Composite solid polymer elecrolyte membranes

• US 20020045085A1
• Filed: 12/28/2000
• Published: 04/18/2002
• Est. Priority Date: 08/29/1997
• Status: Active Grant

• Current Assignee: Foster-Miller Incorporated (Thermo Fisher Scientific Incorporated)
• Original Assignee: Foster-Miller Incorporated (Thermo Fisher Scientific Incorporated)
• Inventors: Osenar, Paul, Formato, Richard M., Landrau, Nelson, Kovar, Robert F., Rubin, Leslie S.
• Granted Patent: US 7,052,793 B2
• Time in Patent Office: Days
• US Class Current: 429/33
• CPC Class Codes: B01D 2323/30 Cross-linking
• CPC Class Codes: B01D 61/44 Ion-selective electrodialysis
• CPC Class Codes: B01D 67/0088 Physical treatment with compounds, e.g. swelling, coating or impregnation
• CPC Class Codes: B01D 67/0093 Chemical modification
• CPC Class Codes: B01D 69/141 Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
• CPC Class Codes: B01D 69/1411 containing dispersed material in a continuous matrix
• CPC Class Codes: B01D 71/32 containing fluorine atoms
• CPC Class Codes: B01D 71/52 Polyethers
• CPC Class Codes: B01D 71/5222 Polyetherketone, polyetheretherketone, or polyaryletherketone
• CPC Class Codes: B01D 71/5223 Polyphenylene oxide, phenyl ether polymers or polyphenylethers
• CPC Class Codes: B01D 71/56 Polyamides, e.g. polyester-amides
• CPC Class Codes: B01D 71/62 Polycondensates having nitrogen-containing heterocyclic rings in the main chain
• CPC Class Codes: B01D 71/64 Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
• CPC Class Codes: B01D 71/643 Polyether-imides
• CPC Class Codes: B01D 71/66 Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
• 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: C08J 2379/06 Polyhydrazides; Polytriazoles; Polyamino-triazoles; Polyoxadiazoles
• CPC Class Codes: C08J 2381/06 Polysulfones; Polyethersulfones
• CPC Class Codes: C08J 5/2275 Heterogeneous membranes
• CPC Class Codes: H01M 8/0289 : Means for holding the electrolyte solid polymer electrolytes H01M8/1018
• CPC Class Codes: H01M 8/1007 : with both reactants being gaseous or vaporised H01M8/12 takes precedence
• CPC Class Codes: H01M 8/1009 : with one of the reactants being liquid, solid or liquid-charged H01M8/12 takes precedence
• CPC Class Codes: H01M 8/1023 : having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes
• 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 8/1039 : 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 8/106 : characterised by the chemical composition of the porous support
• CPC Class Codes: H01M 8/1062 : characterised by the physical properties of the porous support, e.g. its porosity or thickness
• 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 60/10 : Energy storage using batteries
• 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

The present invention relates to composite solid polymer electrolyte membranes (SPEMs) which include a porous polymer substrate interpenetrated with an ion-conducting material. SPEMs of the present invention are useful in electrochemical applications, including fuel cells and electrodialysis.

Claims

1. A composite solid polymer electrolyte membrane (SPEM) comprising a porous polymer substrate interpenetrated with an ion-conducting material, wherein the SPEM is substantially thermally stable to temperatures of at least about 100°

C.

2. The SPEM of claim 1, wherein the SPEM is stable from at least about 100°

C. to at least about 175°

C.

3. The SPEM of claim 1, wherein the SPEM is stable from at least about 100°

C. to at least about 150°

C.

4. The SPEM of claim 1, wherein the SPEM is stable from at least about 120°

C. to at least about 175°

C.

5. The SPEM of claim 1 wherein

(i) the porous polymer substrate comprises a homopolymer or copolymer of a liquid crystalline polymer or a solvent soluble thermoset or thermoplastic aromatic polymer, and

(ii) the ion-conducting material comprises a homopolymer or copolymer of at least one of a sulfonated, phosphonated or carboxylated ion-conducting aromatic polymer or a perfluorinated ionomer.

7. The SPEM of claims 1 or 6, wherein the porous polymer substrate comprises a microinfrastructure substantially interpenetrated with the ion-conducting material.

8. The SPEM of claims 1 or 6, wherein the porous polymer substrate comprises an extruded or cast film.

9. The SPEM of claim 5, wherein the SPEM substantially stable to temperatures of at least about 100°

C.

10. The SPEM of claims 5 or 6, wherein the liquid crystalline polymer substrate comprises a lyotropic liquid crystalline polymer.

11. The SPEM of claim 10, wherein the lyotropic liquid crystalline polymer substrate comprises at least one of a polybenzazole (PBZ) and polyaramid (PAR) polymer.

12. The SPEM of claim 11, wherein the polybenzazole polymer substrate comprises a homopolymer or copolymer of at least one of a polybenzoxazole (PBO), polybenzothiazole (PBT) and polybenzimidazole (PBI) polymer and the polyaramid polymer comprises a homopolymer or copolymer of a polypara-phenylene terephthalamide (PPTA) polymer.

13. The SPEM of claims 5 or 6, wherein the thermoset or thermoplastic aromatic polymer substrate comprises at least one of a polysulfone (PSU), polyimide (PI), polyphenylene oxide (PPO), polyphenylene sulfoxide (PPSO), polyphenylene sulfide (PPS), polyphenylene sulfide sulfone (PPS/SO₂), polyparaphenylene (PPP), polyphenylquinoxaline (PPQ), polyarylketone (PK) and polyetherketone (PEK) polymer.

14. The SPEM of claim 13, wherein the polysulfone polymer substrate comprises at least one of a polyethersulfone (PES), polyetherethersulfone (PEES), polyarylethersulfone (PAS), polyphenylsulfone (PPSU) and polyphenylenesulfone (PPSO₂) polymer;

the polyimide (PI) polymer comprises a polyetherimide (PEI) polymer;

the polyetherketone (PEK) polymer comprises at least one of a polyetherketone (PEK), polyetheretherketone (PEEK), polyetherketone-ketone (PEKK), polyetheretherketone-ketone (PEEKK) and polyetherketoneetherketone-ketone (PEKEKK) polymer; and

the polyphenylene oxide (PPO) polymer comprises a 2,6-diphenyl PPO or 2,6 dimethyl PPO polymer.

15. The SPEM of claims 1 or 6, wherein the pore size of the porous polymer substrate is from about 10 Å

to about 20,000 Å

.

16. The SPEM of claim 15, wherein the pore size is from about 10 Å

to about 2,000 Å

.

17. The SPEM of claim 15, wherein the pore size is from about 500 Å

to about 10,000 Å

.

18. The SPEM of claims 1 or 6, wherein the ion-conducting material has an ion-conductivity from about 0.01 S/cm to about 0.50 S/cm.

19. The SPEM of claim 18, wherein the ion-conducting material has an ion-conductivity greater than about 0.1 S/cm.

20. The SPEM of claims 5 or 6, wherein the ion-conducting aromatic polymer comprises wholly aromatic ion-conducting polymer.

21. The SPEM of claims 5 or 6, wherein the ion-conducting aromatic polymer comprises a sulfonated, phosphonated or carboxylated polyimide polymer.

22. The SPEM of claim 21, wherein the polyimide polymer is fluorinated.

23. The SPEM of claim 20, wherein the sulfonated wholly-aromatic ion-conducting polymer comprises a sulfonated derivative of at least one of a polysulfone (PSU), polyphenylene oxide (PPO), polyphenylene sulfoxide (PPSO), polyphenylene sulfide (PPS), polyphenylene sulfide sulfone (PPS/SO₂), polyparaphenylene (PPP), polyphenylquinoxaline (PPQ), polyarylketone (PK), polyetherketone (PEK), polybenzazole (PBZ) and polyaramid (PAR) polymer.

24. The SPEM of claim 23, wherein

(i) the polysulfone polymer comprises at least one of a polyethersulfone (PES), polyetherethersulfone (PEES), polyarylsulfone, polyarylethersulfone (PAS), polyphenylsulfone (PPSU) and polyphenylenesulfone (PPSO₂) polymer,

(ii) the polybenzazole (PBZ) polymer comprises a polybenzoxaxole (PBO) polymer;

(iii) the polyetherketone (PEK) polymer comprises at least one of a polyetherketone (PEK), polyetheretherketone (PEEK), polyetherketone-ketone (PEKK), polyetheretherketone-ketone (PEEKK) and polyetherketoneetherketone-ketone (PEKEKK) polymer; and

(iv) the polyphenylene oxide (PPO) polymer comprises at least one of a 2,6-diphenyl PPO, 2,6-dimethyl PPO and 1,4-poly phenylene oxide polymer.

25. The SPEM of claims 5 or 6, wherein the perfluorinated ionomer comprises a homopolymer or copolymer of a perfluorovinyl ether sulfonic acid.

26. The SPEM of claim 25, wherein the perfluorovinyl ether sulfonic acid is carboxylic-(COOH), phosphonic-(PO(OH)₂) or sulfonic-(SO₃H) substituted.

27. The SPEM of claim 1, wherein the ion-conducting material comprises at least one of a polystyrene sulfonic acid (PSSA), poly(triluorostyrene) sulfonic acid, polyvinyl phosphonic acid (PVPA), polyacrylic acid and polyvinyl sulfonic acid (PVSA) polymer.

28. The SPEM of claims 1 or 6, wherein the porous polymer substrate comprises a homopolymer or copolymer of at least one of a substituted or unsubstituted polybenzazole polymer, and wherein the ion-conducting material comprises a sulfonated derivative of a homopolymer or copolymer of at least one of a polysulfone (PSU), polyphenylene sulfoxide (PPSO) and polyphenylene sulfide sulfone (PPS/SO₂) polymer.

29. The SPEM of claim 28, wherein the polysulfone polymer comprises at least one of a polyethersulfone (PES) and polyphenylsulfone (PPSU) polymer.

30. The SPEM of claims 1 or 6, wherein the SPEM has a specific resistance from about 0.02 to about 20 Ω

*cm².

31. The SPEM of claims 1 or 6, wherein the SPEM has a specific resistance of less than about 0.2 Ω

*cm².

32. The SPEM of claims 1 or 6, wherein the SPEM has a thickness from about 0.1 mil. to about 5.0 mil.

33. The SPEM of claim 32, wherein the thickness is about 1 mil.

34. A method of producing a composite solid polymer electrolyte membrane (SPEM) in accordance with claims 1 or 6, comprising the steps of preparing a mixture of a polymer substrate and an ion-conducting material in a common solvent and casting or extruding a composite membrane from the mixture.

35. A method of producing a composite solid polymer electrolyte membrane (SPEM) in accordance with claims 1 or 6, comprising the steps of preparing a mixture of the polymer substrate and the ion-conducting material and extruding or casting a composite film directly from the mixture.

37. A method of producing a composite solid polymer electrolyte membrane (SPEM) in accordance with claims 1 or 6, comprising the steps of solubilizing the ion-conducting polymer and imbibing the porous polymer substrate with the ion-conducting polymer.

38. A method of producing a composite solid polymer electrolyte membrane (SPEM) in accordance with claims 1 or 6, comprising the steps of preparing the polymer substrate and subsequently impregnating the substrate with appropriate monomers which are then polymerized in-situ to form the SPEM.

39. A device comprising a composite solid polymer electrolyte membrane in accordance with claims 1 or 6.

40. The device of claim 39, wherein the device is a fuel cell.

41. The device of claim 40, wherein the fuel cell is a direct methanol fuel cell or a hydrogen fuel cell.

42. A method of decreasing methanol crossover rate in the fuel cell of claim 41 by using the SPEM of claim 1 in an electrochemical reaction in the fuel cell.

43. The device of claim 40, wherein the fuel cell is used to supply power to an electronic device.

44. The device of claim 39, wherein the device is a system for membrane-based water electrolysis or chloralkali electrolysis.

45. The device of claim 39, wherein the device is a dialysis, electrodialysis or electrolysis system.

46. The device of claim 39, wherein the device is a pervaporation or gas separation system.

47. The device of claim 39, wherein the device is a water splitting system for recovering acids and bases from waste water solutions.

48. The device of claim 39, wherein the device is an electrode separator in a battery.

49. The device of claim 41, wherein the methanol permeation rate in the direct methanol fuel cell is less than about 50 mA/cm² of equivalent current density at 0.5V.

50. The SPEM of claims 1 or 6, wherein the ion-conducting material is crosslinked.

6. A composite solid polymer electrolyte membrane (SPEM) comprising a porous polymer substrate interpenetrated with an ion-conducting material, wherein

(i) the porous polymer substrate comprises a homopolymer or copolymer of a liquid crystalline polymer or a solvent soluble thermoset or thermoplastic aromatic polymer, and

(ii) the ion-conducting material comprises a homopolymer or copolymer of at least one of a sulfonated, phosphonated or carboxylated ion-conducting aromatic polymer or a perfluorinated ionomer.

36. A method of producing a composite solid polymer electrolyte membrane (SPEM) comprising the steps of performing a sulfonation reaction within the pores of a polymer substrate, wherein the SPEM is substantially thermally stable to temperatures of at least about 100°

C.