US20040018937A1 - Methods for forming catalytic coating on a substrate - Google Patents
Methods for forming catalytic coating on a substrate Download PDFInfo
- Publication number
- US20040018937A1 US20040018937A1 US10/369,145 US36914503A US2004018937A1 US 20040018937 A1 US20040018937 A1 US 20040018937A1 US 36914503 A US36914503 A US 36914503A US 2004018937 A1 US2004018937 A1 US 2004018937A1
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- United States
- Prior art keywords
- catalytic
- substrate
- fluid
- coating
- noncatalytic
- 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
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 178
- 239000000758 substrate Substances 0.000 title claims abstract description 154
- 238000000576 coating method Methods 0.000 title claims abstract description 125
- 239000011248 coating agent Substances 0.000 title claims abstract description 121
- 238000000034 method Methods 0.000 title claims abstract description 121
- 239000012530 fluid Substances 0.000 claims abstract description 207
- 239000000446 fuel Substances 0.000 claims description 63
- 239000000463 material Substances 0.000 claims description 61
- 239000012528 membrane Substances 0.000 claims description 44
- 238000009792 diffusion process Methods 0.000 claims description 35
- 239000003792 electrolyte Substances 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 20
- 239000002001 electrolyte material Substances 0.000 claims description 18
- 229920000554 ionomer Polymers 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 239000010970 precious metal Substances 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 9
- 230000001590 oxidative effect Effects 0.000 claims description 9
- 239000007800 oxidant agent Substances 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 239000003575 carbonaceous material Substances 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 150000003460 sulfonic acids Chemical class 0.000 claims description 4
- QHSJIZLJUFMIFP-UHFFFAOYSA-N ethene;1,1,2,2-tetrafluoroethene Chemical group C=C.FC(F)=C(F)F QHSJIZLJUFMIFP-UHFFFAOYSA-N 0.000 claims description 3
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 230000001747 exhibiting effect Effects 0.000 claims 3
- 229920000642 polymer Polymers 0.000 claims 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims 2
- 239000004917 carbon fiber Substances 0.000 claims 2
- 239000004744 fabric Substances 0.000 claims 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims 1
- 239000004810 polytetrafluoroethylene Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 description 8
- 238000000151 deposition Methods 0.000 description 8
- 230000008021 deposition Effects 0.000 description 7
- 239000000523 sample Substances 0.000 description 6
- 238000009428 plumbing Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 238000000429 assembly Methods 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 238000011960 computer-aided design Methods 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0241—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8605—Porous electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8803—Supports for the deposition of the catalytic active composition
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8828—Coating with slurry or ink
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8882—Heat treatment, e.g. drying, baking
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0247—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the form
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8803—Supports for the deposition of the catalytic active composition
- H01M4/8807—Gas diffusion layers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8803—Supports for the deposition of the catalytic active composition
- H01M4/881—Electrolytic membranes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8803—Supports for the deposition of the catalytic active composition
- H01M4/8814—Temporary supports, e.g. decal
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04291—Arrangements for managing water in solid electrolyte fuel cell systems
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
-
- 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
Definitions
- the present invention relates generally to fuel cells and particularly, to methods for forming a catalytic coating on a substrate.
- a method of forming a catalytic coating on a substrate is provided.
- a catalytic fluid is prepared and dispensed onto a substrate using a direct writing instrument that has been programmed to dispense the catalytic fluid onto the substrate in a pattern that forms a catalytic coating on the first side of the substrate.
- a method of forming a catalytic coating on a substrate is provided.
- a catalytic fluid is dispensed onto a substrate using a direct writing instrument that has been programmed to dispense the catalytic fluid onto the substrate in a pattern that forms a first coating on a first side of the substrate.
- a noncatalytic fluid is also dispensed onto the first side of the substrate using the same direct writing instrument in a shadow pattern of the first coating to form a second coating on the first side of the substrate.
- a method of preparing an electrolyte membrane for use in a membrane electrode assembly is provided.
- a catalytic fluid is dispensed onto an intermediate material using a direct writing instrument that has been programmed to dispense the catalytic fluid in a pattern that forms a catalytic coating on the intermediate material.
- the catalytic coating is then transferred from the intermediate material to an electrolyte membrane.
- a method of preparing an electrolyte membrane for use in a membrane electrode assembly is provided. According to the method, a catalytic fluid is dispensed onto an electrolyte material using a direct writing instrument.
- a method of preparing a diffusion media for use in a fuel cell is provided. According to the method, a catalytic fluid is dispensed onto a diffusion media using a direct writing instrument.
- a system for preparing a membrane electrode assembly comprises first and second coating stations, first and second drying stations, a cutting station and a carrier device.
- the first coating station comprises a first substrate holding device, and at least one coating head for applying a coating to a first side of a substrate.
- the second coating station comprises a second substrate holding device, and at least one coating head for applying a coating to a second side of a substrate.
- the carrier device is configured to carry the substrate from station to station.
- FIG. 1 is a schematic illustration of a fuel cell system.
- FIG. 2 is a schematic illustration of a vehicle including a fuel cell system.
- FIG. 3 is a schematic illustration of a fuel cell stack employing two fuel cells.
- FIG. 4 is an exploded view of a membrane electrode assembly.
- FIG. 5 is a block diagram of a direct writing instrument according to one embodiment of the present invention.
- FIG. 6 is an illustration of the nozzle and nozzle tip of a direct writing instrument forming a pattern on a substrate according to one embodiment of the present invention.
- FIG. 7 is an illustration of a pattern according to one embodiment of the present invention.
- FIG. 8 is an illustration of a pattern according to one embodiment of the present invention.
- FIG. 9 is an illustration of a membrane electrode assembly according to one embodiment of the present invention.
- FIG. 10 is an illustration of one side of a membrane electrode assembly having a first and a second coating according to one embodiment of the present invention.
- FIG. 11 is an illustration of a membrane electrode assembly system according to one embodiment of the present invention.
- FIG. 12 a is an illustration of an ultrasonic probe applied above to a substrate.
- FIG. 12 b is an illustration of an ultrasonic probe applied below a substrate.
- the fuel cell system 2 for automotive applications is shown. It is to be appreciated, however, that other fuel cell system applications, such as for example, in the area of residential systems, may benefit from the present invention.
- the fuel cell system 2 includes a primary reactor 4 , a water-gas shift reactor 6 , a preferential oxidation (PrOx) reactor 7 , at least one heat exchanger 8 , a tail gas combustor 9 , and a fuel cell 10 .
- PrOx preferential oxidation
- a hydrocarbon fuel such as gasoline or methane
- air and steam are mixed, heated, and delivered to a catalyzed substrate.
- the mixture is split into hydrogen, carbon monoxide, and other process gases, as the mixture flows over and reacts with the catalyst, forming a hydrogen-rich stream.
- Suitable catalyst materials include platinum group metals and base metals. This reaction occurs at temperatures in the range between about 700° C. and about 800° C.
- the hydrogen-rich stream leaving the primary reactor 4 enters the water-gas shift reactor 6 .
- Oxygen from water is used to convert carbon monoxide to carbon dioxide leaving additional hydrogen and increasing system efficiency.
- Operating temperatures of the shift reactor 6 range from about 250° C. to about 450° C.
- the hydrogen-rich stream leaving the shift reactor 6 then enters into the PrOx reactor 7 , where the final cleanup of carbon monoxide takes place before the hydrogen-rich stream enters the fuel cell stack. Air is added to supply the oxygen needed to convert most of the remaining carbon monoxide to carbon dioxide, leaving additional hydrogen behind.
- Operating temperatures in the PrOx reactor 7 range from about 80° C. to about 200° C. Combined, the three reactors extract hydrogen from the fuel, and reduce or eliminate harmful emissions.
- the three reactors are quickly heated to their operating temperatures before the fuel is introduced.
- the heat exchanger 8 is therefore used to regulate the various temperatures throughout the fuel cell system 2 .
- the heat exchanger 8 preheats the steam and air streams before entering into the primary reactor 4 .
- the waste heat from the hydrogen-rich stream exits the primary reactor 4 .
- the hydrogen-rich stream then is supplied to the fuel cell 10 , which may comprise a stack of fuel cells, and reacted with oxygen from a source, such as air, to produce electricity, which can be used to power a load 11 .
- the small quantities of unused hydrogen that leave the fuel cell 10 are consumed in the tail gas combustor 9 which operates at a temperature between about 300° C. to about 800° C. It is to be appreciated that while a series of reactors is described as being the hydrogen source, any hydrogen source is applicable to the present invention.
- FIG. 2 a vehicle is shown having a vehicle body 90 , and a fuel cell system having a fuel cell processor 4 and a fuel cell stack 15 .
- a discussion of the present invention as embodied in a fuel cell stack and a fuel cell, is provided hereafter in reference to FIGS. 3 - 9 .
- FIG. 3 depicts a fuel cell stack 15 having a pair of membrane-electrode-assemblies (MEAs) 20 and 22 separated from each other by an electrically conductive fluid distribution plate 30 .
- Plate 30 serves as a bi-polar plate having a plurality of fluid flow channels 35 , 37 for distributing fuel and oxidant gases to the MEAs 20 and 22 .
- fluid flow channel we mean a path, region, area, or any domain on the plate that is used to transport fluid in, out, along, or through at least a portion of the plate.
- the MEAs 20 and 22 , and plate 30 are stacked together between clamping plates 40 and 42 , and electrically conductive fluid distribution plates 32 and 34 . Plates 32 and 34 serve as end plates having only one side containing channels 36 and 38 , respectively, for distributing fuel and oxidant gases to the MEAs 20 and 22 , as opposed to both sides of the plate.
- Nonconductive gaskets 50 , 52 , 54 , and 56 provide seals and electrical insulation between the several components of the fuel cell stack.
- Gas permeable diffusion media material 60 , 62 , 64 , and 66 press up against the electrode faces of the MEAs 20 and 22 .
- Plates 32 and 34 press up against the diffusion media material 60 and 66 respectively, while the plate 30 presses up against the diffusion media material 62 on the anode face of MEA 20 , and against diffusion media material 64 on the cathode face of MEA 22 .
- An oxidizing fluid such as O 2
- O 2 is supplied to the cathode side of the fuel cell stack from storage tank 70 via appropriate supply plumbing 86 .
- a reducing fluid such as H 2
- the reducing fluid may be derived from a mixture of methane or gasoline, air, and water according to a reforming process in the presence of a catalyst.
- Exhaust plumbing (not shown) for both the H 2 and O 2 /air sides of the MEAs will also be provided.
- Additional plumbing 80 , 82 , and 84 is provided for supplying liquid coolant to the plate 30 and plates 32 and 34 . Appropriate plumbing for exhausting coolant from the plates 30 , 32 , and 34 is also provided, but not shown.
- membrane electrode assembly 20 comprising an anode layer 102 , a cathode layer 106 , and an electrolyte 104 separating the anode layer 102 and the cathode layer 106 .
- Membrane electrode assembly 20 and membrane electrode assembly 22 are identical.
- the present invention is being described in relation to membrane electrode assembly 20 , it is to be appreciated that the present invention can be applied to membrane electrode assembly 22 and membrane electrode assemblies in general.
- the anode layer 102 and the cathode layer 106 are coatings formed in such a manner that they are in intimate contact with the electrolyte material once the fuel cell 10 (FIG. 1) is assembled.
- Methods of forming a catalytic coating on a substrate will now be explained.
- the first step in the method is to prepare a catalytic fluid.
- the catalytic fluid is a solution of ionomer, precious metal catalyst, solvent and water.
- a solution of ionomer and precious metal catalyst istypically prepared on a support in a mixture of the solvent and water. Different amounts maybe used depending on the desired viscosity of the catalytic fluid and the carbon to ionomer ratio desired.
- the support used for the solution of the ionomer and precious metal catalyst is typically carbon having a high surface area.
- the amount of carbon is generally between about 5 grams and about 20 grams.
- the catalytic solution comprises about 4% by wt. of precious metal, about 4% by wt. of ionomer, about 4% by wt. of carbon, about 28% by wt. of water and about 60% by wt. of solvent.
- the precious metal catalyst can be selected from platinum, platinum alloys and combinations thereof.
- the solvent can be selected from isopropyl alcohol, ethanol, butanol, and combinations thereof.
- the catalytic fluid can be prepared to exhibit a viscosity between about 70 cp and about 2000 cp, and more specifically, a viscosity of about 300 cp.
- the catalytic fluid can be prepared to exhibit an ionomer to carbon ratio of about 0.8 to about 2.0.
- the amount of solid in the solution is between about 8% by wt. and about 20% by wt., and more specifically about 12% by wt.
- the catalytic fluid is prepared, it is dispensed onto a substrate 110 using a direct writing instrument.
- direct writing we mean depositing fluid directly onto a surface of a substrate in a pattern defined by the motion of the instrument, the motion of the substrate, or both.
- the deposited fluid forms a relatively well-defined line or area of deposition, relative to the overall dimensions of the deposition surface or the deposited pattern. Relative motion between the fluid source and the deposition substrate increases the extent of the well-defined line or area of deposition to create a more extensive deposited pattern.
- FIG. 5 shows one embodiment of a direct writing instrument according to the present invention.
- the direct writing instrument 150 comprises a design system 152 , a writing system controller 154 and a writing system 160 .
- the writing system 160 further comprises a fluid dispensing system 168 , a nozzle 166 , a nozzle tip 167 , and a substrate holding device 162 .
- the design system 152 stores a pattern that is drawn on a graphic display.
- the design system 152 electronically communicates with the writing system controller 154 such that the writing system controller 154 knows the pattern and controls the writing system 160 in a manner that allows the writing system 160 to draw the pattern stored in the design system 152 on the substrate 110 .
- the writing system controller 154 electronically communicates with the fluid dispensing system 168 and the substrate holding device 162 . Therefore, the writing system controller 154 allows the fluid dispensing system 168 to deliver the catalytic fluid to the nozzle 166 .
- the catalytic fluid is dispensed through the nozzle tip 167 onto the substrate 110 .
- the catalytic fluid may be carried to the fluid dispensing system 168 by any suitable means.
- the writing system controller 154 allows the substrate holding device 162 to move in a variety of positions that form the pattern 170 stored in the design system.
- the substrate 110 is accurately placed under the nozzle tip 167 while the catalytic fluid is being dispensed onto the substrate 110 .
- the nozzle 166 and the nozzle tip 167 do not move, but remain stationary while dispensing the catalytic fluid.
- the pressure of the nozzle tip 167 is controlled such that no direct surface contact with the substrate 110 occurs.
- the substrate holding device 162 remains stationary while the nozzle 166 and nozzle tip 167 move over the substrate 110 while dispensing the catalytic fluid.
- the design system 152 may be any computer-aided-design (CAD) interface that allows the design of a pattern via a graphics editor, digitizing tablet, or interface through a generic photo plotter interface.
- CAD computer-aided-design
- the nozzle 166 may be heated to allow the catalytic fluid to remain in a molten state so that it will easily dispense through the nozzle tip 167 .
- the width and thickness of the line, or lines, 169 forming the pattern 170 depend upon the nozzle tip diameter, the volumetric flowrate of the fluid to the nozzle tip, and the writing speed.
- the writing speed may vary depending upon the movement of the substrate 110 relative to the nozzle tip 167 or the movement of the nozzle tip 167 the substrate.
- the nozzle tip 167 can produce at least one line having a width between about 0.002 inches to about 0.25 inches. If more than one line is desired, a space up to about 0.0005 inches can be made between the lines.
- the line thickness can be up to 0.010 inches per pass with the nozzle.
- the line can have tolerances of about +/ ⁇ 0.000025 inches.
- the instrument writes at a speed between about 0.05 inches per second to about 5.0 inches per second.
- the instrument 150 operates on a minimum grid pitch of 0.0005 inches.
- the pattern 170 formed on the substrate 110 can be selected from a rectangular spiral, a straight line, a series of lines, or any suitable geometric pattern.
- An example of a pattern 170 having a line, or series of lines, 169 forming a rectangular spiral is shown in FIG. 7.
- the spacing between adjacent lines can be adjusted. For the case of no spacing between adjacent lines, the pattern 170 would form a single continuous coating over the entire substrate 110 .
- FIG. 8 shows a pattern 170 having a series of lines 169 formed by a direct writing instrument according to one embodiment of the present invention.
- the substrate 110 is dried by a heat source having a temperature between about 70° C. and about 100 ° C.
- the pattern once dried, forms a coating on the substrate 110 .
- the heat source is selected from an infrared heater, convective oven, heated jets, or any other suitable heating device for removing solvent from the catalytic fluid.
- the substrate 110 is subjected to the heat for a time sufficient to evaporate primarily all of the solvent in the coating, more specifically between about 2 minutes to about 10 minutes.
- the method of making the membrane electrode assembly may vary depending upon the substrate upon which the catalytic fluid is dispensed.
- the substrate is generally selected from an intermediate material, a diffusion media material, or electrolyte membrane material.
- the substrate is an intermediate material then the catalytic solution is deposited in the programmed pattern onto the intermediate material by a direct writing instrument.
- the coated substrate is then dried at a temperature between about 70° C. to about 100° C., typically in an oven.
- a secondary ionomer solution may be applied to the substrate and dried.
- the application of the ionomer solution is typically performed by spraying.
- the coating formed on the intermediate material is then transferred to an electrolyte membrane material typically using a hot-press transfer.
- a second fluid that is nonreactive may be applied onto the intermediate material after the deposition of catalytic fluid or simultaneously with the catalytic fluid.
- the coating formed on the intermediate material is then transferred to an electrolyte membrane material.
- the intermediate material is typically selected from polytetrafluoroethlyene, ethylene tetrafluoroethylene, or variations thereof.
- the noncatalytic fluid is described in detail below.
- a second substrate that can be used in the present invention is a diffusion media material. If the diffusion media material is used, the catalytic fluid is prepared as described above and then deposited onto the diffusion media material using a direct writing instrument as described above in any of the patterns described above. The coated diffusion media material is then subjected to drying.
- the diffusion media material can be any suitable diffusion media material used in fuel cells.
- a second fluid that is noncatalytic fluid may be applied onto the diffusion media material after the deposition of catalytic fluid or simultaneously with the catalytic fluid.
- the substrate can be the electrolyte membrane material. Therefore, the catalytic fluid is deposited directly onto the electrolyte membrane material. The coated electrolyte membrane material is then subjected to drying.
- the electrolyte membrane material may be a proton conducting membrane, such as perfluorinated sulfonic acid, or some variation thereof.
- a second fluid that is noncatalytic may be applied onto the electrolyte membrane material after the deposition of catalytic fluid or simultaneously with the catalytic fluid, thereby forming a catalytic coating and a noncatalytic coating on one side of the electrolyte membrane material.
- an MEA 180 having both the catalytic coating 182 and the noncatalytic coating 184 is shown.
- the noncatalytic fluid forms a noncatalytic coating 184 when dried.
- the noncatalytic fluid is deposited in such a manner that it “shadows” the catalytic fluid.
- shadow we mean that one fluid follows the outline of the other fluid such that one fluid is not deposited directly over the other fluid.
- the noncatalytic fluid fills in the spaces between the lines of catalytic fluid on the substrate 202 .
- the noncatalytic fluid comprises a material that exhibits a high electrical conductivity, a high thermal conductivity, and low porosity.
- the noncatalytic fluid may be a carbonaceous material, carbon black, graphite, or combinations thereof.
- the carbonaeous material may also comprise a polymeric binder such as polyimide, polyethylene terephthalate, and combinations thereof.
- the viscosity of the noncatalytic fluid can be adjusted as appropriate to readily fill regions between catalytic coatings illustrated in FIG. 9. Generally, the noncatalytic fluid exhibits a viscosity between about 300 cp and about 10,000 cp.
- the noncatalytic fluid can be dispensed such that it is thicker on the substrate than the catalytic fluid.
- an MEA 180 having a catalytic coating 182 and a noncatalytic coating 184 is shown.
- the catalytic fluid can be deposited in a pattern that allows the lines of the catalytic coating 182 to align with channels in a flow field plate.
- the noncatalytic fluid can then be deposited in pattern that allows the lines of the noncatalytic coating 184 to align with the lands 186 in the flow field plate. This can be accomplished on both sides of the substrate 202 such that the catalytic fluid forming the catalytic anode coating 182 a is aligned with the channels 185 of the anode flow field plate.
- the noncatalytic coating 184 lies between the spaces of the catalytic fluid or catalytic anode coating 182 a , forming a noncatalytic coating 184 on the lands 186 of the anode flow field plate.
- the catalytic fluid forming the catalytic cathode coating 182 b is aligned with the channels 187 of the cathode flow field plate.
- the noncatalytic fluid is deposited between the spaces of the catalytic fluid or catalytic cathode coating 182 b , forming a noncatalytic coating 184 on the lands 186 of the cathode flow field plate.
- the catalytic anode coating 182 a and catalytic cathode coating 182 b are shown to be narrower than the opening of the channels 185 , 187 , respectively. It is to be appreciated that the catalytic anode coating 182 a and the catalytic cathode coating 182 b may be formed such that the coating is as wide as channels 185 , 817 or wider. This concept is explained in more detail in application Ser. No. 10/201,828.
- the fuel cell may eliminate the use of the diffusion media material in a fuel cell.
- the resulting fuel cell would be identical to the fuel cell 10 shown in FIG. 3, however, the diffusion media 60 , 62 , 64 , and 66 would not be present.
- an MEA fabrication system 200 according to one embodiment of the present invention is shown.
- the system has three primary stations: a first coating station, a second coating station, and a die cutting station.
- the substrate 202 is placed on a feed roll 212 where the substrate 202 is pulled from station to station by rollers 216 , 218 , 224 , and 226 .
- the substrate 202 is pulled over a first substrate holding device 214 .
- a nozzle 210 a dispenses catalytic fluid directly onto the first side 202 a of the substrate 202 .
- the catalytic fluid is typically dispensed in the form of a pattern, as described above.
- the substrate 202 is then pulled to first drying area 215 .
- the first drying area 215 can be an array of heated jets, an infrared heater, convection oven, or any other suitable device for removing a majority of solvent from the catalytic fluid.
- the first drying area 215 typically maintains a temperature between about 70° C. and about 100° C. While in first drying area 215 the catalytic fluid dries to the substrate 202 and forms a catalytic coating on the substrate 202 .
- the catalytic coating may be either an anode coating or a cathode coating.
- the substrate 202 is pulled to a second coating station.
- the substrate 202 is pulled over a second substrate holding device 228 .
- a catalytic fluid is deposited onto the second side 202 b of the substrate 202 .
- the catalytic fluid may be dispensed onto the substrate 202 in a manner that forms a pattern as discussed above.
- the substrate 202 is turned in a manner that allows the first side 202 a of the substrate 202 to face the opposite side such that nozzle 220 a is placing catalytic fluid on the second side 202 b of the substrate 202 .
- the second drying area 222 can be an array of heated jets, an infrared heater, convection oven, or any other suitable device for removing a majority of solvent from the catalytic fluid.
- the second drying area 222 typically maintains a temperature between about 70° C. to about 100° C. While in second drying area 222 , the catalytic fluid deposited on the second side 202 b of the substrate 202 forms a catalytic coating over the substrate 202 .
- the catalytic coating may be either an anode coating or a cathode coating.
- the substrate 202 is then pulled to a cutting station 230 where the substrate 202 is cut into separate pieces such that each piece of substrate 202 has both an anode coating and a cathode coating.
- the substrate 202 may be further cut in such a manner as to not interrupt a pattern that may have been formed on the substrate 202 by the fluid.
- more than one nozzle 210 a , 210 b , 220 a , and 220 b can be used at each station to deposit more than one fluid onto the substrate 202 at a time. While only two nozzles are shown at each station, it is to be appreciated that an array of nozzles can be present. When more than one fluid is deposited at a time, one fluid may shadow the other fluid.
- the noncatalytic fluid is described above as being the second fluid, it is to be appreciated that the second fluid can be any desired fluid.
- the second fluid can be a fluid containing a high amount of precious metal that is deposited near the inlet and exit of the MEA. Then a fluid have a lower amount of precious metal can be deposited in the center of the MEA, thereby, alleviating a portion of the durability and mass transfer losses.
- the nozzles 210 a , 210 b , 220 a , and 220 b are typically attached to a direct writing instrument as described above.
- the fluid is typically dispensed onto the substrate 202 in the form of one of the patterns as described above.
- the catalytic fluid is prepared as described above.
- the first and second substrate holding devices 214 and 228 can be vacuum tables or any other suitable device for holding the substrate in place.
- Ultrasonic energy can be applied to assist with coating of the substrate 202 .
- An ultrasonic probe 250 can be placed over the catalytic fluid 240 and the noncatalytic fluid 242 as the fluids are dispensed from nozzles 210 a and 210 b onto the substrate 202 .
- the ultrasonic probe 250 transmits acoustic energy 251 through the air above the contact line 241 of the catalytic fluid 240 and the noncatalytic fluid 242 as shown in FIG. 12 a .
- FIG. 12 a Referring specifically to FIG.
- the ultrasonic probe 250 can be placed below the substrate 202 to transmit acoustic energy 251 through the substrate 202 as the catalytic fluid 240 and the noncatalytic fluid 242 are dispensed from nozzles 210 a and 210 b .
- the acoustic energy 251 is transmitted at the contact line 241 of the catalytic fluid 240 and the noncatalytic fluid 242 .
- the acoustic energy 251 is applied continuously to the contact line 241 , such that surface tension at the liquid-liquid interface is continuously lowered at the point of application, thereby enabling better fluid flow and creating a smooth interface between fluids 240 and 242 .
- FIGS. 12 a and 12 b are shown using nozzles 210 a and 210 b which operate at the first coating station, it is to be appreciated that FIGS. 12 a and 12 b also show nozzles 220 a and 220 b which operate at the second coating station.
- the acoustic energy 251 can be used in any suitable method system for making the MEA having two fluids, comprising both a catalytic and noncatalytic fluid, dispensed onto a substrate both a catalytic fluid and a noncatalytic fluid. It is further to be appreciated that while this step is explained using acoustic energy from an ultrasonic probe, any instrument or energy that can relieve surface tension at the liquid-liquid interface can be used.
Abstract
Description
- This application is a continuation-in-part of U.S. patent application Ser. No. 10/201,828, filed Jul. 24, 2002.
- The present invention relates generally to fuel cells and particularly, to methods for forming a catalytic coating on a substrate.
- According to the present invention, methods for forming a catalytic coating on a substrate are provided.
- In one embodiment, a method of forming a catalytic coating on a substrate is provided. According to the method, a catalytic fluid is prepared and dispensed onto a substrate using a direct writing instrument that has been programmed to dispense the catalytic fluid onto the substrate in a pattern that forms a catalytic coating on the first side of the substrate.
- In another embodiment, a method of forming a catalytic coating on a substrate is provided. According to the method, a catalytic fluid is dispensed onto a substrate using a direct writing instrument that has been programmed to dispense the catalytic fluid onto the substrate in a pattern that forms a first coating on a first side of the substrate. A noncatalytic fluid is also dispensed onto the first side of the substrate using the same direct writing instrument in a shadow pattern of the first coating to form a second coating on the first side of the substrate.
- In still another embodiment, a method of preparing an electrolyte membrane for use in a membrane electrode assembly is provided. According to the method a catalytic fluid is dispensed onto an intermediate material using a direct writing instrument that has been programmed to dispense the catalytic fluid in a pattern that forms a catalytic coating on the intermediate material. The catalytic coating is then transferred from the intermediate material to an electrolyte membrane.
- In still yet another embodiment, a method of preparing an electrolyte membrane for use in a membrane electrode assembly is provided. According to the method, a catalytic fluid is dispensed onto an electrolyte material using a direct writing instrument.
- In still another embodiment, a method of preparing a diffusion media for use in a fuel cell is provided. According to the method, a catalytic fluid is dispensed onto a diffusion media using a direct writing instrument.
- In yet another embodiment, a system for preparing a membrane electrode assembly is provided. The system comprises first and second coating stations, first and second drying stations, a cutting station and a carrier device. The first coating station comprises a first substrate holding device, and at least one coating head for applying a coating to a first side of a substrate. The second coating station comprises a second substrate holding device, and at least one coating head for applying a coating to a second side of a substrate. The carrier device is configured to carry the substrate from station to station.
- These and other features and advantages of the invention will be more fully understood from the following description of the invention taken together with the accompanying drawings. It is noted that the scope of the claims is defined by the recitations therein and not by the specific discussion of features and advantages set forth in the present description.
- The following detailed description can be best understood when read in conjunction with the following drawings, where like structure is indicated with like reference numerals and in which:
- FIG. 1 is a schematic illustration of a fuel cell system.
- FIG. 2 is a schematic illustration of a vehicle including a fuel cell system.
- FIG. 3 is a schematic illustration of a fuel cell stack employing two fuel cells.
- FIG. 4 is an exploded view of a membrane electrode assembly.
- FIG. 5 is a block diagram of a direct writing instrument according to one embodiment of the present invention.
- FIG. 6 is an illustration of the nozzle and nozzle tip of a direct writing instrument forming a pattern on a substrate according to one embodiment of the present invention.
- FIG. 7 is an illustration of a pattern according to one embodiment of the present invention.
- FIG. 8 is an illustration of a pattern according to one embodiment of the present invention.
- FIG. 9 is an illustration of a membrane electrode assembly according to one embodiment of the present invention.
- FIG. 10 is an illustration of one side of a membrane electrode assembly having a first and a second coating according to one embodiment of the present invention.
- FIG. 11 is an illustration of a membrane electrode assembly system according to one embodiment of the present invention.
- FIG. 12a is an illustration of an ultrasonic probe applied above to a substrate.
- FIG. 12b is an illustration of an ultrasonic probe applied below a substrate.
- Skilled artisans appreciate that elements in the figures are illustrated for simplicity and clarity and have not necessarily been drawn to scale. For example, the dimensions of some of the elements in the figures may be exaggerated relative to other elements to help to improve understanding of embodiments of the present invention.
- Referring to FIG. 1, a fuel cell system2 for automotive applications is shown. It is to be appreciated, however, that other fuel cell system applications, such as for example, in the area of residential systems, may benefit from the present invention. As illustrated, the fuel cell system 2 includes a
primary reactor 4, a water-gas shift reactor 6, a preferential oxidation (PrOx)reactor 7, at least oneheat exchanger 8, atail gas combustor 9, and afuel cell 10. An explanation of these components and the operation of the fuel cell system 2 follows. It is to be appreciated that while one particular fuel cell system design is described, the present invention may be applicable to any fuel cell system design where catalytic coatings are utilized. - In the primary reactor4 a hydrocarbon fuel, such as gasoline or methane, air and steam are mixed, heated, and delivered to a catalyzed substrate. Here, the mixture is split into hydrogen, carbon monoxide, and other process gases, as the mixture flows over and reacts with the catalyst, forming a hydrogen-rich stream. Suitable catalyst materials include platinum group metals and base metals. This reaction occurs at temperatures in the range between about 700° C. and about 800° C.
- The hydrogen-rich stream leaving the
primary reactor 4 enters the water-gas shift reactor 6. Oxygen from water is used to convert carbon monoxide to carbon dioxide leaving additional hydrogen and increasing system efficiency. Operating temperatures of theshift reactor 6 range from about 250° C. to about 450° C. The hydrogen-rich stream leaving theshift reactor 6 then enters into thePrOx reactor 7, where the final cleanup of carbon monoxide takes place before the hydrogen-rich stream enters the fuel cell stack. Air is added to supply the oxygen needed to convert most of the remaining carbon monoxide to carbon dioxide, leaving additional hydrogen behind. Operating temperatures in the PrOxreactor 7 range from about 80° C. to about 200° C. Combined, the three reactors extract hydrogen from the fuel, and reduce or eliminate harmful emissions. - The three reactors are quickly heated to their operating temperatures before the fuel is introduced. The
heat exchanger 8 is therefore used to regulate the various temperatures throughout the fuel cell system 2. Typically, theheat exchanger 8 preheats the steam and air streams before entering into theprimary reactor 4. The waste heat from the hydrogen-rich stream exits theprimary reactor 4. - The hydrogen-rich stream then is supplied to the
fuel cell 10, which may comprise a stack of fuel cells, and reacted with oxygen from a source, such as air, to produce electricity, which can be used to power aload 11. The small quantities of unused hydrogen that leave thefuel cell 10 are consumed in thetail gas combustor 9 which operates at a temperature between about 300° C. to about 800° C. It is to be appreciated that while a series of reactors is described as being the hydrogen source, any hydrogen source is applicable to the present invention. - Referring to FIG. 2, a vehicle is shown having a
vehicle body 90, and a fuel cell system having afuel cell processor 4 and afuel cell stack 15. A discussion of the present invention as embodied in a fuel cell stack and a fuel cell, is provided hereafter in reference to FIGS. 3-9. - FIG. 3 depicts a
fuel cell stack 15 having a pair of membrane-electrode-assemblies (MEAs) 20 and 22 separated from each other by an electrically conductivefluid distribution plate 30.Plate 30 serves as a bi-polar plate having a plurality offluid flow channels MEAs MEAs plate 30, are stacked together between clampingplates 40 and 42, and electrically conductivefluid distribution plates Plates side containing channels MEAs -
Nonconductive gaskets diffusion media material MEAs Plates diffusion media material plate 30 presses up against thediffusion media material 62 on the anode face ofMEA 20, and againstdiffusion media material 64 on the cathode face ofMEA 22. - An oxidizing fluid, such as O2, is supplied to the cathode side of the fuel cell stack from
storage tank 70 viaappropriate supply plumbing 86. While the oxidizing fluid is being supplied to the cathode side, a reducing fluid, such as H2, is supplied to the anode side of the fuel cell fromstorage tank 72, via appropriate supply plumbing 88. The reducing fluid may be derived from a mixture of methane or gasoline, air, and water according to a reforming process in the presence of a catalyst. Exhaust plumbing (not shown) for both the H2 and O2/air sides of the MEAs will also be provided.Additional plumbing plate 30 andplates plates - Referring to FIG. 4, an exploded view of
membrane electrode assembly 20 is shown comprising ananode layer 102, acathode layer 106, and anelectrolyte 104 separating theanode layer 102 and thecathode layer 106.Membrane electrode assembly 20 andmembrane electrode assembly 22 are identical. For simplicity purposes, the present invention is being described in relation tomembrane electrode assembly 20, it is to be appreciated that the present invention can be applied tomembrane electrode assembly 22 and membrane electrode assemblies in general. - Generally, the
anode layer 102 and thecathode layer 106 are coatings formed in such a manner that they are in intimate contact with the electrolyte material once the fuel cell 10 (FIG. 1) is assembled. Methods of forming a catalytic coating on a substrate will now be explained. The first step in the method is to prepare a catalytic fluid. Generally, the catalytic fluid is a solution of ionomer, precious metal catalyst, solvent and water. A solution of ionomer and precious metal catalyst istypically prepared on a support in a mixture of the solvent and water. Different amounts maybe used depending on the desired viscosity of the catalytic fluid and the carbon to ionomer ratio desired. Generally, between about 30 grams and about 250 grams of solvent is mixed with between about 130 grams and about 200 grams of water and between about 5 grams and about 30 grams of ionomer and between about 5 grams and about 20 grams of precious metal catalyst are mixed together to form a solution. The support used for the solution of the ionomer and precious metal catalyst is typically carbon having a high surface area. The amount of carbon is generally between about 5 grams and about 20 grams. More specifically, the catalytic solution comprises about 4% by wt. of precious metal, about 4% by wt. of ionomer, about 4% by wt. of carbon, about 28% by wt. of water and about 60% by wt. of solvent. - The precious metal catalyst can be selected from platinum, platinum alloys and combinations thereof. The solvent can be selected from isopropyl alcohol, ethanol, butanol, and combinations thereof. The catalytic fluid can be prepared to exhibit a viscosity between about 70 cp and about 2000 cp, and more specifically, a viscosity of about 300 cp. The catalytic fluid can be prepared to exhibit an ionomer to carbon ratio of about 0.8 to about 2.0. The amount of solid in the solution is between about 8% by wt. and about 20% by wt., and more specifically about 12% by wt.
- Once the catalytic fluid is prepared, it is dispensed onto a
substrate 110 using a direct writing instrument. By “direct writing,” we mean depositing fluid directly onto a surface of a substrate in a pattern defined by the motion of the instrument, the motion of the substrate, or both. In direct writing, the deposited fluid forms a relatively well-defined line or area of deposition, relative to the overall dimensions of the deposition surface or the deposited pattern. Relative motion between the fluid source and the deposition substrate increases the extent of the well-defined line or area of deposition to create a more extensive deposited pattern. - FIG. 5 shows one embodiment of a direct writing instrument according to the present invention. The
direct writing instrument 150 comprises adesign system 152, awriting system controller 154 and awriting system 160. Thewriting system 160 further comprises afluid dispensing system 168, anozzle 166, anozzle tip 167, and asubstrate holding device 162. Thedesign system 152 stores a pattern that is drawn on a graphic display. Thedesign system 152 electronically communicates with thewriting system controller 154 such that thewriting system controller 154 knows the pattern and controls thewriting system 160 in a manner that allows thewriting system 160 to draw the pattern stored in thedesign system 152 on thesubstrate 110. - Referring to FIGS. 5 and 6, the
writing system controller 154 electronically communicates with thefluid dispensing system 168 and thesubstrate holding device 162. Therefore, thewriting system controller 154 allows thefluid dispensing system 168 to deliver the catalytic fluid to thenozzle 166. The catalytic fluid is dispensed through thenozzle tip 167 onto thesubstrate 110. The catalytic fluid may be carried to thefluid dispensing system 168 by any suitable means. - The
writing system controller 154 allows thesubstrate holding device 162 to move in a variety of positions that form thepattern 170 stored in the design system. By moving thesubstrate holding device 167 in various positions, thesubstrate 110 is accurately placed under thenozzle tip 167 while the catalytic fluid is being dispensed onto thesubstrate 110. In this manner, thenozzle 166 and thenozzle tip 167 do not move, but remain stationary while dispensing the catalytic fluid. Also, the pressure of thenozzle tip 167 is controlled such that no direct surface contact with thesubstrate 110 occurs. In another embodiment, thesubstrate holding device 162 remains stationary while thenozzle 166 andnozzle tip 167 move over thesubstrate 110 while dispensing the catalytic fluid. - The
design system 152 may be any computer-aided-design (CAD) interface that allows the design of a pattern via a graphics editor, digitizing tablet, or interface through a generic photo plotter interface. Thenozzle 166 may be heated to allow the catalytic fluid to remain in a molten state so that it will easily dispense through thenozzle tip 167. The width and thickness of the line, or lines, 169 forming thepattern 170 depend upon the nozzle tip diameter, the volumetric flowrate of the fluid to the nozzle tip, and the writing speed. The writing speed may vary depending upon the movement of thesubstrate 110 relative to thenozzle tip 167 or the movement of thenozzle tip 167 the substrate. Thus, the line thickness can be determined by the following equation: t=Q/(Vw), wherein Q=volumetric flow rate, w=line width, V=writing speed, and t=the line thickness. Viscosity of the fluid determines how close the line width is to the nozzle tip diameter, i.e. a low viscosity fluid will flow, therefore the line width is greater than the nozzle tip diameter while a high viscosity fluid does not flow as well, therefore, the line width is about equivalent to the nozzle tip diameter. - The
nozzle tip 167 can produce at least one line having a width between about 0.002 inches to about 0.25 inches. If more than one line is desired, a space up to about 0.0005 inches can be made between the lines. The line thickness can be up to 0.010 inches per pass with the nozzle. The line can have tolerances of about +/−0.000025 inches. The instrument writes at a speed between about 0.05 inches per second to about 5.0 inches per second. Theinstrument 150 operates on a minimum grid pitch of 0.0005 inches. - The
pattern 170 formed on thesubstrate 110 can be selected from a rectangular spiral, a straight line, a series of lines, or any suitable geometric pattern. An example of apattern 170 having a line, or series of lines, 169 forming a rectangular spiral is shown in FIG. 7. The spacing between adjacent lines can be adjusted. For the case of no spacing between adjacent lines, thepattern 170 would form a single continuous coating over theentire substrate 110. FIG. 8 shows apattern 170 having a series oflines 169 formed by a direct writing instrument according to one embodiment of the present invention. - Typically, after the pattern is formed on the
substrate 110, thesubstrate 110 is dried by a heat source having a temperature between about 70° C. and about 100 ° C. The pattern, once dried, forms a coating on thesubstrate 110. The heat source is selected from an infrared heater, convective oven, heated jets, or any other suitable heating device for removing solvent from the catalytic fluid. Thesubstrate 110 is subjected to the heat for a time sufficient to evaporate primarily all of the solvent in the coating, more specifically between about 2 minutes to about 10 minutes. - The method of making the membrane electrode assembly may vary depending upon the substrate upon which the catalytic fluid is dispensed. The substrate is generally selected from an intermediate material, a diffusion media material, or electrolyte membrane material.
- If the substrate is an intermediate material then the catalytic solution is deposited in the programmed pattern onto the intermediate material by a direct writing instrument. The coated substrate is then dried at a temperature between about 70° C. to about 100° C., typically in an oven. After the substrate is dry, a secondary ionomer solution may be applied to the substrate and dried. The application of the ionomer solution is typically performed by spraying. The coating formed on the intermediate material is then transferred to an electrolyte membrane material typically using a hot-press transfer. In one embodiment of the present invention, a second fluid that is nonreactive may be applied onto the intermediate material after the deposition of catalytic fluid or simultaneously with the catalytic fluid. The coating formed on the intermediate material is then transferred to an electrolyte membrane material. The intermediate material is typically selected from polytetrafluoroethlyene, ethylene tetrafluoroethylene, or variations thereof. The noncatalytic fluid is described in detail below.
- A second substrate that can be used in the present invention is a diffusion media material. If the diffusion media material is used, the catalytic fluid is prepared as described above and then deposited onto the diffusion media material using a direct writing instrument as described above in any of the patterns described above. The coated diffusion media material is then subjected to drying. The diffusion media material can be any suitable diffusion media material used in fuel cells. In one embodiment of the present invention, a second fluid that is noncatalytic fluid may be applied onto the diffusion media material after the deposition of catalytic fluid or simultaneously with the catalytic fluid.
- As an alternative, the substrate can be the electrolyte membrane material. Therefore, the catalytic fluid is deposited directly onto the electrolyte membrane material. The coated electrolyte membrane material is then subjected to drying. The electrolyte membrane material may be a proton conducting membrane, such as perfluorinated sulfonic acid, or some variation thereof.
- In one embodiment of the present invention, a second fluid that is noncatalytic may be applied onto the electrolyte membrane material after the deposition of catalytic fluid or simultaneously with the catalytic fluid, thereby forming a catalytic coating and a noncatalytic coating on one side of the electrolyte membrane material. Referring to FIG. 9, an
MEA 180 having both thecatalytic coating 182 and thenoncatalytic coating 184 is shown. The noncatalytic fluid forms anoncatalytic coating 184 when dried. The noncatalytic fluid is deposited in such a manner that it “shadows” the catalytic fluid. By “shadow” we mean that one fluid follows the outline of the other fluid such that one fluid is not deposited directly over the other fluid. When used, the noncatalytic fluid fills in the spaces between the lines of catalytic fluid on thesubstrate 202. - The noncatalytic fluid comprises a material that exhibits a high electrical conductivity, a high thermal conductivity, and low porosity. The noncatalytic fluid may be a carbonaceous material, carbon black, graphite, or combinations thereof. The carbonaeous material may also comprise a polymeric binder such as polyimide, polyethylene terephthalate, and combinations thereof. The viscosity of the noncatalytic fluid can be adjusted as appropriate to readily fill regions between catalytic coatings illustrated in FIG. 9. Generally, the noncatalytic fluid exhibits a viscosity between about 300 cp and about 10,000 cp. The noncatalytic fluid can be dispensed such that it is thicker on the substrate than the catalytic fluid.
- Referring to FIG. 10, one embodiment of an
MEA 180 having acatalytic coating 182 and anoncatalytic coating 184 is shown. The catalytic fluid can be deposited in a pattern that allows the lines of thecatalytic coating 182 to align with channels in a flow field plate. The noncatalytic fluid can then be deposited in pattern that allows the lines of thenoncatalytic coating 184 to align with thelands 186 in the flow field plate. This can be accomplished on both sides of thesubstrate 202 such that the catalytic fluid forming thecatalytic anode coating 182 a is aligned with thechannels 185 of the anode flow field plate. Therefore, thenoncatalytic coating 184 lies between the spaces of the catalytic fluid orcatalytic anode coating 182 a, forming anoncatalytic coating 184 on thelands 186 of the anode flow field plate. Similarly on the cathode side of theMEA 180, the catalytic fluid forming thecatalytic cathode coating 182 b is aligned with thechannels 187 of the cathode flow field plate. Thus, the noncatalytic fluid is deposited between the spaces of the catalytic fluid orcatalytic cathode coating 182 b, forming anoncatalytic coating 184 on thelands 186 of the cathode flow field plate. Thecatalytic anode coating 182 a andcatalytic cathode coating 182 b are shown to be narrower than the opening of thechannels catalytic anode coating 182 a and thecatalytic cathode coating 182 b may be formed such that the coating is as wide aschannels 185, 817 or wider. This concept is explained in more detail in application Ser. No. 10/201,828. - When the noncatalytic fluid is used, to form a
noncatalytic coating 184 on thesubstrate 202 and the substrate is an electrolyte membrane material, the fuel cell may eliminate the use of the diffusion media material in a fuel cell. Thus, the resulting fuel cell would be identical to thefuel cell 10 shown in FIG. 3, however, thediffusion media - Referring to FIG. 11, an
MEA fabrication system 200 according to one embodiment of the present invention is shown. The system has three primary stations: a first coating station, a second coating station, and a die cutting station. Thesubstrate 202 is placed on afeed roll 212 where thesubstrate 202 is pulled from station to station byrollers substrate 202 is pulled over a firstsubstrate holding device 214. Once over the firstsubstrate holding device 214, anozzle 210 a dispenses catalytic fluid directly onto thefirst side 202 a of thesubstrate 202. The catalytic fluid is typically dispensed in the form of a pattern, as described above. Thesubstrate 202 is then pulled tofirst drying area 215. Thefirst drying area 215 can be an array of heated jets, an infrared heater, convection oven, or any other suitable device for removing a majority of solvent from the catalytic fluid. Thefirst drying area 215 typically maintains a temperature between about 70° C. and about 100° C. While infirst drying area 215 the catalytic fluid dries to thesubstrate 202 and forms a catalytic coating on thesubstrate 202. The catalytic coating may be either an anode coating or a cathode coating. - Next, the
substrate 202 is pulled to a second coating station. In the second coating station, thesubstrate 202 is pulled over a secondsubstrate holding device 228. A catalytic fluid is deposited onto thesecond side 202 b of thesubstrate 202. The catalytic fluid may be dispensed onto thesubstrate 202 in a manner that forms a pattern as discussed above. While being pulled throughfirst drying area 215, thesubstrate 202 is turned in a manner that allows thefirst side 202 a of thesubstrate 202 to face the opposite side such thatnozzle 220 a is placing catalytic fluid on thesecond side 202 b of thesubstrate 202. After the catalytic fluid is placed onto thesecond side 202 b of thesubstrate 202, thesubstrate 202 is pulled to asecond drying area 222. Thesecond drying area 222 can be an array of heated jets, an infrared heater, convection oven, or any other suitable device for removing a majority of solvent from the catalytic fluid. Thesecond drying area 222 typically maintains a temperature between about 70° C. to about 100° C. While insecond drying area 222, the catalytic fluid deposited on thesecond side 202 b of thesubstrate 202 forms a catalytic coating over thesubstrate 202. The catalytic coating may be either an anode coating or a cathode coating. - The
substrate 202 is then pulled to a cuttingstation 230 where thesubstrate 202 is cut into separate pieces such that each piece ofsubstrate 202 has both an anode coating and a cathode coating. Thesubstrate 202 may be further cut in such a manner as to not interrupt a pattern that may have been formed on thesubstrate 202 by the fluid. - As FIG. 11 shows, more than one
nozzle substrate 202 at a time. While only two nozzles are shown at each station, it is to be appreciated that an array of nozzles can be present. When more than one fluid is deposited at a time, one fluid may shadow the other fluid. Although the noncatalytic fluid is described above as being the second fluid, it is to be appreciated that the second fluid can be any desired fluid. For example, the second fluid can be a fluid containing a high amount of precious metal that is deposited near the inlet and exit of the MEA. Then a fluid have a lower amount of precious metal can be deposited in the center of the MEA, thereby, alleviating a portion of the durability and mass transfer losses. - The
nozzles substrate 202 in the form of one of the patterns as described above. The catalytic fluid is prepared as described above. The first and secondsubstrate holding devices - Referring to FIGS. 12a and 12 b, an additional step to the method of applying more than one fluid to the substrate is shown. Ultrasonic energy can be applied to assist with coating of the
substrate 202. Anultrasonic probe 250 can be placed over thecatalytic fluid 240 and thenoncatalytic fluid 242 as the fluids are dispensed fromnozzles substrate 202. Theultrasonic probe 250 transmitsacoustic energy 251 through the air above thecontact line 241 of thecatalytic fluid 240 and thenoncatalytic fluid 242 as shown in FIG. 12a. Referring specifically to FIG. 12b, theultrasonic probe 250 can be placed below thesubstrate 202 to transmitacoustic energy 251 through thesubstrate 202 as thecatalytic fluid 240 and thenoncatalytic fluid 242 are dispensed fromnozzles acoustic energy 251 is transmitted at thecontact line 241 of thecatalytic fluid 240 and thenoncatalytic fluid 242. - The
acoustic energy 251 is applied continuously to thecontact line 241, such that surface tension at the liquid-liquid interface is continuously lowered at the point of application, thereby enabling better fluid flow and creating a smooth interface betweenfluids nozzles nozzles acoustic energy 251 can be used in any suitable method system for making the MEA having two fluids, comprising both a catalytic and noncatalytic fluid, dispensed onto a substrate both a catalytic fluid and a noncatalytic fluid. It is further to be appreciated that while this step is explained using acoustic energy from an ultrasonic probe, any instrument or energy that can relieve surface tension at the liquid-liquid interface can be used. - While the invention has been described by reference to certain preferred embodiments, it should be understood that numerous changes could be made within the spirit and scope of the inventive concepts described. Accordingly, it is intended that the invention not be limited to the disclosed embodiments, but that it have the full scope permitted by the language of the following claims.
Claims (105)
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/369,145 US20040018937A1 (en) | 2002-07-24 | 2003-02-18 | Methods for forming catalytic coating on a substrate |
DE10333289A DE10333289A1 (en) | 2002-07-24 | 2003-07-22 | Device for forming a catalytic coating on a substrate |
CNA031550045A CN1508896A (en) | 2002-07-24 | 2003-07-24 | Method for forming catalytic dressing on substrate |
JP2003279279A JP3825019B2 (en) | 2002-07-24 | 2003-07-24 | Method for forming a catalytic coating on a substrate |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/201,828 US6916573B2 (en) | 2002-07-24 | 2002-07-24 | PEM fuel cell stack without gas diffusion media |
US10/369,145 US20040018937A1 (en) | 2002-07-24 | 2003-02-18 | Methods for forming catalytic coating on a substrate |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US10/201,828 Continuation-In-Part US6916573B2 (en) | 2002-07-24 | 2002-07-24 | PEM fuel cell stack without gas diffusion media |
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US20040018937A1 true US20040018937A1 (en) | 2004-01-29 |
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ID=30769709
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/201,828 Expired - Lifetime US6916573B2 (en) | 2002-07-24 | 2002-07-24 | PEM fuel cell stack without gas diffusion media |
US10/369,145 Abandoned US20040018937A1 (en) | 2002-07-24 | 2003-02-18 | Methods for forming catalytic coating on a substrate |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
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US10/201,828 Expired - Lifetime US6916573B2 (en) | 2002-07-24 | 2002-07-24 | PEM fuel cell stack without gas diffusion media |
Country Status (6)
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US (2) | US6916573B2 (en) |
JP (1) | JP2006502533A (en) |
CN (1) | CN1856893A (en) |
AU (1) | AU2003263796A1 (en) |
DE (1) | DE10392954T5 (en) |
WO (1) | WO2004010516A2 (en) |
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Also Published As
Publication number | Publication date |
---|---|
CN1856893A (en) | 2006-11-01 |
AU2003263796A1 (en) | 2004-02-09 |
WO2004010516A2 (en) | 2004-01-29 |
WO2004010516A3 (en) | 2005-08-18 |
JP2006502533A (en) | 2006-01-19 |
AU2003263796A8 (en) | 2004-02-09 |
US20040018413A1 (en) | 2004-01-29 |
DE10392954T5 (en) | 2005-07-21 |
US6916573B2 (en) | 2005-07-12 |
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