , Zr(O_a1PCH_a2OH)_aY_b.nH₂O, wherein a 1, a 2, a, and b are the same or different from each other and are integers of 0 to 14, and n is an integer of 0to 50, α

-Zr(O_a1PC_a2H_a3SO_a4H)_a.nH₂O, wherein a1, a2, a3, a4, and a are the same or different from each other and are integers of 0 to 14, and n is an integer of 0 to 50, α

-Zr(O_a1POH).H₂O, wherein a1 is an integer of 0 to 14, and combinations thereof.

3. The method of claim 1, wherein the metal compound includes a metal selected from the group consisting of Cs, Na, K, and combinations thereof.

4. The method of claim 1, wherein the solvent is selected from the group consisting of water;

an alcohol selected from the group consisting of methanol, ethanol, and propanol;

N-methyl-2-pyrrolidinone;

dimethyl formamide;

dimethyl acetamide;

tetrahydrofuran;

dimethyl sulfoxide;

acetone;

methyl ethyl ketone;

tetramethyl urea;

trimethyl phosphate;

butyrolactone;

isophorone;

carbitol acetate;

methylisobutylketone;

N-butyl acetate;

cyclohexanone;

diacetone alcohol;

diisobutyl ketone;

ethylacetoacetate;

glycol ether;

propylene carbonate;

ethylene carbonate;

dimethyl carbonate;

diethyl carbonate; and

mixtures thereof.

5. The method of claim 1, further comprising firing the inorganicion-conductive salt after reacting the metal compound and the inorganic ion conductor in the solvent.

6. The method of claim 5, wherein the firing is performed in the range of 300 to 350°

C.

7. The method of claim 1, wherein the ion-conductive cation polymer resin solution is in a concentration in the range of 0.5 to 30 wt %.

8. The method of claim 1, further comprising adding an inorganic additive to the mixture.

9. The method of claim 8, wherein the inorganic additive is selected from the group consisting of silica, clay, alumina, mica, zeolite, and combinations thereof.

10. The method of claim 8, wherein the inorganic additive is added in an amount in the range of 1 to 20 parts by weight based on 100 parts by weight of the mixture including the inorganic additive.

11. The method of claim 1, wherein the metal compound and the inorganic ion conductor are in a weight ratio of 1:

3 to 1;

6.