Polymer electrolyte membrane for fuel cell and fuel cell system including the same

• US 20070122676A1
• Filed: 11/29/2006
• Published: 05/31/2007
• Est. Priority Date: 11/29/2005
• Status: Active Grant

• Current Assignee: Samsung SDI Company Limited
• Original Assignee: Samsung SDI Company Limited
• Inventors: Song, Min-Kyu
• Granted Patent: US 8,652,706 B2
• Time in Patent Office: Days
• US Class Current: 429/483
• CPC Class Codes: B01D 2325/14 Membrane materials having negatively charged functional groups
• CPC Class Codes: B01D 71/82 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
• CPC Class Codes: C08J 2327/18 Homopolymers or copolymers of tetrafluoroethylene
• CPC Class Codes: C08J 5/2275 Heterogeneous membranes
• CPC Class Codes: C08J 5/2281 fluorine containing heterogeneous membranes
• CPC Class Codes: H01M 8/0289 Means for holding the electrolyte solid polymer electrolytes H01M8/1018
• CPC Class Codes: H01M 8/10 Fuel cells with solid electrolytes
• CPC Class Codes: H01M 8/1023 having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes
• 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 8/1039 halogenated, e.g. sulfonated polyvinylidene fluorides
• CPC Class Codes: H01M 8/1044 Mixtures of polymers, of which at least one is ionically conductive
• 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: 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 includes a polymer matrix comprising a cross-linked curable oligomer with nano-sized proton conductive polymer particles in the polymer matrix. The curable oligomer may include unsaturated functional groups at each end of a chain, and may further include 3 to 14 ethylene oxides. The proton conductive polymer nano particles may include fluorine-based proton conductive polymer nano particles, non-fluorine-based proton conductive polymer nano particles, hydrocarbon-based proton conductive polymer nano particles, and combinations.

Claims

1. A polymer electrolyte membrane for a fuel cell comprising a polymer matrix comprising a cross-linked curable oligomer with nano-sized proton conductive polymer particles in the polymer matrix.

2. The polymer electrolyte membrane of claim 1, wherein the curable oligomer has unsaturated functional groups at each end of a chain.

3. The polymer electrolyte membrane of claim 2, wherein the curable oligomer has 3 to 14 ethylene oxides in the following Chemical Formula 1:

CR₁R₂═

CR₃COO(CH₂CH₂O)_pCOCH═

CR₁R₂ 

 

Chemical Formula 1

where each of R₁, R₂, and R₃ is independently selected from hydrogen and alkyl chains with from 1 to 12 carbons, and p is an integer from 3 to 14.

4. The polymer electrolyte membrane of claim 1, wherein the curable oligomer is provided in an amount from 10 to 90 wt % based on the total weight of the polymer electrolyte membrane.

5. The polymer electrolyte membrane of claim 4, wherein the curable oligomer is provided in an amount from 20 to 80 wt % based on the total weight of the polymer electrolyte membrane.

6. The polymer electrolyte membrane of claim 5, wherein the curable oligomer is provided in an amount from 30 to 70 wt % based on the total weight of the polymer electrolyte membrane.

7. The polymer electrolyte membrane of claim 1, wherein the proton conductive polymer particles comprise a polymer selected from the group consisting of fluorine-based proton conductive polymer nano particles, non-fluorine-based proton conductive polymer nano particles, hydrocarbon-based proton conductive polymer nano particles, and combinations thereof.

8. The polymer electrolyte membrane of claim 7, wherein the proton conductive polymer particles comprise fluorine-based proton conductive polymers with a cation exchange group at a side chain selected from the group consisting of a sulfonic acid group, a carboxylic acid group, a phosphoric acid group, a phosphonic acid group, and a derivative thereof.

9. The polymer electrolyte membrane of claim 7, wherein the proton conductive polymer particles comprise fluorine-based proton conductive polymer with an ion-exchange ratio from 3 to 33, and an equivalent weight from 500 to 2000.

10. The polymer electrolyte membrane of claim 1, wherein the proton conductive polymer is provided in an amount from 10 to 90 wt % based on the total weight of the polymer electrolyte membrane.

11. The polymer electrolyte membrane of claim 10, wherein the proton conductive polymer is provided in an amount from 20 to 80 wt % based on the total weight of the polymer electrolyte membrane.

12. The polymer electrolyte membrane of claim 11, wherein the proton conductive polymer is provided in an amount from 30 to 70 wt % based on the total weight of the polymer electrolyte membrane.

13. The polymer electrolyte membrane of claim 1, wherein the proton conductive polymer comprises a sulfonized bi- or tri-block copolymer comprising a hydrophilic monomer and a hydrophobic monomer.

14. The polymer electrolyte membrane of claim 1, wherein the polymer electrolyte membrane further comprises an additive.

15. The polymer electrolyte membrane of claim 14, wherein the additive comprises a hydrophilic inorganic ion conductor.

16. The polymer electrolyte membrane of claim 15, wherein the hydrophilic inorganic ion conductor comprises a material 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 where each of a1, a2, a, b1, b2, b4, b5, and b is independently an integer from 0 to 14 and n is an integer from 0 to 50, v-Zr(PO_a1,H_a2PO_a3)_a(HO_b1PC_b2H_b3SO_b4H)_b.nH₂O where each of a1, a2, a3, a, b1, b2, b3, b4, and b is independently an integer from 0 to 14 and n is an integer from 0 to 50, Zr(O_a1PC_a2H_a3)_aY_b where each of a1, a2, a3, a, and b is independently an integer from 0 to 14, Zr(O_a1PCH_a2OH)_aY_b.nH₂O wherein each of a1, a2, a, and b is independently an integer from 0 to 14 and n is an integer from 0 to 50, α

-Zr(O_a1PC_a2H_a3SO_a4H)_a.nH₂O where each of a1, a2, a3, a4, and a is independently an integer from 0 to 14 and n is an integer from 0 to 50, α

-Zr(O_a1POH).H₂O where a1 is an integer from 0 to 14, (P₂O₅)_a(ZrO₂)_b glass where each of a and b is independently an integer from 0 to 14, P₂O₅—

ZrO₂—

SiO₂ glass, and combinations thereof.

17. A fuel cell system comprising an electricity generating element, a fuel supplier adapted to supply the electricity generating element with a fuel, and an oxidant supplier adapted to supply the electricity generating element with an oxidant, wherein the electricity generating element comprises a membrane-electrode assembly and a pair of separators on opposite sides of the membrane-electrode assembly, the membrane-electrode assembly comprises a polymer electrolyte membrane and an anode and a cathode on opposite sides of the polymer electrolyte membrane, and the polymer electrolyte membrane comprises:

a polymer matrix including a cross-linked curable oligomer, and

a plurality of nano-sized proton conductive polymer particles in the polymer matrix.

18. The fuel cell system of claim 17, wherein the curable oligomer has unsaturated functional groups at both ends of a chain.

19. The fuel cell system of claim 18, wherein the curable oligomer has 3 to 14 ethylene oxides and is represented by Chemical Formula 1:

CR₁R₂═

CR₃COO(CH₂CH₂O)pCOCH═

CR₁R₂ 

 

Chemical Formula 1

where each of R₁, R₂, and R₃ is independently selected from a hydrogen atom, and an alkyl chain having from 1 to 12 carbon atoms, and p is an integer from 3 to 14.

20. The fuel cell system of claim 19, wherein the curable oligomer is provided in an amount from 10 to 90 wt % based on the total weight of the polymer electrolyte membrane.

21. The fuel cell system of claim 20, wherein the curable oligomer is provided in an amount from 20 to 80 wt % based on the total weight of the polymer electrolyte membrane.

22. The fuel cell system of claim 21, wherein the curable oligomer is provided in an amount from 30 to 70 wt % based on the total weight of the polymer electrolyte membrane.

23. The fuel cell system of claim 19, wherein the proton conductive polymer comprises a polymer selected from the group consisting of a fluorine-based proton conductive polymer, a non-fluorine-based proton conductive polymer, a hydrocarbon-based proton conductive polymer, and combinations thereof.

24. The fuel cell system of claim 23, wherein the proton conductive polymer comprises a fluorine-based proton conductive polymer including a cation exchange group at a side chain selected from the group consisting of a sulfonic acid group, a carboxylic acid group, a phosphoric acid group, a phosphonic acid group, and a derivative thereof.

25. The fuel cell system of claim 24, wherein the fluorine-based proton conductive polymer has an ion-exchange ratio from 3 to 33 and an equivalent weight from 500 to 2000.

26. The fuel cell system of claim 17, wherein the proton conductive polymer is provided in an amount from 10 to 90 wt % based on the entire weight of the polymer electrolyte membrane.

27. The fuel cell system of claim 26, wherein the proton conductive polymer is provided in an amount from 20 to 80 wt % based on the entire weight of the polymer electrolyte membrane.

28. The fuel cell system of claim 27, wherein the proton conductive polymer is provided in an amount from 30 to 70 wt % based on the entire weight of the polymer electrolyte membrane.

29. The fuel cell system of claim 17, wherein the proton conductive polymer comprises a sulfonized bi- or tri-block copolymer comprising a hydrophilic monomer and a hydrophobic monomer.

30. The fuel cell system of claim 17, wherein the polymer electrolyte membrane further comprises an additive.

31. The fuel cell system of claim 30, wherein the additive comprises a hydrophilic inorganic ion conductor.

32. The fuel cell system of claim 31, wherein the inorganic ion conductor comprises a material 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 where each of a1, a2, a, b1, b2, b4, b5, and b is independently an integer from 0 to 14 and n is an integer from 0 to 50, v-Zr(PO_a1,H_a2PO_a3)_a(HO_b1PC_b2H_b3SO_b4H)_b.nH₂O where each of a1, a2, a3, a, b1, b2, b3, b4, and b is independently an integer from 0 to 14 and n is an integer from 0 to 50, Zr(O_a1PC_a2H_a3)_aY_b where each of a1, a2, a3, a, and b is independently an integer from 0 to 14, Zr(O_a1PCH_a2OH)_aY_b.nH₂O wherein each of a1, a2, a, and b is independently an integer from 0 to 14 and n is an integer from 0 to 50, α

-Zr(O_a1PC_a2H_a3SO_a4H)_a.nH₂O where each of a1, a2, a3, a4, and a is independently an integer from 0 to 14 and n is an integer from 0 to 50, α

-Zr(O_a1POH).H₂O where a1 is an integer from 0 to 14, (P₂O₅)_a(ZrO₂)_b glass where each of a and b is independently an integer from 0 to 14, P₂O₅—

ZrO₂—

SiO₂ glass, and combinations thereof.