US20070009778A1 - Proton conducting membrane using a solid acid - Google Patents
Proton conducting membrane using a solid acid Download PDFInfo
- Publication number
- US20070009778A1 US20070009778A1 US11/516,827 US51682706A US2007009778A1 US 20070009778 A1 US20070009778 A1 US 20070009778A1 US 51682706 A US51682706 A US 51682706A US 2007009778 A1 US2007009778 A1 US 2007009778A1
- Authority
- US
- United States
- Prior art keywords
- membrane
- solid acid
- solid
- binder
- acid material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 219
- 239000011973 solid acid Substances 0.000 title claims abstract description 190
- 239000000463 material Substances 0.000 claims abstract description 95
- 239000011230 binding agent Substances 0.000 claims abstract description 42
- 229920000642 polymer Polymers 0.000 claims abstract description 39
- 239000011521 glass Substances 0.000 claims abstract description 4
- 239000000446 fuel Substances 0.000 claims description 58
- 229910019142 PO4 Inorganic materials 0.000 claims description 47
- 239000002131 composite material Substances 0.000 claims description 47
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- 239000001257 hydrogen Substances 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- MEAHOQPOZNHISZ-UHFFFAOYSA-M cesium;hydrogen sulfate Chemical compound [Cs+].OS([O-])(=O)=O MEAHOQPOZNHISZ-UHFFFAOYSA-M 0.000 claims description 21
- 229910009112 xH2O Inorganic materials 0.000 claims description 21
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 19
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 19
- 239000004020 conductor Substances 0.000 claims description 16
- 229910052909 inorganic silicate Inorganic materials 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 14
- 230000007704 transition Effects 0.000 claims description 14
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- 239000012071 phase Substances 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
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- 239000002184 metal Substances 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 229910052792 caesium Inorganic materials 0.000 claims description 8
- 229910017251 AsO4 Inorganic materials 0.000 claims description 7
- 229910003202 NH4 Inorganic materials 0.000 claims description 7
- 229910052785 arsenic Inorganic materials 0.000 claims description 7
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- 239000000919 ceramic Substances 0.000 claims description 7
- 238000011065 in-situ storage Methods 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 229910052711 selenium Inorganic materials 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 229910052712 strontium Inorganic materials 0.000 claims description 7
- 238000003487 electrochemical reaction Methods 0.000 claims description 6
- 238000007731 hot pressing Methods 0.000 claims description 6
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- 239000010703 silicon Substances 0.000 claims description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 4
- 229910018143 SeO3 Inorganic materials 0.000 claims description 4
- 239000002322 conducting polymer Substances 0.000 claims description 4
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- 150000002500 ions Chemical class 0.000 claims description 4
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- 238000010438 heat treatment Methods 0.000 claims description 3
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- NWUWMQRSDSSETA-UHFFFAOYSA-N thallane Chemical compound [TlH3] NWUWMQRSDSSETA-UHFFFAOYSA-N 0.000 claims description 3
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- 239000000155 melt Substances 0.000 claims 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims 1
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- KKYVHXQQGXVRAM-UHFFFAOYSA-N phosphoric acid selenic acid Chemical compound P(=O)(O)(O)O.[Se](=O)(=O)(O)O KKYVHXQQGXVRAM-UHFFFAOYSA-N 0.000 claims 1
- YXJYBPXSEKMEEJ-UHFFFAOYSA-N phosphoric acid;sulfuric acid Chemical compound OP(O)(O)=O.OS(O)(=O)=O YXJYBPXSEKMEEJ-UHFFFAOYSA-N 0.000 claims 1
- 229920000728 polyester Polymers 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 54
- -1 hydronium ions Chemical class 0.000 description 36
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- FLJPGEWQYJVDPF-UHFFFAOYSA-L caesium sulfate Chemical compound [Cs+].[Cs+].[O-]S([O-])(=O)=O FLJPGEWQYJVDPF-UHFFFAOYSA-L 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
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- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
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- 230000008569 process Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000010128 melt processing Methods 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
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- 239000002685 polymerization catalyst Substances 0.000 description 3
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- 229910052714 tellurium Inorganic materials 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- 229910003209 (NH4)3H(SeO4)2 Inorganic materials 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
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- 238000006731 degradation reaction Methods 0.000 description 2
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- 238000005984 hydrogenation reaction Methods 0.000 description 2
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- 229910052763 palladium Inorganic materials 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
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- 239000002904 solvent Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical class OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 2
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- 238000005979 thermal decomposition reaction Methods 0.000 description 2
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- 229910052905 tridymite Inorganic materials 0.000 description 2
- 229910019670 (NH4)H2PO4 Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 description 1
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- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
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- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
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- B01D53/32—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/122—Ionic conductors
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- H01G11/52—Separators
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- H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
- H01M6/181—Cells with non-aqueous electrolyte with solid electrolyte with polymeric electrolytes
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- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
- H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
- H01M8/0625—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material in a modular combined reactor/fuel cell structure
- H01M8/0631—Reactor construction specially adapted for combination reactor/fuel cell
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- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
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- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
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- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
- H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/10—Single element gases other than halogens
- B01D2257/108—Hydrogen
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D2325/26—Electrical properties
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
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- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0405—Purification by membrane separation
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- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/047—Composition of the impurity the impurity being carbon monoxide
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
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- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present application describes a proton conducting membrane formed using an solid acid in its solid phase. More specifically, the present application teaches a proton conducting membrane, formed using an solid acid mixed with a supporting binder material, that is impermeable to fluids such as gas and is water, can operate without hydration, and has high proton Ha conductivity.
- Proton conducting materials have a number of applications.
- Proton conducting membranes are widely utilized in devices which use a chemical reaction to produce or store electricity, or use electricity to drive a chemical process.
- Materials which conduct both protons and electrons (“mixed proton and electron conductors”) are utilized in related applications.
- Electrochemical devices depend on the flow of protons, or the flow of both protons and electrons through a proton conducting membrane.
- Exemplary electrochemical devices include a fuel cell, an electrolysis cell, a hydrogen separation cell, a battery, a supercapacitor, and a membrane reactor. There are other electrochemical devices which also use a proton conducting membrane.
- Fuel cells are attractive alternatives to combustion engines for the generation of electricity because of their higher efficiency and the lower level of pollutants they produce.
- a fuel cell generates electricity from the electrochemical reaction of a fuel e.g. methane, methanol, gasoline, or hydrogen, with oxygen normally obtained from air.
- a direct hydrogen/air fuel cell system stores hydrogen and then delivers it to the fuel cell as needed.
- hydrogen is generated on site from a hydrocarbon fuel, cleaned it of carbon monoxide (CO), and subsequently fed to the fuel cell.
- CO carbon monoxide
- DMFC direct methanol fuel cell
- NafionTM a perfluorinated sulphonic acid polymer
- Other hydrated polymers have also been used as proton conductive materials.
- Membranes of modified perfluorinated sulfonic acid polymers, polyhydrocarbon sulfonic acid polymers, and composites thereof are also known. These and related polymers are used in hydrated form. Proton transport occurs by the motion of hydronium ions, H 3 O + . Water is necessary in order to facilitate proton conduction. Loss of water immediately results in degradation of the conductivity. Moreover, this degradation is irreversible—a simple reintroduction of water to the system does not restore the conductivity. Thus, the electrolyte membranes of these hydrated polymer-based fuel cells must be kept humidified during operation. This introduces a host of balance-of-plant needs for water recirculation and temperature control.
- a second limitation derives from the need to maintain water in the membrane.
- the temperature of operation cannot exceed 100° C. without cell pressurization.
- High temperature operation could be desirable, however, to increase catalyst efficiency in generating protons at the anode (in both H 2 and direct methanol fuel cells) and to improve catalyst tolerance to carbon monoxide (“CO”).
- CO is often present in the fuel that is used in the fuel cells. The CO can poison the precious metal catalysts. This is particularly problematic in indirect hydrogen/air fuel cells for which hydrogen is generated on site. High temperatures also benefit the reduction reaction on the cathode.
- Alternate proton conducting materials which do not require humidification, which can be operated at slightly elevated temperatures, and/or which are impermeable to methanol, are desirable for fuel cell applications.
- a proton conducting membrane is utilized to separate hydrogen from other gases such as CO and/or CO 2 .
- Palladium is often used for this application. Palladium is permeable to molecular hydrogen, but not in general to other gases. There are drawbacks to the use of this material. It is expensive and the hydrogen diffusion rate is low. It would be desirable to develop new materials which are less expensive and exhibit higher proton/hydrogen transport rates.
- materials utilized in other electrochemical devices such as electrolysis cells, batteries, supercapacitors, etc.
- liquid acid electrolytes which are highly corrosive
- solid polymer proton conductors which require humidification or exhibit insufficient proton conductivity.
- High conductivity, high chemical and thermal stability solid membranes with good mechanical properties are desirable for all of these applications.
- a proton conducting material is formed using an solid acid.
- the solid acid can be of the general form M a H b (XO t ) c or M a H b (XO t ) c .nH 2 O,
- M is one or more of the species in the group consisting of Li, Be, Na, Mg, K, Ca, Rb, Sr, Cs, Ba, Tl and NH 4 + or Cu + ;
- X is one or more of the species in the group consisting of Si, P, S, As, Se, Te, Cr and Mn;
- a, b, c, n and t are rational numbers.
- Solid acids do not rely on the presence of hydronium ions for proton transport, thus they do not require hydration for use as proton conductors.
- a preferred solid acid used according to this specification is a solid phase solid acid that exhibits a superprotonic phase, a phase in which the solid has disorder in its crystal structure and a very high proton conductivity.
- An embodiment uses a structural binder or matrix material to enhance the mechanical integrity and/or chemical stability of the membrane.
- That structural binder can be many different kinds of materials in the different embodiments.
- the structural binder can be a polymer, a ceramic, or an oxide glass.
- Another embodiment uses an electronically conducting material as a matrix. This creates a membrane which conducts both protons and electrons.
- the resulting material can be used for a proton conducting material in a device that relies on the flow of protons or the flow of both protons and electrons across a membrane, herein an “electrochemical” device e.g. a fuel cell, a hydrogen separation membrane, or a electrolysis cell.
- an “electrochemical” device e.g. a fuel cell, a hydrogen separation membrane, or a electrolysis cell.
- FIG. 1 shows an exemplary hydrogen/air fuel cell using an solid acid supported by a binder as its proton conducting membrane.
- FIG. 2 shows an exemplary direct methanol fuel cell using an solid acid supported by a binder as its proton conducting membrane
- FIG. 3 shows a hydrogen separation membrane for the removal of CO and other gases from hydrogen
- FIG. 4 shows another type of hydrogen separation membrane made of a proton conducting composite
- FIGS. 5 and 6 show a membrane reactor.
- the present application teaches using an solid acid as a proton conducting membrane.
- a solid acid can be of the general form M a H b (XO t ) c .nH 2 O,
- M is one or more of the species in the group consisting of Li, Be, Na, Mg, K, Ca, Rb, Sr, Cs, Ba, Ti and NH 4 + ;
- X is one or more of the species in the group consisting of Si, P, S, As, Se, Te, Cr and Mn;
- a, b, c, n and t are rational numbers; with t preferably being 3 or 4, and where t ⁇ 0.
- the solid acids used herein are compounds, such as CsHSO 4 , whose properties are intermediate between those of a normal acid, such as H 2 SO 4 , and a normal salt, such as Cs 2 SO 4 .
- a normal acid such as H 2 SO 4
- a normal salt such as Cs 2 SO 4
- the chemical formula of the solid acids of the type used according to the present specification can be written as a combination of the salt and the acid.
- solid acids are comprised of oxyanions, for example SO 4 , SO 3 SeO 4 , SeO 3 , SiO 4 , PO 4 or AsO 4 , etc., which are linked together via O—H . . . O hydrogen bonds.
- the structure may contain more than one type of XO 4 or XO 3 group, and may also contain more than one type of M species.
- Certain solid acids are solid materials at room temperature.
- solid acids are contemplated by this specification.
- One example of a material that can be used as the solid acid is CsHSO 4 , which is intermediate between Cs 2 SO 4 (a normal salt) and H 2 SO 4 (a normal acid).
- the solid acid can be written as 0.5 Cs 2 SO 4 *0.5 H 2 SO 4 .
- Another example, using the same salt and the same acid, is 1.5 Cs 2 SO 4 *0.5 H 2 SO 4 , to give Cs 3 H(SO 4 ) 2 .
- Cs 2 (HSO 4 )(H 2 PO 4 ) may be preferred for electrochemical devices where high conductivity is critical.
- (NH 4 ) 3 H(SO 4 ) 2 may be preferred where low cost is critical.
- CaNaHSiO 4 may be preferred where chemical stability is critical.
- Solid acids have certain characteristics that can be advantageous when used as a proton conducting membrane.
- the proton transport process does not rely on the motion of hydronium ions, thus solid acids need not be humidified and their conductivity is substantially independent of humidity.
- Another advantage is that solid acids are generally stable against thermal decomposition at elevated temperatures.
- the thermal decomposition temperature for some of the solid acids described in this specification e.g., CaNaHSiO 4 , can be as high as 350° C. Since solid acids need not be humidified, solid acid based membranes can be operated at elevated temperatures, e.g. temperatures above 100° C.
- the conductivity of solid acids may be made purely protonic, or both electronic and protonic depending on the choice of the X element in the chemical formula M a H b (XO 4 ) c .nH 2 O or M a H b (XO 3 ) c .nH 2 O. That is, by using a given amount of a variable valence element such as Cr or Mn for X, the solid acid can be made to conduct electrons as well as protons.
- a variable valence element such as Cr or Mn for X
- solid acids are dense, inorganic materials, they are impermeable to gases and other fluids that may be present in the electrochemical environment, e.g., gases and hydrocarbon liquids.
- the materials are also relatively inexpensive.
- Solid acids exhibit another advantageous property for applications in proton conducting membranes. Under certain conditions of temperature and pressure, the crystal structure of a solid acid can become disordered. Concomitant with this disorder is an high conductivity, as high as 10 ⁇ 3 to 10 ⁇ 2 ⁇ ⁇ 1 cm ⁇ 1 . Because of the high proton conductivity of the structurally disordered state, it is known as a superprotonic phase. The proton transport is believed to be facilitated by rapid XO 4 or am XO 3 group reorientations, which occur because of the disorder.
- Solid acids that undergo a superprotonic transition include:
- the superprotonic phases of solid acids have increased conductivity.
- An interesting embodiment is a solid acid operated at a temperature above the superprotonic transition temperature, and below the decomposition or melt temperature.
- solid acids are water soluble. They can also be difficult to process into large area membranes, and they often have poor mechanical properties. Some solid acids, such as CaNaHSiO 4 and other silicates, are not soluble in water.
- a disclosed embodiment includes a composite comprised of an solid acid embedded in a supporting matrix.
- the solid acid part of the composite provides the desired electrochemical activity, whereas the matrix provides mechanical support and also may increase chemical stability.
- Different materials are contemplated herein for use as the supporting matrix.
- the preferred embodiment is a composite material comprised of a solid acid embedded in a supporting matrix and operated at a slightly elevated temperature.
- the solid acid is in its superprotonic phase, exhibits high conductivity, and provides the desired electrochemical functions; the support matrix may provide mechanical support, and it may also serve to protect the solid acid from water in the environment.
- a high temperature of operation can render the solid acid into its superprotonic state.
- a high temperature of operation can also ensure that any water present in the electrochemical device will be present in the form of steam rather than liquid water, making the H 2 O less likely to attack the solid acid.
- FIG. 1 A hydrogen/air fuel cell is shown in FIG. 1 , in which the proton conducting membrane is a solid acid/matrix composite of the type described herein. Because the membrane need not be humidified, the fuel cell system can be simpler than one which uses a hydrated polymer membrane. The humidification system normally required for fuel cell utilizing a Nafion or related polymer membrane can be eliminated in FIG. 1 . Hence, less rigid temperature monitoring and control may be used in the solid acid based system as compared with Nafion based fuel cell systems. These differences allow a less-costly fuel cell system.
- the fuel cell shown in FIG. 1 can be operated at temperatures above 100° C.
- the tolerance of the Pt/Ru catalysts to carbon monoxide CO poisoning increases with increasing temperature.
- a fuel cell such as shown in FIG. 1 operated at a temperature above 100° C. may withstand higher concentrations of CO in the hydrogen fuel than a Nafion based fuel cell which is typically operated at a temperature lower than 100° C.
- the high temperature of operation also enhances the kinetics of the electrochemical reactions, and can thereby result in a fuel cell with higher overall efficiency than one based on Nafion or other hydrated polymers.
- FIG. 2 A direct methanol fuel cell is shown in FIG. 2 .
- the proton conducting membrane is a solid acid/matrix composite of the type described herein. Because the membrane need not be humidified, the fuel cell system is much simpler and thus less costly than state of the art direct methanol fuel cell systems.
- the humidification system normally required for fuel cell utilizing a Nafion or related polymer membrane is eliminated in FIG. 2 .
- temperature monitoring and control in the solid acid based system does not need to be as tight as in Nafion based fuel cell systems. Because the solid acid based membrane need not be humidified, the fuel cell may be operated at elevated temperatures. High temperatures can enhance the kinetics of the electrochemical reactions. This can result in a fuel cell with very high efficiency.
- Another significant advantage of the fuel cell shown in FIG. 2 over state of the art direct methanol fuel cells results from the decreased permeability of the membrane to methanol.
- state of the art direct methanol fuel cells in which Nafion or another hydrated polymer serves as the membrane, methanol cross-over through the polymeric membrane lowers fuel cell efficiencies.
- the impermeability of a solid acid membrane can improve this efficiency.
- the Ru/Pt catalyst in a hydrogen/air fuel cell is sensitive to CO poisoning, particularly at temperatures close to ambient. Therefore, in an indirect hydrogen/air fuel cell, the hydrogen produced by the reformer is often cleaned, of e.g. CO to below 50 ppm, before it enters the fuel cell for electrochemical reaction.
- a hydrogen separation membrane is shown for the removal of CO and other gases from hydrogen.
- the hydrogen separation membrane is made of a mixed proton and electron conducting membrane, as described herein. Hydrogen gas, mixed with other undesirable gases, is introduced onto one side of the membrane. Clean hydrogen gas is extracted from the other side of the membrane.
- H+ and e ⁇ On the inlet side of the membrane, hydrogen gas is dissociated into H+ and e ⁇ . Because the membrane is both proton conducting and electron conducting, both of these species can migrate through the membrane. However, the membrane is if substantially impermeable to other gases and fluids. Hence, CO and other undesirable gases or fluids cannot so migrate.
- the H+ and e ⁇ On the outlet side of the membrane, the H+ and e ⁇ recombine to form hydrogen gas. The overall process is driven by the hydrogen chemical potential gradient, which is high on the inlet side of the membrane and low on the outlet side of the membrane.
- FIG. 4 Another type of hydrogen separation membrane is shown in FIG. 4 .
- the membrane is made of a proton conducting composite of the type described herein, and is connected to a current source. Hydrogen gas, mixed with other undesirable gases, is introduced onto one side of the membrane and clean hydrogen gas is extracted from the other side of the membrane. Application of a current causes the hydrogen gas to dissociate into H+ and e ⁇ . Because the membrane conducts only protons, these protons are the only species which can migrate through the membrane. The electrons migrate through the current source to the outlet side of the membrane, where the H+ and e ⁇ recombine to form hydrogen gas.
- the membrane is substantially impervious to other gases and fluids. Hence, CO and other undesirable gases or fluids cannot migrate through the proton conducting membrane. The overall process is driven by electric current applied via the current source.
- FIG. 5 a membrane reactor is shown, in which a mixed proton and electron conducting membrane of the type described herein is utilized.
- the general reaction is that reactants A+B react to form products C+D, where D is hydrogen gas.
- D is hydrogen gas.
- Use of a mixed proton and electron conducting membrane in this reactor can enhance the reaction to give yields that exceed thermodynamic equilibrium values.
- the reactants form products C+H2.
- the hydrogen concentration builds up and the forward reaction is slowed.
- the hydrogen is immediately extracted from the reaction region via transport through the membrane, and the forward reaction is enhanced.
- Examples of reactions in which yield could be enhanced by using such a membrane reactor include (1) the steam reformation of methane (natural gas) to produce syngas: CH4+H2O ⁇ CO+3H2; (2) the steam reformation of CO to produce CO2 and H2: CO+H2O ⁇ CO2+H2; (3) the decomposition of H2S to H2 and S, (4) the decomposition of NH3 to H2 and N2; (4) the dehydrogenation of propane to polypropylene; and (5) the dehydrogenation of alkanes and aromatic compounds to various products.
- FIG. 6 a second type of membrane reaction is shown, again, utilizing a mixed proton and electron conducting membrane of the type described herein.
- the general reaction is that the reactants A+B form the products C+D, where B is hydrogen.
- the hydrogen enters the reaction region via transport through the mixed conducting membrane, whereas the reactant A is introduced at the inlet to the membrane reactor, and is mixed with other species.
- the manner in which the hydrogen is introduced into the reactant stream (through the membrane) ensures that only the reactant A, and none of the other species reacts with hydrogen. This effect is termed selective hydrogenation.
- the mixed proton and electron conducting membranes described herein provide an advantage over state-of-the-art membranes in that the conductivity is high at temperatures as low as 100° C., and the membranes are relatively inexpensive. Selective hydrogenation at temperatures close to ambient may have particular application in synthesis of pharmaceutically important compounds which cannot withstand high temperatures.
- the solid acid is mixed with a supporting structure that is electrochemically unreactive, to form a composite.
- a first embodiment uses a solid acid mixed with a melt-processable polymer as the supporting matrix structure.
- the solid acid (CHS) was prepared from aqueous solutions containing stoichiometric amounts of Cs 2 CO 3 and H 2 SO 4 .
- Crystalline CsHSO 4 and a small amount ( ⁇ 8 wt %) of the related compound Cs 5 H 3 (SO 4 ) 4 .xH 2 O (which also exhibits superprotonic behavior) were obtained upon introduction of methanol into the solution.
- Composite membranes of the solid acid and poly(vinylidene fluoride) were prepared by simple melt-processing methods. The two components were lightly ground together then hot-pressed at 180° C. and 10 kpsi for 15 minutes. Volume ratios of CHS:PVDF from 100% CsHSO 4 to 100% PVDF were prepared in 10 vol % increments.
- thermoset polymer Another example of a composite contains a solid acid and a thermoset polymer, which can be mixed in with the solid acid in monomer or prepolymer form, and then polymerized in situ.
- the solid acid (CHS) was prepared from aqueous solutions containing stoichiometric amounts of Cs 2 CO 3 and H 2 SO 4 .
- Crystalline CsHSO 4 and a small amount ( ⁇ 8 wt %) of the related compound Cs 5 H 3 (SO 4 ) 4 .xH 2 O (which also exhibits superprotonic behavior) were obtained upon introduction of methanol into the solution.
- Composite membranes of the solid acid and the polyester resin marketed under the name Castoglas by Buehler, Inc. were synthesized simply by lightly grinding the solid acid and pre-polymer together and then adding the polymerization/crosslinking catalyst. A material with a 50:50 volume ratio was prepared.
- thermoset polymer—solid acid composite comprises the solid acid (NH 3 ) 3 H(SO 4 ) 2 and the polymer poly(dicyclopentadiene) or poly DCPD.
- the solid acid, TAHS was prepared from aqueous solutions of (NH 4 ) 2 SO 4 and H 2 SO 4 .
- the solid acid was ground then mixed with the monomer dicyclopentadiene.
- the polymerization catalyst was introduced into the mixture, which was then poured onto a Teflon plate and pressed into a thin film. The film was cured at 100° C. for approximately 2 hours. Materials with 25 and 17 vol % TAHS were prepared.
- Another method for preparing solid acid/polymer composites is suspension coasting. For this, CsHSO 4 was dissolved in a water/ethanol solution. The polymer PVDF was then dispersed into this solution. A composite membrane was formed by casting the suspension and allowing the solvents to evaporate.
- Composite membranes comprised of a solid acid and a non-polymeric matrix material, such as a ceramic or an oxide glass can be prepared in the following manner. The solid acid is synthesized form aqueous solution and the matrix material is synthesized separately. The two components are mixed and ground together. The mixture is then hot pressed, preferably at a temperature which causes the solid acid to melt and flow, to yield a dense composite membrane.
- M is one or more of the species in the group consisting of Li, Be, Na, Mg, K, Ca, Rb, Sr, Cs, Ba, Tl and NH 4 + ;
- X is one or more of the species in the group consisting of Si, P, S, As, Se, and Te;
- a, b, c, and n are rational numbers, and n can be zero.
- the first approach for introducing electronic conductivity into solid acid based materials is to prepare a composite comprised of the solid acid and a second substance which has a high electronic conductivity.
- This second substance may be an electronically conducting polymer, such as poly(aniline), or a typical metal, such as aluminum or copper.
- the electronically conducting component is a metal
- the processing methods described above may be used to prepare such composite membranes.
- the second approach for introducing electronic conductivity into solid acid based materials is to perform direct chemical substitutions with variable valence ions.
- a portion of the sulfur in CsHSO 4 may be replaced by chromium, which can be present in an oxidation state of anywhere from 2+ to 6+.
- manganese may be introduced on the sulfur site, as this ion exhibits valence states anywhere between 2+ and 7+.
- Chemical substitution may also be performed with respect to the cesium in a compound such as CsHSO 4 . Large ions with variable valence, such as thallium, indium, lead and tin can be used for these substitutions.
- the solid acid so modified may be used in an electrochemical device directly, or may be combined with a supporting matrix material as described above.
- a membrane-electrode assembly is prepared from the CHS—PVDF composite film in which the solid acid to polymer volume ratio is 50:50.
- the electrodes are formed of graphite paper which is impregnated with a complex slurry of platinum powder, PVDF, the solid acid, and Nafion, suspended/dissolved in a water and isopropanol solution. After evaporation of the solvents, the electrodes so prepared are hot-pressed onto the composite membrane.
- the MEA is placed in a fuel cell test station at 140° C. and hydrogen is introduced at the anode and oxygen at the cathode.
- the open cell voltage (OCV) obtained in this manner was 0.88 V.
- the same type of MEA may also be used in the FIG. 2 embodiment.
- a Cs based solid acid such as CsHSO 4 , CsHSeO 4 or Cs 5 H 3 (SO 4 ) 4 .xH 2 O is ground and mixed with a melt-processable polymer binder, such as poly(vinylidene fluoride), and hot-pressed.
- a melt-processable polymer binder such as poly(vinylidene fluoride)
- the result forms a solid composite membrane which is proton conducting even in dry atmospheres.
- the composite membrane being comprised of two components whicha re substantially impermeable to fluids, may be less permeable than NafionTM.
- a Cs based solid acid such as Cs 3 (HSO 4 ) 2 (H 1.5 (S 0.5 P 0.5 )O 4 ), Cs 3 (HSO 4 ) 2 (H 2 P 4 ), Cs 5 (HSO 4 ) 3 (H 2 PO 4 ) 2 or Cs 2 (HSO 4 )(H 2 PO 4 ) is ground and mixed with a melt-processable polymer binder, such as poly(vinylidene fluoride), and hot-pressed.
- a melt-processable polymer binder such as poly(vinylidene fluoride
- a NH 4 based solid acid such as (NH 4 ) 3 H (SO 4 ) 2 or (NH 4 ) 3 H(SeO 4 ) 2 is ground and mixed with a melt-processable polymer binder, such as Crystar 101 thermoplastic, and hot-pressed.
- a melt-processable polymer binder such as Crystar 101 thermoplastic
- An solid acid silicate of general formula M a H b SiO 4 such as CaNaHSiO 4 , Cs 3 HSiO 4 , (NH 4 ) 3 HSiO 4 , is used as a membrane. Some of these materials are water insoluble and may have sufficient structural integrity that a binder is not required in some applications.
- a Cs or NH 4 based solid acid such as CsHSO 4 , Cs 2 (HSO 4 )(H 2 PO 4 ), Cs 5 H 3 (SO 4 ) 4 .xH 2 O or (NH 4 ) 3 H(SO 4 ) 2 is mixed with the prepolymer of a resin such as “castoglas”, a commercial product from Buehler, Inc.
- the polymerization/crosslinking catalyst is added to the mixture, and a solid composite membrane so formed.
- the in situ polymerization/crosslinking can lead to a higher impermeability than composites formed by melt-processing.
- a Cs or NH 4 based solid acid such as CsHSO 4 , Cs 2 (HSO 4 )(H 2 PO 4 ), Cs 5 H 3 (SO 4 ) 4 .xH 2 O or (NH 4 ) 3 H(SO 4 ) 2 is mixed with a monomer such as dicyclopentadiene.
- a polymerization catalyst is then added to the mixture, and a solid composite membrane comprised of the solid acid and poly(dicyclopentadiene) is formed.
- the in situ polymerization of the polymer can lead to a higher impermeability than composites formed by melt-processing.
- Use of a NH 4 based solid acid can result in an inexpensive membrane.
- a Cs or NH 4 based solid acid such as CsHSO 4 , Cs 2 (HSO 4 )(H 2 PO 4 ), Cs 5 H 3 (SO 4 ) 4 xH 2 O or (NH 4 ) 3 H(SO 4 ) 2 is dissolved in water, and added to a suspension of an insoluble polymer such as poly(vinylidene fluoride) suspended in a fluid such as ethanol. The mixture is cast and the liquids (water and ethanol) allowed to evaporate. This procedure yields a composite membrane which is proton conducting even in dry atmospheres. The casting step can produce very thin membranes, with thicknesses on the order of one hundred microns.
- a Cs or NH 4 based solid acid such as CsHSO 4 , Cs 2 (HSO 4 )(H 2 PO 4 ), Cs 5 H 3 (SO 4 ) 4 .xH2O or (NH 4 ) 3 H (SO 4 ) 2 is ground and mixed with a ceramic, such as Al 2 O 3 , or an oxide glass, such as amorphous SiO 2 .
- the mixed powders are compressed by hot-pressing.
- the resulting composite membrane may be stable to higher temperatures than those in which the binder is a polymer.
- a Cs or NH 4 based solid acid such as CsHSO 4 , Cs 2 (HSO 4 )(H 2 PO 4 ), Cs 5 H 3 (SO 4 ) 4 .xH 2 O or (NH 4 ) 3 H(SO 4 ) 2 is dissolved in water.
- the solution is introduced into a porous membrane comprised of an inert binder such as TeflonTM, SiO 2 , or Al 2 O 3 .
- the water is allowed to evaporate, leaving the solid acid to fill the pores of the binder.
- the result is a composite membrane which is proton conducting even in dry atmospheres.
- a Cs or NH 4 based solid acid such as CsHSO 4 , Cs 2 (HSO 4 )(H 2 PO 4 ), Cs 5 H 3 (SO 4 ) 4 .xH 2 O or (NH 4 ) 3 H(SO 4 ) 2 , which is only proton conducting, is ground and mixed with an electronically conducting polymer such as poly(anylene).
- the composite membrane formed can conduct both protons and electrons.
- An solid acid silicate of general formula M a H b SiO 4 such as CaNaHSiO 4 , Cs 3 HSiO 4 or (NH 4 ) 3 HSiO 4 , is ground and mixed with an electronically conducting polymer such as poly(anilene).
- the composite membrane formed can conduct both protons and electrons.
- a proton conducting solid acid such as CsHSO 4 , Cs 2 (HSO 4 )(H 2 PO 4 ), (NH 4 ) 3 H(SO 4 ) 2 or CaNaHSiO 4 , and a metal, such as Ag, Au, or Cu, are ground and mixed.
- the mixed powders are compressed by hot-pressing.
- the composite membrane formed can conduct both protons and electrons, and may be stable to higher temperatures than a composite in which the electron conducting component is a polymer.
- a proton conducting solid acid such as CsHSO 4 , Cs 2 (HSO 4 )(H 2 PO 4 ), (NH 4 ) 3 H(SO 4 ) 2 or CaNaHSiO 4 , and a metal, such as Ag, Au, or Cu, are ground and mixed.
- a polymeric material is also added.
- a solid composite membrane is prepared either by hot-pressing, if the polymer is melt-processable such as poly(vinylidene fluoride), or by in situ polymerization, if the polymer is in situ polymerizable such as poly(dicyclopentadiene).
- the composite membrane is both proton and electron conducting, and may have superior mechanical properties to a composite containing only a solid acid and a metal.
- a mixed electron and proton conducting solid acid such as CsHCr x S 1-x O 4 or (NH 4 ) 3 H(Cr x S 1-x O 4 ) 2 in which one of the X elements has a variable valence, is mixed with an inert polymeric binder.
- the polymer is melt-processable, such as poly(vinylidene fluoride)
- a membrane is formed by hot-pressing.
- the polymer can be polymerized in situ, a membrane is formed by mixing the solid acid, the monomer and the polymerization catalyst. The resulting membrane conducts both protons and electrons, and may be more stable in oxidizing atmospheres than a composite containing metal particles.
- a Cs or NH 4 based solid acid such as CsHSO 4 , Cs 2 (HSO 4 )(H 2 PO 4 ), Cs 5 H 3 (SO 4 ) 4 .xH 2 O or (NH 4 ) 3 H(SO 4 ) 2 is prepared from aqueous solution, ground, and then pressed into a thin membrane.
- the membrane is used in an electrochemical device at a temperature above the superprotonic transition temperature and above 100° C., so that the proton conductivity of the solid acid is high and any H 2 O that may be present in the device exists in the form of steam rather than liquid water.
- a mixed electron and proton conducting solid acid such as CsHCr x S 1-x O 4 or (NH 4 ) 3 H (Cr x S 1-x O 4 ) 2 in which one of the X elements has a variable valence, is prepared from aqueous solution or by solid state reaction. The powder is then ground and pressed into a thin membrane. The membrane is used in an electrochemical device at a temperature above the superprotonic transition temperature and above 100° C., so that the conductivity of the solid acid is high and any H 2 O that may be present in the device exists in the form of steam rather than liquid water.
- a composite comprised of one or more of the solid acids listed in Table 1 and one or more of inert binders listed in Table 2. If one or more of the components in the composite is electronically conducting, the composite membrane will be capable of conducting both protons and electrons. Electronically conducting substances are indicated. TABLE 1 Solid acid compounds. Sulfates and selenates and sulfate-phosphates selenate phosphates silicates CsHSO 4 CsHSeO 4 CaNaHSiO 4 Cs 3 H(SO 4 ) 2 Cs 3 H(SeO 4 ) 2 CaH 2 SiO 4 Cs 5 H 3 (SO 4 ) 4 . x H 2 O Cs 5 H 3 (SeO 4 ) 4 .
- x H 2 O Rb 5 H 3 (SeO 4 ) 4 .
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Abstract
A solid acid material is used as a proton conducting membrane in an electrochemical device. The solid acid material can be one of a plurality of different kinds of materials. A binder can be added, and that binder can be either a nonconducting or a conducting binder. Nonconducting binders can be, for example, a polymer or a glass. A conducting binder enables the device to be both proton conducting and electron conducting.
Description
- This application is a divisional application of and claims priority to U.S. application Ser. No. 09/439,377, filed Nov. 15, 1999, which claims the benefit of U.S. provisional applications Ser. No. 60/116,741, filed Jan. 22, 1999, Ser. No. 60/146,946, filed Aug. 2, 1999, Ser. No. 60/146,943 filed Aug. 2, 1999, and Ser. No. 60/151,811, filed Aug. 30, 1999.
- The invention described herein was made in the performance of work under a NASA contract and is subject to the provisions of Public Law 96-517 (U.C.C. 202) in which the Contractor has elected to retain title.
- The present application describes a proton conducting membrane formed using an solid acid in its solid phase. More specifically, the present application teaches a proton conducting membrane, formed using an solid acid mixed with a supporting binder material, that is impermeable to fluids such as gas and is water, can operate without hydration, and has high proton Ha conductivity.
- Proton conducting materials have a number of applications. Proton conducting membranes are widely utilized in devices which use a chemical reaction to produce or store electricity, or use electricity to drive a chemical process. Materials which conduct both protons and electrons (“mixed proton and electron conductors”) are utilized in related applications.
- Electrochemical devices depend on the flow of protons, or the flow of both protons and electrons through a proton conducting membrane. Exemplary electrochemical devices include a fuel cell, an electrolysis cell, a hydrogen separation cell, a battery, a supercapacitor, and a membrane reactor. There are other electrochemical devices which also use a proton conducting membrane.
- An important use for proton conducting membranes is in fuel cells. Fuel cells are attractive alternatives to combustion engines for the generation of electricity because of their higher efficiency and the lower level of pollutants they produce. A fuel cell generates electricity from the electrochemical reaction of a fuel e.g. methane, methanol, gasoline, or hydrogen, with oxygen normally obtained from air.
- There are three common types of fuel cells used at temperatures close to ambient. A direct hydrogen/air fuel cell system stores hydrogen and then delivers it to the fuel cell as needed.
- In an indirect hydrogen/air fuel cell, hydrogen is generated on site from a hydrocarbon fuel, cleaned it of carbon monoxide (CO), and subsequently fed to the fuel cell.
- A direct methanol fuel cell (“DMFC”), feeds methanol/water solution directly to the fuel cell, e.g., without any fuel processing. One type of DMFC has been described, for example, in U.S. Pat. No. 5,559,638. There are various advantages and disadvantages inherent within all three configurations. All are, to a greater or lesser extent, limited by the performance of the proton conducting membrane.
- Nafion™, a perfluorinated sulphonic acid polymer, is often used as a membrane material for fuel cells which operate at temperatures close to ambient. Other hydrated polymers have also been used as proton conductive materials. Membranes of modified perfluorinated sulfonic acid polymers, polyhydrocarbon sulfonic acid polymers, and composites thereof are also known. These and related polymers are used in hydrated form. Proton transport occurs by the motion of hydronium ions, H3O+. Water is necessary in order to facilitate proton conduction. Loss of water immediately results in degradation of the conductivity. Moreover, this degradation is irreversible—a simple reintroduction of water to the system does not restore the conductivity. Thus, the electrolyte membranes of these hydrated polymer-based fuel cells must be kept humidified during operation. This introduces a host of balance-of-plant needs for water recirculation and temperature control.
- A second limitation derives from the need to maintain water in the membrane. In order to maintain hydration, the temperature of operation cannot exceed 100° C. without cell pressurization. High temperature operation could be desirable, however, to increase catalyst efficiency in generating protons at the anode (in both H2 and direct methanol fuel cells) and to improve catalyst tolerance to carbon monoxide (“CO”). CO is often present in the fuel that is used in the fuel cells. The CO can poison the precious metal catalysts. This is particularly problematic in indirect hydrogen/air fuel cells for which hydrogen is generated on site. High temperatures also benefit the reduction reaction on the cathode.
- Another limitation of hydrated polymer electrolytes occurs in applications in methanol fuel cells. These polymers can be permeable to methanol. Direct transport of the fuel (i.e. methanol) across the membrane to the air cathode results in losses in efficiency.
- Alternate proton conducting materials, which do not require humidification, which can be operated at slightly elevated temperatures, and/or which are impermeable to methanol, are desirable for fuel cell applications.
- In the field of hydrogen separation, a proton conducting membrane is utilized to separate hydrogen from other gases such as CO and/or CO2. Palladium is often used for this application. Palladium is permeable to molecular hydrogen, but not in general to other gases. There are drawbacks to the use of this material. It is expensive and the hydrogen diffusion rate is low. It would be desirable to develop new materials which are less expensive and exhibit higher proton/hydrogen transport rates.
- In general, materials utilized in other electrochemical devices such as electrolysis cells, batteries, supercapacitors, etc., include liquid acid electrolytes, which are highly corrosive, and solid polymer proton conductors, which require humidification or exhibit insufficient proton conductivity. High conductivity, high chemical and thermal stability solid membranes with good mechanical properties are desirable for all of these applications.
- The present specification defines a new kind of material for a proton conducting membrane. Specifically, a proton conducting material is formed using an solid acid. The solid acid can be of the general form MaHb(XOt)c or MaHb(XOt)c.nH2O,
- where:
- M is one or more of the species in the group consisting of Li, Be, Na, Mg, K, Ca, Rb, Sr, Cs, Ba, Tl and NH4 + or Cu+;
- X is one or more of the species in the group consisting of Si, P, S, As, Se, Te, Cr and Mn; and
- a, b, c, n and t are rational numbers.
- Solid acids do not rely on the presence of hydronium ions for proton transport, thus they do not require hydration for use as proton conductors.
- A preferred solid acid used according to this specification is a solid phase solid acid that exhibits a superprotonic phase, a phase in which the solid has disorder in its crystal structure and a very high proton conductivity.
- An embodiment uses a structural binder or matrix material to enhance the mechanical integrity and/or chemical stability of the membrane. That structural binder can be many different kinds of materials in the different embodiments. In particular, the structural binder can be a polymer, a ceramic, or an oxide glass.
- Another embodiment uses an electronically conducting material as a matrix. This creates a membrane which conducts both protons and electrons.
- The resulting material can be used for a proton conducting material in a device that relies on the flow of protons or the flow of both protons and electrons across a membrane, herein an “electrochemical” device e.g. a fuel cell, a hydrogen separation membrane, or a electrolysis cell.
-
FIG. 1 shows an exemplary hydrogen/air fuel cell using an solid acid supported by a binder as its proton conducting membrane. -
FIG. 2 shows an exemplary direct methanol fuel cell using an solid acid supported by a binder as its proton conducting membrane -
FIG. 3 shows a hydrogen separation membrane for the removal of CO and other gases from hydrogen; -
FIG. 4 shows another type of hydrogen separation membrane made of a proton conducting composite; and -
FIGS. 5 and 6 show a membrane reactor. - The present application teaches using an solid acid as a proton conducting membrane.
- A solid acid can be of the general form MaHb(XOt)c.nH2O,
- where:
- M is one or more of the species in the group consisting of Li, Be, Na, Mg, K, Ca, Rb, Sr, Cs, Ba, Ti and NH4 +;
- X is one or more of the species in the group consisting of Si, P, S, As, Se, Te, Cr and Mn; and
- a, b, c, n and t are rational numbers; with t preferably being 3 or 4, and where t≧0.
- The solid acids used herein are compounds, such as CsHSO4, whose properties are intermediate between those of a normal acid, such as H2SO4, and a normal salt, such as Cs2SO4. In general, the chemical formula of the solid acids of the type used according to the present specification can be written as a combination of the salt and the acid.
- In general, solid acids are comprised of oxyanions, for example SO4, SO3 SeO4, SeO3, SiO4, PO4 or AsO4, etc., which are linked together via O—H . . . O hydrogen bonds. The structure may contain more than one type of XO4 or XO3 group, and may also contain more than one type of M species.
- Certain solid acids are solid materials at room temperature.
- Many different solid acids are contemplated by this specification. One example of a material that can be used as the solid acid is CsHSO4, which is intermediate between Cs2SO4 (a normal salt) and H2SO4 (a normal acid). In this case, the solid acid can be written as 0.5 Cs2SO4*0.5 H2SO4. Another example, using the same salt and the same acid, is 1.5 Cs2SO4*0.5 H2SO4, to give Cs3H(SO4)2.
- Other examples are:
- CsH2PO4, Cs5(HSO4)3(H2PO4)2, Cs2(HSO4)(H2PO4), Cs3(HSO4)2(H2PO4), Cs3(HSO4)2(H1.5(S0.5P0.5)O4), Cs5H3(SO4)4.xH2O, TlHSO4, CsHSeO4, Cs2(HSeO4)(H2PO4), Cs3H(SeO4)2(NH4)3H(SO4)2, (NH4)2(HSO4)(H2PO4), Rb3H(SO4)2, Rb3H(SeO4)2, Cs1.5Li1.5H(SO4)2, Cs2Na(HSO4)3, TlH3(SeO3)2, CsH2AsO4(NH4)2(HSO4)(H2AsO4), CaNaHSiO4
- The preferred material for any specific electrochemical device depends on the application. For example, Cs2(HSO4)(H2PO4) may be preferred for electrochemical devices where high conductivity is critical. (NH4)3H(SO4)2 may be preferred where low cost is critical. CaNaHSiO4 may be preferred where chemical stability is critical.
- Solid acids have certain characteristics that can be advantageous when used as a proton conducting membrane. The proton transport process does not rely on the motion of hydronium ions, thus solid acids need not be humidified and their conductivity is substantially independent of humidity. Another advantage is that solid acids are generally stable against thermal decomposition at elevated temperatures. The thermal decomposition temperature for some of the solid acids described in this specification, e.g., CaNaHSiO4, can be as high as 350° C. Since solid acids need not be humidified, solid acid based membranes can be operated at elevated temperatures, e.g. temperatures above 100° C.
- The conductivity of solid acids may be made purely protonic, or both electronic and protonic depending on the choice of the X element in the chemical formula MaHb(XO4)c.nH2O or MaHb(XO3)c.nH2O. That is, by using a given amount of a variable valence element such as Cr or Mn for X, the solid acid can be made to conduct electrons as well as protons.
- Another advantage is caused by the structure of the solid acids themselves. Since solid acids are dense, inorganic materials, they are impermeable to gases and other fluids that may be present in the electrochemical environment, e.g., gases and hydrocarbon liquids.
- The materials are also relatively inexpensive.
- This combination of properties: good conductivity in dry environments, conductivity which can be controlled to be either purely proton conducting or both electron and-proton conducting, impermeability to gases and hydrocarbon liquids, serviceability at elevated temperatures, e.g. temperatures over 100° C. and relatively low cost, render solid acids as useful materials for use as membranes in electrochemical devices.
- Solid acids exhibit another advantageous property for applications in proton conducting membranes. Under certain conditions of temperature and pressure, the crystal structure of a solid acid can become disordered. Concomitant with this disorder is an high conductivity, as high as 10−3 to 10−2 Ω−1cm−1. Because of the high proton conductivity of the structurally disordered state, it is known as a superprotonic phase. The proton transport is believed to be facilitated by rapid XO4 or am XO3 group reorientations, which occur because of the disorder.
- Many solid acids enter a superprotonic state at a temperature between 50 and 150° C. at ambient pressures. The transition into the superprotonic phase may be either sharp or gradual. The superprotonic phase is marked by an increase in conductivity, often by several orders of magnitude. At temperatures above the transition temperature, the solid acid is superprotonic and retains its high proton conductivity until the decomposition or melting temperature is reached.
- Solid acids that undergo a superprotonic transition include:
- CsHSO4, Cs2(HSO4)(H2PO4), Cs3(HSO4)2(H2PO4), Cs3(HSO4)2(H1.5(S0.5P0.5)O4), Cs5H3(SO4)4.xH2O, CsHSeO4, Cs3H(SeO4)2, (NH4)3H(SO4)2, Rb3H(SeO4)2.
- The superprotonic phases of solid acids have increased conductivity. An interesting embodiment is a solid acid operated at a temperature above the superprotonic transition temperature, and below the decomposition or melt temperature.
- Despite the many advantageous properties of solid acids, problems can be encountered in trying to implement them in electrochemical devices because many solid acids are water soluble. They can also be difficult to process into large area membranes, and they often have poor mechanical properties. Some solid acids, such as CaNaHSiO4 and other silicates, are not soluble in water.
- Because of these difficulties, a disclosed embodiment includes a composite comprised of an solid acid embedded in a supporting matrix. The solid acid part of the composite provides the desired electrochemical activity, whereas the matrix provides mechanical support and also may increase chemical stability. Different materials are contemplated herein for use as the supporting matrix.
- In light of the properties of solid acids outlined above, the preferred embodiment is a composite material comprised of a solid acid embedded in a supporting matrix and operated at a slightly elevated temperature. In such a composite, the solid acid is in its superprotonic phase, exhibits high conductivity, and provides the desired electrochemical functions; the support matrix may provide mechanical support, and it may also serve to protect the solid acid from water in the environment. A high temperature of operation can render the solid acid into its superprotonic state. A high temperature of operation can also ensure that any water present in the electrochemical device will be present in the form of steam rather than liquid water, making the H2O less likely to attack the solid acid.
- Hydrogen/Air Fuel Cells
- A hydrogen/air fuel cell is shown in
FIG. 1 , in which the proton conducting membrane is a solid acid/matrix composite of the type described herein. Because the membrane need not be humidified, the fuel cell system can be simpler than one which uses a hydrated polymer membrane. The humidification system normally required for fuel cell utilizing a Nafion or related polymer membrane can be eliminated inFIG. 1 . Hence, less rigid temperature monitoring and control may be used in the solid acid based system as compared with Nafion based fuel cell systems. These differences allow a less-costly fuel cell system. - Because the membrane need not be humidified, the fuel cell shown in
FIG. 1 can be operated at temperatures above 100° C. The tolerance of the Pt/Ru catalysts to carbon monoxide CO poisoning increases with increasing temperature. Thus, a fuel cell such as shown inFIG. 1 , operated at a temperature above 100° C. may withstand higher concentrations of CO in the hydrogen fuel than a Nafion based fuel cell which is typically operated at a temperature lower than 100° C. - The high temperature of operation also enhances the kinetics of the electrochemical reactions, and can thereby result in a fuel cell with higher overall efficiency than one based on Nafion or other hydrated polymers.
- Direct Methanol Fuel Cells
- A direct methanol fuel cell is shown in
FIG. 2 . The proton conducting membrane is a solid acid/matrix composite of the type described herein. Because the membrane need not be humidified, the fuel cell system is much simpler and thus less costly than state of the art direct methanol fuel cell systems. The humidification system.normally required for fuel cell utilizing a Nafion or related polymer membrane is eliminated inFIG. 2 . Furthermore, temperature monitoring and control in the solid acid based system does not need to be as tight as in Nafion based fuel cell systems. Because the solid acid based membrane need not be humidified, the fuel cell may be operated at elevated temperatures. High temperatures can enhance the kinetics of the electrochemical reactions. This can result in a fuel cell with very high efficiency. - Another significant advantage of the fuel cell shown in
FIG. 2 over state of the art direct methanol fuel cells results from the decreased permeability of the membrane to methanol. In state of the art direct methanol fuel cells, in which Nafion or another hydrated polymer serves as the membrane, methanol cross-over through the polymeric membrane lowers fuel cell efficiencies. The impermeability of a solid acid membrane can improve this efficiency. - Hydrogen Separation Membranes
- The Ru/Pt catalyst in a hydrogen/air fuel cell is sensitive to CO poisoning, particularly at temperatures close to ambient. Therefore, in an indirect hydrogen/air fuel cell, the hydrogen produced by the reformer is often cleaned, of e.g. CO to below 50 ppm, before it enters the fuel cell for electrochemical reaction.
- In
FIG. 3 , a hydrogen separation membrane is shown for the removal of CO and other gases from hydrogen. The hydrogen separation membrane is made of a mixed proton and electron conducting membrane, as described herein. Hydrogen gas, mixed with other undesirable gases, is introduced onto one side of the membrane. Clean hydrogen gas is extracted from the other side of the membrane. - On the inlet side of the membrane, hydrogen gas is dissociated into H+ and e−. Because the membrane is both proton conducting and electron conducting, both of these species can migrate through the membrane. However, the membrane is if substantially impermeable to other gases and fluids. Hence, CO and other undesirable gases or fluids cannot so migrate. On the outlet side of the membrane, the H+ and e− recombine to form hydrogen gas. The overall process is driven by the hydrogen chemical potential gradient, which is high on the inlet side of the membrane and low on the outlet side of the membrane.
- Another type of hydrogen separation membrane is shown in
FIG. 4 . The membrane is made of a proton conducting composite of the type described herein, and is connected to a current source. Hydrogen gas, mixed with other undesirable gases, is introduced onto one side of the membrane and clean hydrogen gas is extracted from the other side of the membrane. Application of a current causes the hydrogen gas to dissociate into H+ and e− . Because the membrane conducts only protons, these protons are the only species which can migrate through the membrane. The electrons migrate through the current source to the outlet side of the membrane, where the H+ and e− recombine to form hydrogen gas. The membrane is substantially impervious to other gases and fluids. Hence, CO and other undesirable gases or fluids cannot migrate through the proton conducting membrane. The overall process is driven by electric current applied via the current source. - Membrane Reactors
- In
FIG. 5 a membrane reactor is shown, in which a mixed proton and electron conducting membrane of the type described herein is utilized. The general reaction is that reactants A+B react to form products C+D, where D is hydrogen gas. Use of a mixed proton and electron conducting membrane in this reactor can enhance the reaction to give yields that exceed thermodynamic equilibrium values. On the inlet side of the membrane reactor, the reactants form products C+H2. Under equilibrium conditions, the hydrogen concentration builds up and the forward reaction is slowed. With the use of the mixed hydrogen and electron conducting membrane, the hydrogen is immediately extracted from the reaction region via transport through the membrane, and the forward reaction is enhanced. Examples of reactions in which yield could be enhanced by using such a membrane reactor include (1) the steam reformation of methane (natural gas) to produce syngas: CH4+H2O→CO+3H2; (2) the steam reformation of CO to produce CO2 and H2: CO+H2O→CO2+H2; (3) the decomposition of H2S to H2 and S, (4) the decomposition of NH3 to H2 and N2; (4) the dehydrogenation of propane to polypropylene; and (5) the dehydrogenation of alkanes and aromatic compounds to various products. - In
FIG. 6 a second type of membrane reaction is shown, again, utilizing a mixed proton and electron conducting membrane of the type described herein. In this case, the general reaction is that the reactants A+B form the products C+D, where B is hydrogen. The hydrogen enters the reaction region via transport through the mixed conducting membrane, whereas the reactant A is introduced at the inlet to the membrane reactor, and is mixed with other species. The manner in which the hydrogen is introduced into the reactant stream (through the membrane) ensures that only the reactant A, and none of the other species reacts with hydrogen. This effect is termed selective hydrogenation. - The mixed proton and electron conducting membranes described herein provide an advantage over state-of-the-art membranes in that the conductivity is high at temperatures as low as 100° C., and the membranes are relatively inexpensive. Selective hydrogenation at temperatures close to ambient may have particular application in synthesis of pharmaceutically important compounds which cannot withstand high temperatures.
- According to a first class of materials, the solid acid is mixed with a supporting structure that is electrochemically unreactive, to form a composite. A first embodiment uses a solid acid mixed with a melt-processable polymer as the supporting matrix structure.
- The solid acid (CHS) was prepared from aqueous solutions containing stoichiometric amounts of Cs2CO3 and H2SO4. Crystalline CsHSO4 and a small amount (˜8 wt %) of the related compound Cs5H3(SO4)4.xH2O (which also exhibits superprotonic behavior) were obtained upon introduction of methanol into the solution. Composite membranes of the solid acid and poly(vinylidene fluoride) were prepared by simple melt-processing methods. The two components were lightly ground together then hot-pressed at 180° C. and 10 kpsi for 15 minutes. Volume ratios of CHS:PVDF from 100% CsHSO4 to 100% PVDF were prepared in 10 vol % increments.
- Another example of a composite contains a solid acid and a thermoset polymer, which can be mixed in with the solid acid in monomer or prepolymer form, and then polymerized in situ.
- The solid acid (CHS) was prepared from aqueous solutions containing stoichiometric amounts of Cs2CO3 and H2SO4. Crystalline CsHSO4 and a small amount (˜8 wt %) of the related compound Cs5H3(SO4)4.xH2O (which also exhibits superprotonic behavior) were obtained upon introduction of methanol into the solution. Composite membranes of the solid acid and the polyester resin marketed under the name Castoglas by Buehler, Inc. were synthesized simply by lightly grinding the solid acid and pre-polymer together and then adding the polymerization/crosslinking catalyst. A material with a 50:50 volume ratio was prepared.
- Another example of a thermoset polymer—solid acid composite comprises the solid acid (NH3)3H(SO4)2 and the polymer poly(dicyclopentadiene) or poly DCPD.
- The solid acid, TAHS, was prepared from aqueous solutions of (NH4)2SO4 and H2SO4. The solid acid was ground then mixed with the monomer dicyclopentadiene. The polymerization catalyst was introduced into the mixture, which was then poured onto a Teflon plate and pressed into a thin film. The film was cured at 100° C. for approximately 2 hours. Materials with 25 and 17 vol % TAHS were prepared.
- Another method for preparing solid acid/polymer composites is suspension coasting. For this, CsHSO4 was dissolved in a water/ethanol solution. The polymer PVDF was then dispersed into this solution. A composite membrane was formed by casting the suspension and allowing the solvents to evaporate. Composite membranes comprised of a solid acid and a non-polymeric matrix material, such as a ceramic or an oxide glass can be prepared in the following manner. The solid acid is synthesized form aqueous solution and the matrix material is synthesized separately. The two components are mixed and ground together. The mixture is then hot pressed, preferably at a temperature which causes the solid acid to melt and flow, to yield a dense composite membrane.
- The nature of the chemical bonding in solid acids of general formula MaHb(XO4)c.nH2O or MaHb(XO3)c.nH2O where:
- M is one or more of the species in the group consisting of Li, Be, Na, Mg, K, Ca, Rb, Sr, Cs, Ba, Tl and NH4 +;
- X is one or more of the species in the group consisting of Si, P, S, As, Se, and Te; and
- a, b, c, and n are rational numbers, and n can be zero.
- leads to materials which are inherently poor conductors of electrons. These compounds can be used in devices which require both proton and electron transport directly through the membrane if a mechanism for electron transport is introduced.
- The first approach for introducing electronic conductivity into solid acid based materials is to prepare a composite comprised of the solid acid and a second substance which has a high electronic conductivity. This second substance may be an electronically conducting polymer, such as poly(aniline), or a typical metal, such as aluminum or copper. Where the electronically conducting component is a metal, it may be advantageous to introduce a chemically and electrically inert polymer into the composite simply to serve as a binder and provide the membrane with good mechanical properties. The processing methods described above may be used to prepare such composite membranes.
- The second approach for introducing electronic conductivity into solid acid based materials is to perform direct chemical substitutions with variable valence ions. For example, a portion of the sulfur in CsHSO4 may be replaced by chromium, which can be present in an oxidation state of anywhere from 2+ to 6+. Similarly, manganese may be introduced on the sulfur site, as this ion exhibits valence states anywhere between 2+ and 7+. Chemical substitution may also be performed with respect to the cesium in a compound such as CsHSO4. Large ions with variable valence, such as thallium, indium, lead and tin can be used for these substitutions. The solid acid so modified may be used in an electrochemical device directly, or may be combined with a supporting matrix material as described above.
- In the
FIG. 1 embodiment, a membrane-electrode assembly (MEA) is prepared from the CHS—PVDF composite film in which the solid acid to polymer volume ratio is 50:50. The electrodes are formed of graphite paper which is impregnated with a complex slurry of platinum powder, PVDF, the solid acid, and Nafion, suspended/dissolved in a water and isopropanol solution. After evaporation of the solvents, the electrodes so prepared are hot-pressed onto the composite membrane. The MEA is placed in a fuel cell test station at 140° C. and hydrogen is introduced at the anode and oxygen at the cathode. The open cell voltage (OCV) obtained in this manner was 0.88 V. The same type of MEA may also be used in theFIG. 2 embodiment. - A Cs based solid acid such as CsHSO4, CsHSeO4 or Cs5H3(SO4)4.xH2O is ground and mixed with a melt-processable polymer binder, such as poly(vinylidene fluoride), and hot-pressed. The result forms a solid composite membrane which is proton conducting even in dry atmospheres. The composite membrane, being comprised of two components whicha re substantially impermeable to fluids, may be less permeable than Nafion™.
- A Cs based solid acid such as Cs3(HSO4)2(H1.5(S0.5P0.5)O4), Cs3(HSO4)2(H2P4), Cs5(HSO4)3(H2PO4)2 or Cs2(HSO4)(H2PO4) is ground and mixed with a melt-processable polymer binder, such as poly(vinylidene fluoride), and hot-pressed. The result forms a solid composite membrane which is proton conducting even in dry atmospheres. The membrane is also less permeable to fluids than Nafion™.
- A NH4 based solid acid such as (NH4)3H (SO4)2 or (NH4)3H(SeO4)2 is ground and mixed with a melt-processable polymer binder, such as Crystar 101 thermoplastic, and hot-pressed. The result forms a solid composite membrane which is proton conducting even in dry atmospheres. The membrane is less permeable to fluids than Nafion™ and is also less expensive.
- An solid acid silicate of general formula MaHbSiO4, such as CaNaHSiO4, Cs3HSiO4, (NH4)3HSiO4, is used as a membrane. Some of these materials are water insoluble and may have sufficient structural integrity that a binder is not required in some applications.
- A Cs or NH4 based solid acid, such as CsHSO4, Cs2(HSO4)(H2PO4), Cs5H3(SO4)4.xH2O or (NH4)3H(SO4)2 is mixed with the prepolymer of a resin such as “castoglas”, a commercial product from Buehler, Inc. The polymerization/crosslinking catalyst is added to the mixture, and a solid composite membrane so formed. The in situ polymerization/crosslinking can lead to a higher impermeability than composites formed by melt-processing.
- A Cs or NH4 based solid acid, such as CsHSO4, Cs2(HSO4)(H2PO4), Cs5H3(SO4)4.xH2O or (NH4)3H(SO4)2 is mixed with a monomer such as dicyclopentadiene. A polymerization catalyst is then added to the mixture, and a solid composite membrane comprised of the solid acid and poly(dicyclopentadiene) is formed. The in situ polymerization of the polymer can lead to a higher impermeability than composites formed by melt-processing. Use of a NH4 based solid acid can result in an inexpensive membrane.
- A Cs or NH4 based solid acid, such as CsHSO4, Cs2(HSO4)(H2PO4), Cs5H3(SO4)4xH2O or (NH4)3H(SO4)2 is dissolved in water, and added to a suspension of an insoluble polymer such as poly(vinylidene fluoride) suspended in a fluid such as ethanol. The mixture is cast and the liquids (water and ethanol) allowed to evaporate. This procedure yields a composite membrane which is proton conducting even in dry atmospheres. The casting step can produce very thin membranes, with thicknesses on the order of one hundred microns.
- A Cs or NH4 based solid acid, such as CsHSO4, Cs2(HSO4)(H2PO4), Cs5H3(SO4)4.xH2O or (NH4)3H (SO4)2 is ground and mixed with a ceramic, such as Al2O3, or an oxide glass, such as amorphous SiO2. The mixed powders are compressed by hot-pressing. The resulting composite membrane may be stable to higher temperatures than those in which the binder is a polymer.
- A Cs or NH4 based solid acid, such as CsHSO4, Cs2(HSO4)(H2PO4), Cs5H3(SO4)4.xH2O or (NH4)3H(SO4)2 is dissolved in water. The solution is introduced into a porous membrane comprised of an inert binder such as Teflon™, SiO2, or Al2O3. The water is allowed to evaporate, leaving the solid acid to fill the pores of the binder. The result is a composite membrane which is proton conducting even in dry atmospheres.
- A Cs or NH4 based solid acid, such as CsHSO4, Cs2(HSO4)(H2PO4), Cs5H3(SO4)4.xH2O or (NH4)3H(SO4)2, which is only proton conducting, is ground and mixed with an electronically conducting polymer such as poly(anylene). The composite membrane formed can conduct both protons and electrons.
- An solid acid silicate of general formula MaHbSiO4, such as CaNaHSiO4, Cs3HSiO4 or (NH4)3HSiO4, is ground and mixed with an electronically conducting polymer such as poly(anilene). The composite membrane formed can conduct both protons and electrons.
- A proton conducting solid acid, such as CsHSO4, Cs2(HSO4)(H2PO4), (NH4)3H(SO4)2 or CaNaHSiO4, and a metal, such as Ag, Au, or Cu, are ground and mixed. The mixed powders are compressed by hot-pressing. The composite membrane formed can conduct both protons and electrons, and may be stable to higher temperatures than a composite in which the electron conducting component is a polymer.
- A proton conducting solid acid, such as CsHSO4, Cs2(HSO4)(H2PO4), (NH4)3H(SO4)2 or CaNaHSiO4, and a metal, such as Ag, Au, or Cu, are ground and mixed. A polymeric material is also added. A solid composite membrane is prepared either by hot-pressing, if the polymer is melt-processable such as poly(vinylidene fluoride), or by in situ polymerization, if the polymer is in situ polymerizable such as poly(dicyclopentadiene). The composite membrane is both proton and electron conducting, and may have superior mechanical properties to a composite containing only a solid acid and a metal.
- A mixed electron and proton conducting solid acid, such as CsHCrxS1-xO4 or (NH4)3H(CrxS1-xO4)2 in which one of the X elements has a variable valence, is mixed with an inert polymeric binder. If the polymer is melt-processable, such as poly(vinylidene fluoride), a membrane is formed by hot-pressing. If the polymer can be polymerized in situ, a membrane is formed by mixing the solid acid, the monomer and the polymerization catalyst. The resulting membrane conducts both protons and electrons, and may be more stable in oxidizing atmospheres than a composite containing metal particles.
- A Cs or NH4 based solid acid, such as CsHSO4, Cs2(HSO4)(H2PO4), Cs5H3(SO4)4.xH2O or (NH4)3H(SO4)2 is prepared from aqueous solution, ground, and then pressed into a thin membrane. The membrane is used in an electrochemical device at a temperature above the superprotonic transition temperature and above 100° C., so that the proton conductivity of the solid acid is high and any H2O that may be present in the device exists in the form of steam rather than liquid water.
- A mixed electron and proton conducting solid acid, such as CsHCrxS1-xO4 or (NH4)3H (CrxS1-xO4)2 in which one of the X elements has a variable valence, is prepared from aqueous solution or by solid state reaction. The powder is then ground and pressed into a thin membrane. The membrane is used in an electrochemical device at a temperature above the superprotonic transition temperature and above 100° C., so that the conductivity of the solid acid is high and any H2O that may be present in the device exists in the form of steam rather than liquid water.
- A composite comprised of one or more of the solid acids listed in Table 1 and one or more of inert binders listed in Table 2. If one or more of the components in the composite is electronically conducting, the composite membrane will be capable of conducting both protons and electrons. Electronically conducting substances are indicated.
TABLE 1 Solid acid compounds. Sulfates and selenates and sulfate-phosphates selenate phosphates silicates CsHSO4 CsHSeO4 CaNaHSiO4 Cs3H(SO4)2 Cs3H(SeO4)2 CaH2SiO4 Cs5H3(SO4)4.xH2O Cs5H3(SeO4)4.xH2O CsH3SiO4 Cs3(HSO4)2(H1.5(S0.5P0.5)O4) Cs3(HSeO4)2(H1.5(Se0.5P0.5)O4) Cs2H2SiO4 Cs3(HSO4)2(H2PO4) Cs3(HSeO4)2(H2PO4) Cs3HSiO4 Cs2(HSO4) (H2PO4) Cs2(HSeO4) (H2PO4) NH4H3SiO4 Cs5(HSO4)3(H2PO4)2 Cs5(HSeO4)3(H2PO4)2 (NH4)2H2SiO4 CsH2PO4 (NH4)3HSiO4 NH4HSO4 NH4HSeO4 RbH3SiO4 (NH4)3H(SO4)2 (NH4)3H(SeO4)2 Rb2H2SiO4 (NH4)5H3(SO4)4.xH2O (NH4)5H3(SeO4)4.xH2O Rb3HSiO4 (NH4)2(HSO4) (H2PO4) (NH4)2(HSeO4) (H2PO4) KH3SiO4 (NH4)H2PO4 K2H2SiO4 RbHSO4 RbHSeO4 K3HSiO4 Rb3H(SO4)2 Rb3H(SeO4)2 NaH3SiO4 Rb5H3(SO4).xH2O Rb5H3(SeO4)4.xH2O Na2H2SiO4 Rb2(HSO4) (H2PO4) Rb2(HSeO4) (H2PO4) Na3HSiO4 RbH2PO4 BaCsHSiO4 -
TABLE 2 Binder or matrix materials ceramic/oxide metal or Polymer glass semiconductor poly(vinylidene fluoride) SiO2 Ag* poly(dicyclopentadiene) Al2O3 Au* poly(tetraflouroethelyne) MgO Cu* [Teflon] poly(ether-ether ketone) cordierite Al* po1y (ether sulfone) Ni* Silicones [dimethyl Fe* siloxane polymers] poly(pyrrole)* Zn* poly(aniline)* graphite* silicon*
*electronically conducting
- Other modifications are within the disclosed embodiment. For example, the above has described the materials having a superprotonic transition upon heating. Certain materials may have their superprotonic transition temperature below room temperature. Thus, there may be no apparent superprotonic transition and the material would be disordered at room temperature. These solid acids with structural disorder even prior to heating are also contemplated.
Claims (114)
1. A proton conducting membrane, formed of a solid acid material in a solid phase.
2. A membrane as in claim 1 wherein said solid acid material is of a type that is capable of a superprotonic transition.
3. A membrane as in claim 1 wherein said solid acid material is of the general form MaHb(XOt)c.
4. A membrane as in claim 3 wherein t is 3 or 4.
5. A membrane as in claim 1 wherein said solid acid material is of the general form CsaHb(XOt)c.
6. A membrane as in claim 3 where X is silicon.
7. A membrane as in claim 4 wherein M is Cs.
8. A membrane as in claim 4 wherein M is NH4.
9. A membrane as in claim 4 wherein said solid acid is of the form MaHb(XOt)c.nH2O.
10. A membrane as in claim 4 wherein X is P.
11. A membrane as in claim 3 , wherein said solid acid is CsH2PO4.
12. A membrane as in claim 3 , wherein said solid acid is Cs5(HSO4)3(H2PO4)2.
13. A membrane as in claim 3 , wherein said solid acid is Cs2(HSO4)x(H2PO4)y.
14. A membrane as in claim 3 , wherein said solid acid is Cs3(HSO4)2(H1.5(S0.5P0.5)O4).
15. A membrane as in claim 3 , wherein said solid acid is Cs5H3(SO4)4.xH2O.
16. A membrane as in claim 3 , wherein said solid acid is TlHSO4.
17. A membrane as in claim 3 , wherein said solid acid is CsH(SeO4)x.
18. A membrane as in claim 3 , wherein said solid acid is Cs2(HSeO4) (H2PO4).
19. A membrane as in claim 3 , wherein said solid acid is (NH4)3H(SO4)2.
20. A membrane as in claim 3 , wherein said solid acid is (NH4)2(HSO4) (H2PO4).
21. A membrane as in claim 3 , wherein said solid acid is Rb3H (SO4)2.
22. A membrane as in claim 3 , wherein said solid acid is Rb3H (SeO4)2.
23. A membrane as in claim 3 , wherein said solid acid is Cs1.5Li1.5H(SO4)2.
24. A membrane as in claim 3 , wherein said solid acid is Cs2Na (HSO4)3.
25. A membrane as in claim 3 , wherein said solid acid is TlH3(SeO3)2.
26. A membrane as in claim 3 , wherein said solid acid is CsH2AsO4.
27. A membrane as in claim 3 , wherein said solid acid is (NH4)2(HSO4) (H2AsO4).
28. A membrane as in claim 3 , wherein said solid acid is CaNaHSiO4.
29. A membrane as in claim 3 , further comprising an electrochemical device, using said membrane for proton transport.
30. A membrane as in claim 1 wherein said solid acid material is formed of a material that is not water soluble.
31. A proton conducting membrane, formed of an solid acid material in a superprotonic phase, said solid acid material being of the general formula MaHb(XOt)c, where t is 3 or 4, the M material is at least one material from the group consisting of Li, Be, Na, Mg, K, Ca, Rb, Sr, Cs, Ba, Tl or NH4 +, and the X material is at least one material from the group consisting of Si, P, S, As, Se, or Te.
32. A membrane as in claim 31 wherein said solid acid is non-water soluble.
33. A method of conducting protons across a barrier, comprising:
forming a membrane from a solid acid material; and
using said solid acid material to conduct protons.
34. A method as in claim 33 , wherein said solid acid is of a type that is capable of a superprotonic transition between a first temperature and a second temperature; and
operating said membrane as a proton conducting membrane at a temperature between said first and second temperatures.
35. A method as in claim 33 wherein said solid acid material is of the general form MaHb(XOt)c.
36. A method as in claim 35 wherein M is Cs.
37. A method as in claim 35 wherein M is NH4 +.
38. A method as in claim 35 wherein X includes silicon.
39. A method as in claim 33 wherein said protons are conducted in a fuel cell.
40. A method as in claim 33 wherein said protons are conducted in a hydrogen separator.
41. A method as in claim 33 wherein said protons are conducted in an electrolysis cell.
42. A method as in claim 33 wherein said protons are conducted in a battery.
43. A proton conducting membrane, comprising:
an solid acid material; and
a structural binder for said solid acid material, forming a membrane with said solid acid material.
44. A membrane as in claim 43 wherein said structural binder is a polymer.
45. A membrane as in claim 44 wherein said solid acid material is a type capable of a superprotonic transition at a specified temperature.
46. A membrane as in claim 43 wherein said solid acid material is a non-water soluble solid acid material.
47. A membrane as in claim 44 wherein said polymer is a melt processable polymer.
49. A membrane as in claim 44 wherein said polymer is an in-situ polymerized polymer.
50. A membrane as in claim 43 wherein said structural binder is a ceramic.
51. A membrane as in claim 43 wherein said structural binder is a glass.
52. A membrane as in claim 43 wherein said structural binder is electronically insulating.
53. A membrane as in claim 43 wherein said structural binder is electrically conducting.
54. A membrane as in claim 53 wherein said conducting material is a conducting polymer.
55. A membrane as in claim 53 wherein said conducting material is a metal.
56. A membrane as in claim 55 wherein said metal is mixed with a polymer.
57. A membrane as in claim 53 wherein said conductor is formed by direct chemical substitution with variable valence ions.
58. A membrane as in claim 43 wherein said structural binder includes silicon.
59. A membrane as in claim 43 wherein said structural binder is a polyester binder.
60. A membrane as in claim 43 wherein said structural binder is electrochemically unreactive.
61. A membrane as in claim 43 wherein said solid acid is of the of the general formula MaHb(XOt)c, where:
the M material is a material from the group consisting of Li, Be, Na, Mg, K, Ca, Rb, Sr, Cs, Ba, Te or NH4 +, and
the X material is from the group consisting of Si, P, S, As, Se, or Te.
62. A membrane as in claim 61 wherein M is Cs.
63. A membrane as in claim 61 wherein X is Si.
64. A membrane as in claim 61 where M is NH4 +.
65. A membrane as in claim 61 wherein said solid acid material is a solid acid material.
66. A membrane as in claim 61 wherein said solid acid material is water insoluble.
67. A membrane as in claim 53 wherein said solid acid material is processed to include variable valence elements.
68. A fuel cell as in claim 67 , wherein said solid-acid material is water insoluble.
69. A fuel cell as in claim 67 , wherein said solid acid material is of the general formula MaHb(XOt)c, where:
the M group is a material from the group consisting of Li, Be, Na, Mg, K, Ca, Rb, Sr, Cs, Ba, Tl or NH4 +, and
the X material is from the group consisting of Si, P, S, As, Se, or Te.
70. A method of operating an electrochemical device comprising:
providing a fuel to a proton conducting membrane; and
carrying out an electrochemical reaction at said proton conducting membrane, without humidifying said membrane.
71. A method as in claim 70 , wherein said carrying out comprises operating at a temperature of 100° degrees C. or higher.
72. A method as in claim 70 , wherein said proton conducting membrane includes an solid acid material.
73. A method as in claim 70 , wherein said proton conducting membrane includes an solid acid material in a superprotonic phase.
74. A method as in claim 72 , wherein said proton conducting membrane includes a binder.
75. A method as in claim 74 , wherein said solid acid material is of the general formula MaHb(XO4)c, where:
the M group is a material from the group consisting of Li, Be, Na, Mg, K, Ca, Rb, Sr, Cs, Ba, Tl or NH4 +, and
the X material is from the group consisting of Si, P, S, As, Se, or Te.
76. A proton and electron conducting membrane, formed of an solid acid material.
77. A membrane as in claim 76 wherein said solid acid material is of a type that is capable of a superprotonic transition at a specified temperature.
78. A membrane as in claim 76 wherein said solid acid material is of the general formula MaHb(XOt)c.
79. A membrane as in claim 76 wherein said solid acid material is a solid acid material.
80. A membrane as in claim 78 where X includes silicon.
81. A membrane as in claim 76 , further comprising a binder for the solid acid material.
82. A membrane as in claim 76 wherein said binder includes a conducting material.
83. A membrane as in claim 82 wherein said conducting material includes a conductive polymer.
84. A membrane as in claim 82 wherein said conducting material includes a metal material.
85. A membrane as in claim 76 wherein said solid acid material has free valence electrons.
86. A method of separating H2 from other materials, comprising:
chemically reacting a H2 at a surface of a proton and electron conducting membrane which is formed of materials including a solid acid material, to decompose said H into H+ and e−; and
using said membrane formed of an solid acid material to allow said H+ and e− to pass while blocking other materials including CO from passing.
87. A proton conducting membrane comprising;
a Cs based solid acid material; and
a melt processable polymer binder for said solid acid material, forming a membrane with said solid acid material.
88. A membrane as in claim 87 wherein said Cs based solid acid is one of CS3(HSO4)2(H1.5(S0.5P0.5)O4), Cs3(HSO4)2(H2PO4), Cs5(HSO4)3(H2PO4)2 or Cs2(HSO4)(H2PO4)CsHSO4, CsHSeO4 or Cs5H3(SO4)4.xH2O.
89. A membrane as in claim 87 wherein said melt processable polymer is polyvinylidine fluoride.
90. A membrane as in claim 87 wherein said membrane is formed by hot pressing.
91. A proton conducting membrane, comprising:
a NH4 based solid acid material; and
a structural binder for said solid acid material, forming a membrane with said solid acid material.
92. A membrane as in claim 91 wherein said structural binder is a melt processable polymer.
93. A membrane as in claim 91 wherein said solid acid is one of CsH2PO4, Cs5(HSO4)3(H2PO4)2, Cs2(HSO4)(H2PO4), Cs3(HSO4)2(H2PO4)2, Cs3(HSO4)2(H1.5(S0.5P0.5)O4), Cs5H3(SO4)4.xH2O, TlHSO4, CsHSeO4, CS2(HSeO4)(H2PO4), Cs3H(SeO4)2(NH4)3H(SO4)2, (NH4)2(HSO4)(H2PO4), Rb3H (SO4)2, Rb3H(SeO4)2, Cs1.5Li1.5H(SO4)2, Cs2Na(HSO4)3, TlH3(SeO3)2, CsH2AsO4(NH4)2(HSO4)(H2AsO4), TeO4, or CaNaHSiO4.
94. A proton conducting membrane, comprising:
a solid acid silicate of the general form MAHBSiO4 used in a proton conducting membrane.
95. A membrane as in claim 94 further comprising a structural binder for said solid acid material.
96. A membrane as in claim 94 wherein said solid acid is one of CaNaHSiO4, Cs3HSiO4 or (NH4)3HSiO4.
97. A proton conducting membrane, comprising:
a Cs or NH4 based solid acid; and
a ceramic or glass binder, forming a structural binder for said solid acid.
98. A device as in claim 97 wherein said binder is porous.
99. A method of using an electrochemical device, comprising:
forming a solid acid material into a proton conducting membrane; and
using said solid acid membrane to conduct protons.
100. A method as in claim 99 further comprising heating said solid solid acid material to a temperature at which it undergoes a superprotonic transition, prior to said using.
101. A method as in claim 99 wherein said solid solid acid compound is a sulfate or sulfate phosphate type solid acid.
102. A method as in claim 99 wherein said solid solid acid compound is a selenate or selenate phosphate solid acid.
103. A method as in claim 99 wherein said solid solid acid is a silicate.
104. A method as in claim 99 wherein said forming comprises adding a binder to said material.
105. A method as in claim 104 wherein said binder is a polymer.
106. A method as in claim 104 wherein said binder is a ceramic/oxide glass.
107. A material as in claim 104 wherein said binder is a conducting metal or semiconductor.
108. A method of operating an electrochemical device, comprising:
forming a membrane using a solid acid material of the general form MaHb(XOt)c; and
using said solid solid acid material to conduct protons in the electrochemical device.
109. A membrane as in claim 31 , wherein said solid acid is a solid solid acid material.
110. A proton conducting membrane, formed of a solid acid material in a superprotonic phase.
111. A method of operating an electrochemical device comprising:
providing a fuel to a proton conducting membrane which includes a carbon monoxide material therein, and
carrying out an electrochemical reaction at said proton conducting membrane, without removing said carbon monoxide material.
112. A method of forming a membrane-electrode assembly, comprising:
forming a composite film including a polymer and an solid acid of the general form MaHb(XOt)c;
forming said composite film onto a backing;
forming electrodes on said backing; and
hot pressing said material to form an assembly.
113. A method as in claim 112 , wherein an solid acid to polymer volume ratio is 50/50.
114. A method as in claim 112 , wherein said backing is graphite paper.
115. A method as in claim 33 , wherein said protons are conducted in a supercapacitor.
Priority Applications (1)
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US11/516,827 US20070009778A1 (en) | 1999-01-22 | 2006-09-06 | Proton conducting membrane using a solid acid |
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US11674199P | 1999-01-22 | 1999-01-22 | |
US14694399P | 1999-08-02 | 1999-08-02 | |
US14694699P | 1999-08-02 | 1999-08-02 | |
US15181199P | 1999-08-30 | 1999-08-30 | |
US09/439,377 US6468684B1 (en) | 1999-01-22 | 1999-11-15 | Proton conducting membrane using a solid acid |
US10/139,043 US7125621B2 (en) | 1999-01-22 | 2002-05-02 | Proton conducting membrane using a solid acid |
US11/516,827 US20070009778A1 (en) | 1999-01-22 | 2006-09-06 | Proton conducting membrane using a solid acid |
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US10/139,043 Continuation US7125621B2 (en) | 1999-01-22 | 2002-05-02 | Proton conducting membrane using a solid acid |
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US20070009778A1 true US20070009778A1 (en) | 2007-01-11 |
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US09/439,377 Expired - Lifetime US6468684B1 (en) | 1999-01-22 | 1999-11-15 | Proton conducting membrane using a solid acid |
US10/139,043 Expired - Lifetime US7125621B2 (en) | 1999-01-22 | 2002-05-02 | Proton conducting membrane using a solid acid |
US11/516,827 Abandoned US20070009778A1 (en) | 1999-01-22 | 2006-09-06 | Proton conducting membrane using a solid acid |
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US09/439,377 Expired - Lifetime US6468684B1 (en) | 1999-01-22 | 1999-11-15 | Proton conducting membrane using a solid acid |
US10/139,043 Expired - Lifetime US7125621B2 (en) | 1999-01-22 | 2002-05-02 | Proton conducting membrane using a solid acid |
Country Status (6)
Country | Link |
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US (3) | US6468684B1 (en) |
EP (1) | EP1171384B1 (en) |
JP (1) | JP3938662B2 (en) |
AU (1) | AU4795200A (en) |
CA (1) | CA2359865C (en) |
WO (1) | WO2000045447A2 (en) |
Cited By (3)
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Publication number | Priority date | Publication date | Assignee | Title |
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US20080308420A1 (en) * | 2005-11-22 | 2008-12-18 | Nippon Sheet Glass Company Limited | Proton Conductive Material, Process for Producing the Same, Hydrogen Concentration Cell, Hydrogen Sensor and Fuel Cell |
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Citations (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4569559A (en) * | 1984-06-04 | 1986-02-11 | Allied Corporation | Height sensing proportioning valve |
US4985315A (en) * | 1988-11-08 | 1991-01-15 | Mtu Friedrichshafen Gmbh | Material for the conduction of protons and method of making the same |
US5344548A (en) * | 1990-12-21 | 1994-09-06 | Eniricerche S.P.A. | Solid state sensor device for the determination of the concentration of gases which can react with hydrogen |
US5436094A (en) * | 1993-03-19 | 1995-07-25 | Mitsui Petrochemical Industries, Ltd. | Bulky synthetic pulp sheet useful as a separator for sealed lead batteries and process for preparing the same |
US5559638A (en) * | 1993-07-29 | 1996-09-24 | Olympus Optical Co., Ltd. | Wide-angle lens system #6 |
US5573648A (en) * | 1995-01-31 | 1996-11-12 | Atwood Systems And Controls | Gas sensor based on protonic conductive membranes |
US5576115A (en) * | 1992-01-17 | 1996-11-19 | Ente Per Le Nuove Tecnologie, L'energia E L'ambiente (Enea) | Composite polymeric electrolyte |
US5591545A (en) * | 1991-11-20 | 1997-01-07 | Honda Giken Kogyo Kabushiki Kaisha | Carbon material and method for producing same |
US5682261A (en) * | 1995-03-07 | 1997-10-28 | Matsushita Electric Industrial Co., Ltd. | Protonic conductor and electrochemical element using the same |
US5766799A (en) * | 1994-03-14 | 1998-06-16 | Hong; Kuochih | Method to reduce the internal pressure of a sealed rechargeable hydride battery |
US6001507A (en) * | 1996-12-24 | 1999-12-14 | Sony Corporation | Non-aqueous electrolyte secondary battery |
US6059943A (en) * | 1997-07-30 | 2000-05-09 | Lynntech, Inc. | Composite membrane suitable for use in electrochemical devices |
US6468684B1 (en) * | 1999-01-22 | 2002-10-22 | California Institute Of Technology | Proton conducting membrane using a solid acid |
US7255962B2 (en) * | 2004-07-01 | 2007-08-14 | California Institute Of Technology | Eulytite solid acid electrolytes for electrochemical devices |
US7416803B2 (en) * | 1999-01-22 | 2008-08-26 | California Institute Of Technology | Solid acid electrolytes for electrochemical devices |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3110571A1 (en) * | 1981-03-18 | 1982-09-30 | Max Planck Gesellschaft | Novel compounds which conduct hydrogen, their preparation and use |
US4659559A (en) | 1985-11-25 | 1987-04-21 | Struthers Ralph C | Gas fueled fuel cell |
FR2751119B1 (en) * | 1996-07-09 | 2002-01-25 | Commissariat Energie Atomique | PROTON CONDUCTIVE MATERIAL, ITS USE FOR THE PREPARATION OF A PROTON CONDUCTIVE MEMBRANE FOR FUEL CELLS AND SUPERCAPACITIES |
-
1999
- 1999-11-15 US US09/439,377 patent/US6468684B1/en not_active Expired - Lifetime
-
2000
- 2000-01-21 EP EP00930068A patent/EP1171384B1/en not_active Expired - Lifetime
- 2000-01-21 CA CA002359865A patent/CA2359865C/en not_active Expired - Lifetime
- 2000-01-21 AU AU47952/00A patent/AU4795200A/en not_active Abandoned
- 2000-01-21 WO PCT/US2000/001783 patent/WO2000045447A2/en active Search and Examination
- 2000-01-21 JP JP2000596609A patent/JP3938662B2/en not_active Expired - Fee Related
-
2002
- 2002-05-02 US US10/139,043 patent/US7125621B2/en not_active Expired - Lifetime
-
2006
- 2006-09-06 US US11/516,827 patent/US20070009778A1/en not_active Abandoned
Patent Citations (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4569559A (en) * | 1984-06-04 | 1986-02-11 | Allied Corporation | Height sensing proportioning valve |
US4985315A (en) * | 1988-11-08 | 1991-01-15 | Mtu Friedrichshafen Gmbh | Material for the conduction of protons and method of making the same |
US5344548A (en) * | 1990-12-21 | 1994-09-06 | Eniricerche S.P.A. | Solid state sensor device for the determination of the concentration of gases which can react with hydrogen |
US5591545A (en) * | 1991-11-20 | 1997-01-07 | Honda Giken Kogyo Kabushiki Kaisha | Carbon material and method for producing same |
US5576115A (en) * | 1992-01-17 | 1996-11-19 | Ente Per Le Nuove Tecnologie, L'energia E L'ambiente (Enea) | Composite polymeric electrolyte |
US5436094A (en) * | 1993-03-19 | 1995-07-25 | Mitsui Petrochemical Industries, Ltd. | Bulky synthetic pulp sheet useful as a separator for sealed lead batteries and process for preparing the same |
US5559638A (en) * | 1993-07-29 | 1996-09-24 | Olympus Optical Co., Ltd. | Wide-angle lens system #6 |
US5766799A (en) * | 1994-03-14 | 1998-06-16 | Hong; Kuochih | Method to reduce the internal pressure of a sealed rechargeable hydride battery |
US5573648A (en) * | 1995-01-31 | 1996-11-12 | Atwood Systems And Controls | Gas sensor based on protonic conductive membranes |
US5682261A (en) * | 1995-03-07 | 1997-10-28 | Matsushita Electric Industrial Co., Ltd. | Protonic conductor and electrochemical element using the same |
US6001507A (en) * | 1996-12-24 | 1999-12-14 | Sony Corporation | Non-aqueous electrolyte secondary battery |
US6059943A (en) * | 1997-07-30 | 2000-05-09 | Lynntech, Inc. | Composite membrane suitable for use in electrochemical devices |
US6468684B1 (en) * | 1999-01-22 | 2002-10-22 | California Institute Of Technology | Proton conducting membrane using a solid acid |
US7125621B2 (en) * | 1999-01-22 | 2006-10-24 | California Institute Of Technology | Proton conducting membrane using a solid acid |
US7416803B2 (en) * | 1999-01-22 | 2008-08-26 | California Institute Of Technology | Solid acid electrolytes for electrochemical devices |
US7255962B2 (en) * | 2004-07-01 | 2007-08-14 | California Institute Of Technology | Eulytite solid acid electrolytes for electrochemical devices |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20030104258A1 (en) * | 1999-01-22 | 2003-06-05 | Haile Sossina M. | Solid acid electrolytes for electrochemical devices |
US7416803B2 (en) * | 1999-01-22 | 2008-08-26 | California Institute Of Technology | Solid acid electrolytes for electrochemical devices |
US20090075149A1 (en) * | 1999-01-22 | 2009-03-19 | Haile Sossina M | Solid acid electrolytes for electrochemical devices |
US8202663B2 (en) * | 1999-01-22 | 2012-06-19 | California Institute Of Technology | Solid acid electrolytes for electrochemical devices |
CN104395746A (en) * | 2012-09-04 | 2015-03-04 | Atonarp株式会社 | Ultrasonic testing device and method of assembly |
US9157890B2 (en) * | 2012-09-04 | 2015-10-13 | Atonarp Inc. | Exchange membrane unit and system including exchange membrane unit |
CN104395746B (en) * | 2012-09-04 | 2016-12-07 | Atonarp株式会社 | Film crosspoint and there is the system of film crosspoint |
CN112111757A (en) * | 2020-09-15 | 2020-12-22 | 中国科学院大连化学物理研究所 | Composite membrane for high-temperature water electrolysis and preparation method and application thereof |
Also Published As
Publication number | Publication date |
---|---|
WO2000045447A8 (en) | 2001-04-12 |
JP3938662B2 (en) | 2007-06-27 |
CA2359865C (en) | 2006-05-23 |
WO2000045447A3 (en) | 2000-11-16 |
AU4795200A (en) | 2000-08-18 |
EP1171384A2 (en) | 2002-01-16 |
CA2359865A1 (en) | 2000-08-03 |
US20030008190A1 (en) | 2003-01-09 |
JP2002536787A (en) | 2002-10-29 |
EP1171384B1 (en) | 2012-10-10 |
WO2000045447A2 (en) | 2000-08-03 |
US6468684B1 (en) | 2002-10-22 |
US7125621B2 (en) | 2006-10-24 |
WO2000045447A9 (en) | 2001-10-18 |
EP1171384A4 (en) | 2004-05-19 |
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