US5599638A
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Aqueous liquid feed organic fuel cell using solid polymer electrolyte membrane
Assignee: California Institute of Technology
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Filing: 1993-10-12
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Granted: 1997-02-04
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Expires: 2013-10-12
Abstract
Abstract A liquid organic fuel cell is provided which employs a solid electrolyte membrane. An organic fuel, such as a methanol/water mixture, is circulated past an anode of a cell while oxygen or air is circulated past a cathode of the cell. The cell solid electrolyte membrane is preferably fabricated from Nafion™. Additionally, a method for improving the performance of carbon electrode structures for use in organic fuel cells is provided wherein a high surface-area carbon particle/Teflon™-binder structure is immersed within a Nafion™/methanol bath to impregnate the electrode with Nafion™. A method for fabricating an anode for use in a organic fuel cell is described wherein metal alloys are deposited onto the electrode in an electro-deposition solution containing perfluorooctanesulfonic acid. A fuel additive containing perfluorooctanesulfonic acid for use with fuel cells employing a sulfuric acid electrolyte is also disclosed. New organic fuels, namely, trimethoxymethane, dimethoxymethane, and trioxane are also described for use with either conventional or improved fuel cells.
Inventors
- 👤 Subbarao Surampudi
- 👤 Sekharipuram R. Narayanan
- 👤 Eugene Vamos
- 👤 Harvey A. Frank
- 👤 Gerald Halpert
- 👤 George A. Olah
- 👤 G. K. Surya Prakash
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-06 23:52
CPC Classifications
H; H01; H01M; H01M4/00; H01M4/86; H01M4/8605; H01M4/88; H01M4/8803; H01M4/8807; H01M4/8825; H01M4/8853; H01M4/90; H01M4/92; H01M4/921; H01M4/925; H01M4/926; H01M8/00; H01M8/02; H01M8/0202; H01M8/023; H01M8/0234; H01M8/0241; H01M8/0243; H01M8/04; H01M8/04082; H01M8/04186; H01M8/10; H01M8/1009; H01M8/1011; H01M8/1016; H01M8/1018; H01M8/102; H01M8/1023; H01M8/1039; H01M8/1041; H01M8/1053; H01M8/22; H01M8/24; H01M8/2455; H01M2300/00; H01M2300/0017; H01M2300/0065; H01M2300/0082; H01M8/0239; H01M8/1004; Y; Y02; Y02E; Y02E60/00; Y02E60/30; Y02E60/50
Claims Analysis
Total Claims: 61
Claim 1
Independent Claim
56 words
In a liquid feed direct fuel cell having an anode, a cathode, an electrolyte, means for circulating an organic fuel past the anode and means for flowing oxygen past the cathode, wherein the improvement comprises: said electrolyte comprising a solid polymer hydrogen ion conductor membrane; and wherein said organic fuel is free of an acid electrolyte.
Claim 2
Dependent Claim
56 words
In a liquid feed direct fuel cell having an anode, a cathode, an electrolyte, means for circulating an organic fuel past the anode and means for flowing oxygen past the cathode, wherein the improvement comprises: said electrolyte comprising a solid polymer hydrogen ion conductor membrane; and wherein said organic fuel is free of an acid electrolyte.
Claim 3
Dependent Claim
20 words
The fuel cell of claim 1, wherein, said membrane is composed of a co-polymer of tetraflouroethylene and perflourocinylether sulfonic acid.
Claim 4
Dependent Claim
17 words
The fuel cell of claim 1, wherein said membrane is composed of a perfluorinated sulfonic acid polymer.
Claim 5
Dependent Claim
17 words
The fuel cell of claim 1, wherein said membrane is composed of a polyhydrocarbon sulfonic acid polymer.
Claim 6
Dependent Claim
22 words
The fuel cell of claim 1, wherein said membrane is composed of a composite of two or more hydrogen ion conductor membranes.
Claim 7
Dependent Claim
22 words
The fuel cell of claim 1, wherein said organic fuel is selected from a group consisting of methanol, formaldehyde, and formic acid.
Claim 8
Dependent Claim
21 words
The fuel cell of claim 1, wherein said organic fuel is selected from a group consisting of dimethoxymethane, trimethoxymethane and trioxane.
Claim 9
Dependent Claim
20 words
The fuel cell of claim 1, wherein said anode is an electrode impregnated with a hydrophilic proton conducting water-insoluble additive.
Claim 10
Dependent Claim
18 words
The fuel cell of claim 8, wherein said additive is a co-polymer of tetrafluoroethylene and perfluorovinylether sulfonic acid.
Claim 11
Dependent Claim
12 words
The fuel cell of claim 8, wherein said additive is montmorrolinite clay.
Claim 12
Dependent Claim
12 words
The fuel cell of claim 8, wherein said additive is an alkoxycellulose.
Claim 13
Dependent Claim
12 words
The fuel cell of claim 8, wherein said additive is a cyclodextrine.
Claim 14
Dependent Claim
14 words
The fuel cell of claim 8, wherein said additive is a mixture of zeolites.
Claim 15
Dependent Claim
13 words
The fuel cell of claim 8, wherein said additive is zirconium hydrogen phosphate.
Claim 16
Dependent Claim
59 words
A liquid feed fuel cell, comprising: an anode; a cathode; a solid cation exchange polymer electrolyte membrane disposed between said anode and said cathode; means for circulating a liquid organic fuel and water solution past said anode, a liquid organic and water fuel solution, said solution being free of sulfuric acid; and means for flowing oxygen past said cathode.
Claim 17
Dependent Claim
59 words
A liquid feed fuel cell, comprising: an anode; a cathode; a solid cation exchange polymer electrolyte membrane disposed between said anode and said cathode; means for circulating a liquid organic fuel and water solution past said anode, a liquid organic and water fuel solution, said solution being free of sulfuric acid; and means for flowing oxygen past said cathode.
Claim 18
Dependent Claim
69 words
A liquid feed fuel cell, comprising: an anode coated with an amount of hydrophilic proton conducting water-insoluble additive to provide ionic and electronic conductivity, wetting and gas evolving properties to said anode; a cathode; a cation exchange polymer electrolyte membrane disposed between said anode and said cathode; means for flowing a liquid comprising organic fuel and water solution past said anode; and means for flowing oxygen past said cathode.
Claim 19
Dependent Claim
69 words
A liquid feed fuel cell, comprising: an anode coated with an amount of hydrophilic proton conducting water-insoluble additive to provide ionic and electronic conductivity, wetting and gas evolving properties to said anode; a cathode; a cation exchange polymer electrolyte membrane disposed between said anode and said cathode; means for flowing a liquid comprising organic fuel and water solution past said anode; and means for flowing oxygen past said cathode.
Claim 20
Dependent Claim
15 words
The fuel cell of claim 16, wherein said membrane is a solid proton exchange membrane.
Claim 21
Dependent Claim
20 words
The fuel cell of claim 17, wherein said membrane is composed of a co-polymer of tetradluoroethylene and perfluorovinylether sulfonic acid.
Claim 22
Dependent Claim
17 words
The fuel cell of claim 17, wherein said membrane is composed of a perfluorinated sulfonic acid polymer.
Claim 23
Dependent Claim
16 words
The fuel cell of claim 17, wherein said membrane is composed of polyhydrocarbon sulfonic acid polymer.
Claim 24
Dependent Claim
21 words
The fuel cell of claim 17, wherein said membrane is composed of a composite of two or more proton exchange membranes.
Claim 25
Dependent Claim
22 words
The fuel cell of claim 16, wherein said organic fuel is selected from a group consisting of methanol, formaldehyde, and formic acid.
Claim 26
Dependent Claim
21 words
The fuel cell of claim 16, wherein said organic fuel is selected from a group consisting of dimethoxymethane, trimethoxymethane and trioxane.
Claim 27
Dependent Claim
17 words
The fuel cell of claim 16, wherein said additive is co-polymer of tetrafluoroethylene and perfluorovinylether sulfonic acid.
Claim 28
Dependent Claim
12 words
The fuel cell of claim 16, wherein said additive is montmorrolinite clay.
Claim 29
Dependent Claim
12 words
The fuel cell of claim 16, wherein said additive is an alkoxycellulose.
Claim 30
Dependent Claim
12 words
The fuel cell of claim 16, wherein said additive is a cyclodextrine.
Claim 31
Dependent Claim
14 words
The fuel cell of claim 16, wherein said additive is a mixture of zeolites.
Claim 32
Dependent Claim
13 words
The fuel cell of claim 16, wherein said additive is zirconium hydrogen phosphate.
Claim 33
Dependent Claim
130 words
A liquid feed fuel cell, comprising: a housing having an anode chamber and a cathode chamber; a co-polymer of tetrafluoroethylene and perfluorovinylether sulfonic acid polymer electrolyte membrane mounted within said housing and separating said anode and cathode chambers; a cathode formed on a side surface of the membrane facing the cathode chamber; an anode formed on an opposing side of the membrane facing the anode chamber, said anode being impregnated with co-polymer of tetrafluoroethylene and perfluorovinylether sulfonic acid; means for circulating a liquid organic fuel and water solution past said anode; means for flowing oxygen past said cathode; means for withdrawing carbon dioxide from the anode chamber; means for withdrawing unused fuel and water from the anode compartment; and means for withdrawing unused oxygen and water from the cathode chamber.
Claim 34
Dependent Claim
130 words
A liquid feed fuel cell, comprising: a housing having an anode chamber and a cathode chamber; a co-polymer of tetrafluoroethylene and perfluorovinylether sulfonic acid polymer electrolyte membrane mounted within said housing and separating said anode and cathode chambers; a cathode formed on a side surface of the membrane facing the cathode chamber; an anode formed on an opposing side of the membrane facing the anode chamber, said anode being impregnated with co-polymer of tetrafluoroethylene and perfluorovinylether sulfonic acid; means for circulating a liquid organic fuel and water solution past said anode; means for flowing oxygen past said cathode; means for withdrawing carbon dioxide from the anode chamber; means for withdrawing unused fuel and water from the anode compartment; and means for withdrawing unused oxygen and water from the cathode chamber.
Claim 35
Dependent Claim
31 words
An electrode comprising a metal alloy coated with an amount of hydrophilic proton conducting, water insoluble additive to provide ionic and electronic conductivity, wetting and gas evolving properties to the electrode.
Claim 36
Dependent Claim
31 words
An electrode comprising a metal alloy coated with an amount of hydrophilic proton conducting, water insoluble additive to provide ionic and electronic conductivity, wetting and gas evolving properties to the electrode.
Claim 37
Independent Claim
42 words
A method for processing a carbon structure composed of carbon particles supported by a binder, said method comprising the steps of: immersing the carbon structure within a bath containing a liquid perflourinated sulfonic acid polymer; and removing and drying said carbon structure.
Claim 38
Independent Claim
42 words
A method for processing a carbon structure composed of carbon particles supported by a binder, said method comprising the steps of: immersing the carbon structure within a bath containing a liquid perflourinated sulfonic acid polymer; and removing and drying said carbon structure.
Claim 39
Dependent Claim
26 words
The method of claim 32, wherein said polymer is a 1% co-polymer of tetrafluoroethylene and perfluorovinylether sulfonic acid solution and said polymer is dispersed in methanol.
Claim 40
Dependent Claim
27 words
The method of claim 32, wherein said step of immersing said carbon structure in a bath containing a liquid polymer is performed for 5 to 10 minutes.
Claim 41
Dependent Claim
10 words
A structure processed according to the method of claim 32.
Claim 42
Dependent Claim
20 words
An electro-deposition bath for use in fabricating an electrode for use in a liquid feed fuel cell, comprising perfluorooctanesulfonic acid.
Claim 43
Dependent Claim
20 words
An electro-deposition bath for use in fabricating an electrode for use in a liquid feed fuel cell, comprising perfluorooctanesulfonic acid.
Claim 44
Independent Claim
81 words
A method for fabricating an electrode for use in a fuel cell, said method comprising the steps of: providing a bath containing a solution of metallic salts dissolved in sulfuric acid; adding perfluorooctanesulfonic acid to said bath; positioning a electrode having a carbon structure within said bath; positioning an anode within said bath; and applying a voltage between said anode and said electrode until a desired amount of metal in a range of 0.5-4.0 mg/cm 2 becomes deposited onto said electrode.
Claim 45
Independent Claim
81 words
A method for fabricating an electrode for use in a fuel cell, said method comprising the steps of: providing a bath containing a solution of metallic salts dissolved in sulfuric acid; adding perfluorooctanesulfonic acid to said bath; positioning a electrode having a carbon structure within said bath; positioning an anode within said bath; and applying a voltage between said anode and said electrode until a desired amount of metal in a range of 0.5-4.0 mg/cm 2 becomes deposited onto said electrode.
Claim 46
Dependent Claim
15 words
The method of claim 37, wherein said metal salts include hydrogen hexachloroplatinate and potassium pentachloroaquoruthenium.
Claim 47
Dependent Claim
12 words
The method of claim 37, wherein said anode is composed of platinum.
Claim 48
Dependent Claim
17 words
The method of claim 37, wherein said carbon electrode structure includes carbon combined with a polytetrafluoroethylene binder.
Claim 49
Dependent Claim
27 words
The method of claim 37, wherein said carbon electrode includes carbon bound by a 15%, by weight, polytetrafluoroethylene binder and applied on a carbon based fiber layer.
Claim 50
Dependent Claim
18 words
The method of claim 37, wherein said acid is provided with a concentration in the range of 0.01-0.05M.
Claim 51
Dependent Claim
23 words
The method of claim 37, including the further steps of extracting said electrode from said bath and washing said electrode in deionized water.
Claim 52
Independent Claim
147 words
A method for fabricating an electrode having metal ions deposited thereon for use in a liquid organic fuel cell, said method comprising the steps of: providing a bath comprising a solution of hydrogen hexachloroplatinate and potassium pentachloroaquoruthenium dissolved in sulfuric acid, wherein said hydrogen hexachloroplatinate and potassium pentachloroaquoruthenium has a concentration in the range 0.01-0.05M; adding perfluorooctanesulfonic acid to said bath, with a concentration within the range of 0.1-1.0 grams /liter; positioning a carbon electrode structure into said bath, wherein said carbon electrode structure has a mixture of carbon particles with a surface area of about 200 meters/gram a polytetrafluoroethylene binder, with the mixture applied to a fiber-based carbon paper; positioning a platinum anode into said bath; and applying a voltage between said anode and said electrode until a desired amount of platinum and ruthenium in the range of 0.5-4.0 mg/cm 2 become deposited onto said electrode.
Claim 53
Independent Claim
147 words
A method for fabricating an electrode having metal ions deposited thereon for use in a liquid organic fuel cell, said method comprising the steps of: providing a bath comprising a solution of hydrogen hexachloroplatinate and potassium pentachloroaquoruthenium dissolved in sulfuric acid, wherein said hydrogen hexachloroplatinate and potassium pentachloroaquoruthenium has a concentration in the range 0.01-0.05M; adding perfluorooctanesulfonic acid to said bath, with a concentration within the range of 0.1-1.0 grams /liter; positioning a carbon electrode structure into said bath, wherein said carbon electrode structure has a mixture of carbon particles with a surface area of about 200 meters/gram a polytetrafluoroethylene binder, with the mixture applied to a fiber-based carbon paper; positioning a platinum anode into said bath; and applying a voltage between said anode and said electrode until a desired amount of platinum and ruthenium in the range of 0.5-4.0 mg/cm 2 become deposited onto said electrode.
Claim 54
Dependent Claim
10 words
An electrode fabricated according to the method of claim 44.
Claim 55
Dependent Claim
38 words
A liquid feed fuel cell, comprising: an anode; a cathode; a liquid organic fuel, water, acid electrolyte and perfluorooctanesulfonic acid additive solution; means for flowing said solution past said anode; and means for flowing oxygen past said cathode.
Claim 56
Dependent Claim
38 words
A liquid feed fuel cell, comprising: an anode; a cathode; a liquid organic fuel, water, acid electrolyte and perfluorooctanesulfonic acid additive solution; means for flowing said solution past said anode; and means for flowing oxygen past said cathode.
Claim 57
Dependent Claim
44 words
A liquid feed fuel cell, comprising: an anode; a cathode; an electrolyte; a liquid organic fuel selected from a group consisting of trioxane, dimethoxymethane, and trimethoxymethane; means for flowing said liquid organic fuel past said anode; and means for flowing oxygen past said cathode.
Claim 58
Dependent Claim
44 words
A liquid feed fuel cell, comprising: an anode; a cathode; an electrolyte; a liquid organic fuel selected from a group consisting of trioxane, dimethoxymethane, and trimethoxymethane; means for flowing said liquid organic fuel past said anode; and means for flowing oxygen past said cathode.
Claim 59
Dependent Claim
21 words
The fuel cell of claim 47, wherein said fuel is dissolved in water to a concentration of between 0.1 and 2.0M.
Claim 60
Independent Claim
34 words
A method for generating energy comprising the steps of: providing a liquid-feed fuel cell; and operating the liquid-feed fuel cell using an organic fuel selected from a group consisting of trioxane, dimethoxymethane and trimethoxymethane.
Claim 61
Independent Claim
34 words
A method for generating energy comprising the steps of: providing a liquid-feed fuel cell; and operating the liquid-feed fuel cell using an organic fuel selected from a group consisting of trioxane, dimethoxymethane and trimethoxymethane.
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| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
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| 3.5 Years (Year 4) | 2000-02-04 | 2000-08-05 | 2001-02-04 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 2004-02-04 | 2004-08-05 | 2005-02-04 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2008-02-04 | 2008-08-05 | 2009-02-04 | $7700.00 | Window Closed / Lapsed |