초록

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.

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What is claimed is: 1. A method of producing a composite solid polymer electrolyte membrane (SPEM) comprising a porous polymer substrate interpenetrated with an ion-conducting material, said method comprising the steps of preparing a common solution of the substrate polymer and the ion-conducting m

What is claimed is: 1. A method of producing a composite solid polymer electrolyte membrane (SPEM) comprising a porous polymer substrate interpenetrated with an ion-conducting material, said method comprising the steps of preparing a common solution of the substrate polymer and the ion-conducting material and thereafter casting or extruding the composite SPEM from the solution, and wherein (i) the porous substrate polymer comprises a homopolymer or copolymer of a liquid crystalline 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. 2. The method of claim 1, wherein the SPEM is substantially thermally stable to temperatures of at least about 100째 C. 3. The method of claim 1, wherein the SPEM is substantially thermally stable from at least about 100째 C. to at least about 175째 C. 4. The method of claim 1, wherein the liquid crystalline substrate polymer comprises a lyotropic liquid crystalline polymer. 5. The method of claim 4, wherein the lyotropic liquid crystalline substrate polymer comprises at least one of a polybenzazole (PBZ) and polyaramid (PAR) polymer. 6. The method of claim 5, wherein the polybenzazole substrate polymer 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. 7. The method of claim 1, wherein the ion-conducting aromatic polymer comprises a wholly aromatic ion-conducting polymer. 8. The method of claim 1, wherein the ion-conducting aromatic polymer comprises a sulfonated, phosphonated or carboxylated polyimide polymer. 9. The method of claim 8, wherein the polyimide polymer is fluorinated. 10. The method of claim 7, wherein the 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. 11. The method of claim 10, 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. 12. The method of claim 1, wherein the perfluorinated ionomer comprises a homopolymer or copolymer of a perfluorovinyl ether sulfonic acid. 13. The method of claim 12, wherein the perfluorovinyl ether sulfonic acid is carboxylic-(COOH), phosphonic-(PO(OH)2) or sulfonic-(SO3H) substituted. 14. The method of claim 1, wherein the ion-conducting material comprises at least one of a polystyrene sulfonic acid (PSSA), poly(trifluorostyrene) sulfonic acid, polyvinyl phosphonic acid (PVPA), polyacrylic acid and polyvinyl sulfonic acid (PVSA) polymer. 15. The method of claim 1, 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. 16. The method of claim 15, wherein the polysulfone polymer comprises at least one of a polyethersulfone (PBS) and polyphenylsulfone (PPSU) polymer. 17. The method of claim 15, further comprising cross-linking the ion-conducting material to form sulfone crosslinkages. 18. The method of claim 1, further comprising chlorinating or brominating the ion-conducting material. 19. The method of claim 1, further comprising adding antioxidants to the ion-conducting material. 20. The method of claim 1, further comprising purifying the ion-conducting material. 21. The method of claim 20, wherein purifying the ion-conducting material comprises dissolving the ion-conducting material in a suitable solvent and precipitating the ion-conducting material into a suitable non-solvent. 22. The method of claim 20, wherein purifying the ion-conducting material comprises substantially removing overly sulfonated or degraded fractions of the ion-conducting material. 23. The method of claim 1, wherein the common solution of the substrate polymer and ion-conducting material is prepared in a common solvent. 24. The method of claim 23, wherein the common solvent is selected from the group consisting of tetrahydrofuran (THF), dimethylacetamide (DMAc), dimethylformamide (DMF), dimethylsulfoxide (DMSO), N-Methyl-2-pyrrolidinone (NMP), sulfuric acid, phosphoric acid, chlorosulfonic acid, polyphosphoric acid (PPA) and methanesulfonic acid (MSA). 25. A method of producing a composite solid polymer electrolyte membrane (SPEM) comprising a porous polymer substrate interpenetrated with an ion-conducting material, said method comprising the steps of preparing a common solution of the substrate polymer and the ion-conducting material in a common solvent and thereafter casting or extruding the composite SPEM from the common solution, wherein the porous polymer substrate comprises a homopolymer or copolymer of a liquid crystalline polymer and wherein the SPEM is substantially thermally stable to temperatures of at least about 100째 C. 26. A method of producing a composite solid polymer electrolyte membrane (SPEM) comprising a porous polymer substrate interpenetrated with an ion-conducting material, said method comprising the steps of preparing a common solution of the substrate polymer and the ion-conducting material and thereafter extruding or casting a composite film directly from the common solution, wherein the porous polymer substrate comprises a homopolymer or copolymer of a liquid crystalline polymer and wherein the SPEM is substantially thermally stable to temperatures of at least about 100째 C. 27. A method as in any of claims 25-26, wherein the SPEM is stable from at least about 100째 C. to about 175째 C. 28. A method as in any of claims 25-26, wherein the SPEM is stable from at least about 100째 C. to about 150째 C.