US20060172882A1 - Membrane electrode assemblies and method for manufacture - Google Patents
Membrane electrode assemblies and method for manufacture Download PDFInfo
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- US20060172882A1 US20060172882A1 US11/391,973 US39197306A US2006172882A1 US 20060172882 A1 US20060172882 A1 US 20060172882A1 US 39197306 A US39197306 A US 39197306A US 2006172882 A1 US2006172882 A1 US 2006172882A1
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- 239000012528 membrane Substances 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title abstract description 20
- 230000000712 assembly Effects 0.000 title abstract description 6
- 238000000429 assembly Methods 0.000 title abstract description 6
- 238000004519 manufacturing process Methods 0.000 title description 3
- 239000000463 material Substances 0.000 claims abstract description 36
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- 239000004020 conductor Substances 0.000 claims abstract description 19
- 239000010408 film Substances 0.000 claims description 57
- 239000000446 fuel Substances 0.000 claims description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 239000010409 thin film Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- CFQCIHVMOFOCGH-UHFFFAOYSA-N platinum ruthenium Chemical compound [Ru].[Pt] CFQCIHVMOFOCGH-UHFFFAOYSA-N 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 claims 1
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- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 16
- 238000003475 lamination Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920000557 Nafion® Polymers 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
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- 239000011532 electronic conductor Substances 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical group FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
Images
Classifications
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- 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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/043—Processes of manufacture in general involving compressing or compaction
- H01M4/0435—Rolling or calendering
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- H—ELECTRICITY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
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- 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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
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- 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]
-
- 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
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1023—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes
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- 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
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
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- 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
- H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
- H01M8/2404—Processes or apparatus for grouping fuel cells
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- 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
- H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
- H01M8/241—Grouping of fuel cells, e.g. stacking of fuel cells with solid or matrix-supported electrolytes
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- 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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
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- 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
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
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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
-
- 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
- Membrane electrode assemblies are the core of fuel cells such as proton exchange media fuel cells which are well known. See, for example, “Fuel Cell Systems Explained,” Larminie & Dicks, John Wylie & Sons, Ltd. (2000), the contents of which are incorporated herein by reference. Membrane electrode assemblies contain the electron collectors, the catalyst, and the proton exchange medium. Current methods of production of MEAs focus on individual units in which the catalysts are chemically deposited or inked on an electron collector and proton exchange medium. The elements of the unit are then sandwiched together with the application of heat and pressure to produce a single MEA. This prior art method is both costly and not easily scaled up to high volume production.
- the invention is a method for making a membrane electrode assembly including providing an elongate proton exchange membrane film having a front and a back side.
- a first catalyst material is deposited in a repeating cell pattern on the front side of the film to form cathode regions of a plurality of unit cells.
- a second catalyst material is deposited in the repeating pattern on the back side of the film to form anode regions of the unit cells.
- An elongate support film perforated in the repeating cell pattern is provided and electron conductor material is deposited onto the support film in the repeating cell pattern along with electrical contact nubs.
- An adhesive film precut in the repeating cell pattern is also provided and the support and adhesive films are assembled on the front and back sides of the proton exchange membrane film with the repeating patterns of the respective films aligned and with the unit cells connected electrically.
- the assembled films are passed through hot rollers to laminate the films to produce the assembly.
- FIG. 1 is a plan view of a proton exchange membrane film with a deposited catalyst in one embodiment of the invention.
- FIG. 2 is a plan view of a perforated Kapton support film in one embodiment of the invention.
- FIGS. 3 and 4 are plan views of Kapton support film with electron conductor material deposited thereon in one embodiment of the invention.
- FIG. 5 is a plan view of Kapton support film with an adhesive film aligned and laminated thereon in one embodiment of the invention.
- FIG. 6 is a plan view showing the alignment and lamination of proton exchange media over adhesive film in one embodiment of the invention.
- FIG. 7 is a plan view of a completed membrane electrode assembly of the invention in one embodiment of the invention.
- FIG. 8 is a schematic view illustrating the reel-to-reel process of the invention in one embodiment of the invention.
- FIG. 9 is a perspective schematic view of a Z-folded membrane electrode assembly in one embodiment of the invention.
- FIG. 10 is a perspective schematic view of a Z-folded membrane electrode assembly inserted into an endplate in one embodiment of the invention.
- FIG. 11 is a cross-sectional schematic view of a fuel cell using the membrane electrode assembly in one embodiment of the invention.
- FIG. 12 is a schematic illustration of a roll transfer lamination process in one embodiment of the invention.
- FIG. 13 is a planned view of a proton exchange membrane film with a deposited catalyst in one embodiment of the invention.
- FIG. 14 is a planned view of a cell for parallel connection in one embodiment of the invention.
- FIG. 15 is a planned view of a completed parallel connect PEM material cell in one embodiment of the invention.
- FIG. 16 is a planned view of parallel connected cells in one embodiment of the invention.
- FIG. 17 is a planned view of a conventional flooded anode stacked design in one embodiment of the invention.
- FIG. 18 is a schematic illustration of the flooded anode stacked design in one embodiment of the invention.
- FIG. 19 is a schematic illustration of a stacked design utilizing an anode wicking medium in one embodiment of the invention.
- the method for making a membrane electrode assembly includes providing an elongate proton exchange membrane film having a front and back side.
- a first catalyst material is deposited in a repeating cell pattern on the front side of the film to form cathode regions of a plurality of unit cells.
- a second catalyst material is deposited in the repeating pattern on the back side of the film to form anode regions of the unit cells.
- An elongate support film- perforated in the repeating cell pattern is provided and electron conductor material is deposited onto the support film in the repeating cell pattern along with electrical contact nubs.
- An adhesive film pre-cut in the repeating cell pattern is also provided and the support and adhesive films are assembled on the front and back sides of the proton exchange membrane film with the repeating patterns of the respective films aligned and with the unit cells connected electrically.
- a suitable proton exchange membrane film is Nafion® available from Dupont Chemical Corporation. Nafion is basically sulphonated polytetrafluoroethylene.
- a suitable first catalyst material is platinum and a suitable second catalyst material is platinum-ruthenium.
- a suitable support film is Kapton.
- Suitable electronic conductor materials are thin film carbon and thin film metals.
- the unit cells made according to the present invention may be connected electrically in series or in parallel.
- the proton exchange membrane, the support film, and the adhesive film be fed from respective rolls and that the completed membrane electrode assembly is in the form of a continuous roll of material.
- the invention is a fuel cell including a Z-folded strip including a plurality of electrically connected membrane electrode assemblies as described above.
- a pair of endplates support the Z-folded strip to create alternating anode and cathode chambers. Alternating fuel and air manifolds are provided in the endplates to complete a fuel cell.
- the present invention thus produces membrane electrode assemblies in a reel-to-reel process.
- the method according to the invention allows MEAs to be constructed in a continuous process wherein each cell is connected electrically to the next either in series or in parallel as desired. With a series connection the desired voltage is proportional to the number of cells so that one simply chooses the appropriate number of cells and cuts them from the reel to form them into a stack. Alternatively, stacks themselves may be connected in series or parallel.
- the continuous production process of the invention is low cost and scalable to very high volume.
- the cells are internally connected, in series or in parallel, and any desired voltage may be selected by-using the appropriate number of cells.
- a proton exchange membrane (PEM) film 10 is a polymer electrolyte membrane.
- a suitable membrane is a sulphonated fluoropolymer, often fluoroethylene, such as Nafion, a registered trademark of, and available from, the Dupont Chemical Corporation.
- a catalyst 12 is deposited in a repeating pattern on a front surface of the PEM film membrane 10 .
- a catalyst is also deposited on the back surface of the film 10 .
- Contact vias 14 are punched out of the membrane 10 .
- a suitable catalyst 12 is platinum to form a cathode region and a suitable catalyst for the other side of the PEM 10 is platinum-ruthenium to form an anode region.
- the catalysts are deposited by any suitable technique known to those skilled in the art.
- the catalyst pattern will define unit cells in a completed membrane electrode assembly as will become clear in this specification.
- a support film 16 is preferably made of Kapton or other type of polyimide material or other suitable plastic material.
- the Kapton film 16 includes perforations 18 in the same repeating pattern as with the catalyst 12 shown in FIG. 1 .
- the perforations 18 will allow fuel and air to reach the catalysts once the membrane electrode assembly is assembled. It is preferred that the Kapton film 16 be provided on and deployed from a roll.
- electron conductor material 20 and an optional catalyst is deposited on the Kapton film 16 .
- a suitable electron conductor material 20 is carbon or thin film metal such as stainless steel. If desired, an optional catalyst may be deposited on top of the electron conductor material.
- the electron conductor and optional catalyst depositions can be achieved by sputtering through a shadow mask, for example.
- contact nubs 22 are located either on the right or left of the cell pattern depending on whether the Kapton film 16 is laminated on the front or back of the PEM film.
- the contact nubs 22 will eventually be in electrical contact, as will be described below.
- the nubs 22 will thereby form a continuous series electrical connection between cells along the completed membrane electrode assembly on a reel.
- an adhesive film 24 is pre-cut to expose the electron conductor/catalyst on the Kapton film 16 as well as the contact vias 14 .
- a suitable temperature/pressure sensitive adhesive film 24 is based on epoxy, urethane, silicone or acrylate adhesive chemistry.
- the adhesive material 24 is in its low-tack form as it is aligned over the Kapton film 16 and laminated to it. The adhesive film 24 will be heat cured later in the process as described below.
- the PEM film 10 is aligned over the adhesive film 24 /Kapton film 16 combination so that the catalyst area 12 is aligned with the perforations 20 .
- a second adhesive film is also aligned.
- a second processed Kapton film described in FIGS. 3 and 4 is aligned and laminated over the adhesive film 24 .
- FIG. 8 Schematically, Kapton support film 16 is supported on rolls 30 and 32 . Similarly, the adhesive film 24 is supported on rolls 34 and 36 . Finally, the PEM film 10 is supported on a roll 38 . As discussed above, these various layers are aligned and registered and passed through the nip of hot rollers 40 and 42 to produce the completed membrane electrode assembly 44 and as shown in FIG. 7 . It will be appreciated that the individual cells are connected in series electrically. The completed membrane electrode assembly 44 may be wound onto a takeup roll (not shown).
- FIG. 9 illustrates a 5-cell strip of the completed MEA Z-folded to form alternating anode 46 and cathode 48 chambers. Electrical anode contacts are made at 50 and external cathode contacts are made at area 52 beneath the lower anode chamber 46 .
- the cells in the Z-folded MEA of FIG. 9 are connected in series so that individual cell voltages are additive.
- the Z-folded strip is mated to an end plate 52 .
- a second end plate (not shown for clarity) to complete a fuel cell structure.
- the MEA assembly 44 is bonded into a groove in the endplate 52 .
- Alternating fuel manifolds 54 and air manifolds 56 are molded into the end plate 52 which may be made of plastic. In this way, fuel is brought into contact with the anode and air is brought into contact with the cathode of each of the cells in the unit.
- additional cover plates in addition to the two end plates complete the fuel cell stack.
- FIG. 12 An alternative process referred to as a roll transfer lamination process is shown in FIG. 12 .
- the adhesive film 24 is pre-cut around each cell as with the earlier embodiment.
- the PEM material 10 is also pre-cut into squares designed to fit exactly into a cell opening left by the adhesive film 24 .
- the pre-cut PEM material 10 is carried by a backing film 60 that passes over a transfer roll 62 and is discarded on a take up roll 64 .
- the pre-cut PEM material 10 is transferred to the Kapton support film 16 at the location of a compression roller 66 and inserted into the opening left by the adhesive film 24 .
- the thickness of the adhesive film 24 is adjusted to accommodate the thickness of the PEM material 10 . Note that in this embodiment, only one adhesive film is required. As with the earlier embodiment, the material passes through the nip of hot rollers 40 and 42 .
- the process illustrated in FIG. 12 has several advantages. First of all it uses less of the expensive PEM material. Second, the process eliminates one adhesive film but requires the one used to be not only thicker but also to have a specified thickness. Finally, the adhesive film is not required to bond to the PEM material as in the earlier embodiment.
- FIG. 12 The roll transfer lamination process of FIG. 12 will be used to illustrate a parallel electrical connection of the individual cells.
- FIG. 13 is similar to the embodiment of FIG. 1 but note that there are no vias for parallel electrical connection.
- adjacent cells are connected to each other unlike the embodiment of FIG. 4 .
- FIG. 14 all anodes are connected together and all cathodes are connected together resulting in a parallel electrical connection.
- Kapton film with appropriate thin film is required for either anode or cathode use as shown in FIG. 14 .
- This parallel type of connection has the great advantage of not requiring internal connection which can complicate the process.
- the completed parallel connect PEM material is shown in FIGS. 15 and 16 .
- FIGS. 17 and 18 illustrate a conventional flooded anode stack design.
- each cell is cut from the roll, bonded to gasket material 70 and built into a stack as shown in FIG. 18 .
- This design has the advantage of simplicity but the disadvantage that all electrical connections must be done externally as shown at 72 in FIG. 18 .
- the stack is similar to that shown in FIG. 18 except that an anode wicking medium 72 is included in each anode chamber.
- the stack design of FIG. 19 uses the capillary material 72 to bring fuel to the anode chamber.
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- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
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- Life Sciences & Earth Sciences (AREA)
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Abstract
Reel-to-Reel method for making membrane electrode assemblies. A first catalyst is deposited in a repeating cell pattern on a first side of a proton exchange membrane film. A second catalyst is deposited on the back side of the proton exchange membrane. An electron conductor material is deposited on a support film which is adhered by means of an adhesive film to the proton exchange membrane film. The various layers are aligned and laminated together to form the membrane electrode assembly.
Description
- Membrane electrode assemblies (MEA) are the core of fuel cells such as proton exchange media fuel cells which are well known. See, for example, “Fuel Cell Systems Explained,” Larminie & Dicks, John Wylie & Sons, Ltd. (2000), the contents of which are incorporated herein by reference. Membrane electrode assemblies contain the electron collectors, the catalyst, and the proton exchange medium. Current methods of production of MEAs focus on individual units in which the catalysts are chemically deposited or inked on an electron collector and proton exchange medium. The elements of the unit are then sandwiched together with the application of heat and pressure to produce a single MEA. This prior art method is both costly and not easily scaled up to high volume production.
- In one aspect, the invention is a method for making a membrane electrode assembly including providing an elongate proton exchange membrane film having a front and a back side. A first catalyst material is deposited in a repeating cell pattern on the front side of the film to form cathode regions of a plurality of unit cells. A second catalyst material is deposited in the repeating pattern on the back side of the film to form anode regions of the unit cells. An elongate support film perforated in the repeating cell pattern is provided and electron conductor material is deposited onto the support film in the repeating cell pattern along with electrical contact nubs. An adhesive film precut in the repeating cell pattern is also provided and the support and adhesive films are assembled on the front and back sides of the proton exchange membrane film with the repeating patterns of the respective films aligned and with the unit cells connected electrically. The assembled films are passed through hot rollers to laminate the films to produce the assembly.
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FIG. 1 is a plan view of a proton exchange membrane film with a deposited catalyst in one embodiment of the invention. -
FIG. 2 is a plan view of a perforated Kapton support film in one embodiment of the invention. -
FIGS. 3 and 4 are plan views of Kapton support film with electron conductor material deposited thereon in one embodiment of the invention. -
FIG. 5 is a plan view of Kapton support film with an adhesive film aligned and laminated thereon in one embodiment of the invention. -
FIG. 6 is a plan view showing the alignment and lamination of proton exchange media over adhesive film in one embodiment of the invention. -
FIG. 7 is a plan view of a completed membrane electrode assembly of the invention in one embodiment of the invention. -
FIG. 8 is a schematic view illustrating the reel-to-reel process of the invention in one embodiment of the invention. -
FIG. 9 is a perspective schematic view of a Z-folded membrane electrode assembly in one embodiment of the invention. -
FIG. 10 is a perspective schematic view of a Z-folded membrane electrode assembly inserted into an endplate in one embodiment of the invention. -
FIG. 11 is a cross-sectional schematic view of a fuel cell using the membrane electrode assembly in one embodiment of the invention. -
FIG. 12 is a schematic illustration of a roll transfer lamination process in one embodiment of the invention. -
FIG. 13 is a planned view of a proton exchange membrane film with a deposited catalyst in one embodiment of the invention. -
FIG. 14 is a planned view of a cell for parallel connection in one embodiment of the invention. -
FIG. 15 is a planned view of a completed parallel connect PEM material cell in one embodiment of the invention. -
FIG. 16 is a planned view of parallel connected cells in one embodiment of the invention. -
FIG. 17 is a planned view of a conventional flooded anode stacked design in one embodiment of the invention. -
FIG. 18 is a schematic illustration of the flooded anode stacked design in one embodiment of the invention. -
FIG. 19 is a schematic illustration of a stacked design utilizing an anode wicking medium in one embodiment of the invention. - As set forth above, the method for making a membrane electrode assembly includes providing an elongate proton exchange membrane film having a front and back side. A first catalyst material is deposited in a repeating cell pattern on the front side of the film to form cathode regions of a plurality of unit cells. A second catalyst material is deposited in the repeating pattern on the back side of the film to form anode regions of the unit cells. An elongate support film- perforated in the repeating cell pattern is provided and electron conductor material is deposited onto the support film in the repeating cell pattern along with electrical contact nubs. An adhesive film pre-cut in the repeating cell pattern is also provided and the support and adhesive films are assembled on the front and back sides of the proton exchange membrane film with the repeating patterns of the respective films aligned and with the unit cells connected electrically.
- A suitable proton exchange membrane film is Nafion® available from Dupont Chemical Corporation. Nafion is basically sulphonated polytetrafluoroethylene. A suitable first catalyst material is platinum and a suitable second catalyst material is platinum-ruthenium.
- In a preferred embodiment, a suitable support film is Kapton. Suitable electronic conductor materials are thin film carbon and thin film metals. The unit cells made according to the present invention may be connected electrically in series or in parallel.
- It is preferred that the proton exchange membrane, the support film, and the adhesive film be fed from respective rolls and that the completed membrane electrode assembly is in the form of a continuous roll of material.
- In another aspect, the invention is a fuel cell including a Z-folded strip including a plurality of electrically connected membrane electrode assemblies as described above. A pair of endplates support the Z-folded strip to create alternating anode and cathode chambers. Alternating fuel and air manifolds are provided in the endplates to complete a fuel cell.
- The present invention thus produces membrane electrode assemblies in a reel-to-reel process. The method according to the invention allows MEAs to be constructed in a continuous process wherein each cell is connected electrically to the next either in series or in parallel as desired. With a series connection the desired voltage is proportional to the number of cells so that one simply chooses the appropriate number of cells and cuts them from the reel to form them into a stack. Alternatively, stacks themselves may be connected in series or parallel. The continuous production process of the invention is low cost and scalable to very high volume. The cells are internally connected, in series or in parallel, and any desired voltage may be selected by-using the appropriate number of cells.
- With reference to
FIG. 1 , a proton exchange membrane (PEM)film 10 is a polymer electrolyte membrane. A suitable membrane is a sulphonated fluoropolymer, often fluoroethylene, such as Nafion, a registered trademark of, and available from, the Dupont Chemical Corporation. Acatalyst 12 is deposited in a repeating pattern on a front surface of thePEM film membrane 10. A catalyst is also deposited on the back surface of thefilm 10. Contactvias 14 are punched out of themembrane 10. For example, if thePEM 10 is intended for a direct methanol fuel cell, asuitable catalyst 12 is platinum to form a cathode region and a suitable catalyst for the other side of thePEM 10 is platinum-ruthenium to form an anode region. The catalysts are deposited by any suitable technique known to those skilled in the art. The catalyst pattern will define unit cells in a completed membrane electrode assembly as will become clear in this specification. - With reference to
FIG. 2 , asupport film 16 is preferably made of Kapton or other type of polyimide material or other suitable plastic material. The Kaptonfilm 16 includesperforations 18 in the same repeating pattern as with thecatalyst 12 shown inFIG. 1 . Theperforations 18 will allow fuel and air to reach the catalysts once the membrane electrode assembly is assembled. It is preferred that theKapton film 16 be provided on and deployed from a roll. As shown inFIGS. 3 and 4 ,electron conductor material 20 and an optional catalyst is deposited on theKapton film 16. A suitableelectron conductor material 20 is carbon or thin film metal such as stainless steel. If desired, an optional catalyst may be deposited on top of the electron conductor material. The electron conductor and optional catalyst depositions can be achieved by sputtering through a shadow mask, for example. As can be seen inFIGS. 3 and 4 , contactnubs 22 are located either on the right or left of the cell pattern depending on whether theKapton film 16 is laminated on the front or back of the PEM film. The contact nubs 22 will eventually be in electrical contact, as will be described below. Thenubs 22 will thereby form a continuous series electrical connection between cells along the completed membrane electrode assembly on a reel. Those skilled in the art will appreciate that parallel connection is equally possible and will be discussed below. - With reference to
FIG. 5 , anadhesive film 24 is pre-cut to expose the electron conductor/catalyst on theKapton film 16 as well as thecontact vias 14. A suitable temperature/pressure sensitiveadhesive film 24 is based on epoxy, urethane, silicone or acrylate adhesive chemistry. Theadhesive material 24 is in its low-tack form as it is aligned over theKapton film 16 and laminated to it. Theadhesive film 24 will be heat cured later in the process as described below. - With reference to
FIG. 6 , thePEM film 10 is aligned over theadhesive film 24/Kapton film 16 combination so that thecatalyst area 12 is aligned with theperforations 20. As will be described below, a second adhesive film is also aligned. As shown inFIG. 7 , a second processed Kapton film described inFIGS. 3 and 4 is aligned and laminated over theadhesive film 24. - The overall process is shown in general terms in
FIG. 8 . Schematically,Kapton support film 16 is supported onrolls adhesive film 24 is supported onrolls PEM film 10 is supported on aroll 38. As discussed above, these various layers are aligned and registered and passed through the nip ofhot rollers membrane electrode assembly 44 and as shown inFIG. 7 . It will be appreciated that the individual cells are connected in series electrically. The completedmembrane electrode assembly 44 may be wound onto a takeup roll (not shown). -
FIG. 9 illustrates a 5-cell strip of the completed MEA Z-folded to form alternatinganode 46 andcathode 48 chambers. Electrical anode contacts are made at 50 and external cathode contacts are made atarea 52 beneath thelower anode chamber 46. The cells in the Z-folded MEA ofFIG. 9 are connected in series so that individual cell voltages are additive. - As shown in
FIG. 10 , the Z-folded strip is mated to anend plate 52. Those skilled in the art will appreciate there will be a second end plate (not shown for clarity) to complete a fuel cell structure. As shown inFIG. 11 , theMEA assembly 44 is bonded into a groove in theendplate 52. Alternatingfuel manifolds 54 andair manifolds 56 are molded into theend plate 52 which may be made of plastic. In this way, fuel is brought into contact with the anode and air is brought into contact with the cathode of each of the cells in the unit. Those skilled in the art will appreciate that additional cover plates in addition to the two end plates complete the fuel cell stack. - An alternative process referred to as a roll transfer lamination process is shown in
FIG. 12 . In this embodiment, theadhesive film 24 is pre-cut around each cell as with the earlier embodiment. ThePEM material 10 is also pre-cut into squares designed to fit exactly into a cell opening left by theadhesive film 24. Thepre-cut PEM material 10 is carried by abacking film 60 that passes over atransfer roll 62 and is discarded on a take up roll 64. Thepre-cut PEM material 10 is transferred to theKapton support film 16 at the location of acompression roller 66 and inserted into the opening left by theadhesive film 24. The thickness of theadhesive film 24 is adjusted to accommodate the thickness of thePEM material 10. Note that in this embodiment, only one adhesive film is required. As with the earlier embodiment, the material passes through the nip ofhot rollers - The process illustrated in
FIG. 12 has several advantages. First of all it uses less of the expensive PEM material. Second, the process eliminates one adhesive film but requires the one used to be not only thicker but also to have a specified thickness. Finally, the adhesive film is not required to bond to the PEM material as in the earlier embodiment. - The roll transfer lamination process of
FIG. 12 will be used to illustrate a parallel electrical connection of the individual cells.FIG. 13 is similar to the embodiment ofFIG. 1 but note that there are no vias for parallel electrical connection. Note that inFIG. 14 adjacent cells are connected to each other unlike the embodiment ofFIG. 4 . Thus, inFIG. 14 all anodes are connected together and all cathodes are connected together resulting in a parallel electrical connection. Because anodes and cathodes are not connected to each other as in the series embodiment, only one type of Kapton film with appropriate thin film is required for either anode or cathode use as shown inFIG. 14 . This parallel type of connection has the great advantage of not requiring internal connection which can complicate the process. The completed parallel connect PEM material is shown inFIGS. 15 and 16 . -
FIGS. 17 and 18 illustrate a conventional flooded anode stack design. In this design each cell is cut from the roll, bonded togasket material 70 and built into a stack as shown inFIG. 18 . This design has the advantage of simplicity but the disadvantage that all electrical connections must be done externally as shown at 72 inFIG. 18 . - With reference now to
FIG. 19 , the stack is similar to that shown inFIG. 18 except that ananode wicking medium 72 is included in each anode chamber. The stack design ofFIG. 19 uses thecapillary material 72 to bring fuel to the anode chamber. This design provides numerous advantages that are described in the copending and commonly owned patent application Ser. No. 10/251,244, the contents of which are incorporated herein by reference. - Modifications and variations of the invention disclosed herein will occur to those skilled in the art and it is intended that all such modifications and variations be included within the scope of the appended claims.
Claims (17)
1-14. (canceled)
15. A membrane electrode assembly, comprising:
an elongate proton exchange membrane (“PEM”) film having first and second sides;
a plurality of spaced cathodes on the first side of the PEM film;
a plurality of spaced anodes on the second side of the PEM film respectively substantially aligned with the plurality of spaced cathodes such that the substantially aligned anodes and cathodes and portions of the PEM film therebetween define a plurality of spaced unit cells; and
conductive material electrically connecting adjacent unit cells.
16. A membrane electrode assembly as claimed in claim 15 , wherein the spaced unit cells are connected in series.
17. A membrane electrode assembly as claimed in claim 15 , wherein the spaced unit cells are connected in parallel.
18. A membrane electrode assembly as claimed in claim 15 , wherein the conductive material comprises a plurality of contact nubs.
19. A membrane electrode assembly as claimed in claim 18 , wherein
wherein each unit cell has at least one of the contact nubs connected thereto;
the PEM film includes a plurality of contact nub apertures; and
the contact nubs of adjacent unit cells are connected to one another by way of the PEM film contact nub apertures.
20. A membrane electrode assembly as claimed in claim 15 , wherein the PEM film comprises sulphonated polytetravluoroethylene film.
21. A membrane electrode assembly as claimed in claim 15 , wherein
the plurality of spaced cathodes comprise a plurality of spaced cathode catalyst material regions on the PEM film and a plurality of cathode conductor regions associated with the cathode catalyst material regions; and
the plurality of spaced anodes comprise a plurality of spaced anode catalyst material regions on the PEM film and a plurality of anode conductor regions associated with the anode catalyst material regions.
22. A membrane electrode assembly as claimed in claim 21 , wherein the cathode catalyst material comprises platinum.
23. A membrane electrode assembly as claimed in claim 21 , wherein the anode catalyst material comprises platinum-ruthenium.
24. A membrane electrode assembly as claimed in claim 21 , wherein the anode and cathode conductor regions comprise thin film carbon regions.
25. A membrane electrode assembly as claimed in claim 21 , wherein the anode and cathode conductor regions comprise thin film metal regions.
26. A membrane electrode assembly as claimed in claim 21 , wherein
the plurality of spaced cathode conductor regions are carried on a support film having a plurality of spaced perforation regions associated with the spaced cathode conductor regions; and
the plurality of spaced anode conductor regions are carried on a support film having a plurality of spaced perforation regions associated with the spaced anode conductor regions.
27. A membrane electrode assembly as claimed in claim 26 , wherein the support film comprises polyimide film.
28. A membrane electrode assembly as claimed in claim 15 , wherein the PEM film includes a plurality of folds shaped and positioned such that anodes face one another across respective gaps that define fuel chambers and cathodes face one another across respective gaps that define oxidant chambers.
29. A membrane electrode assembly as claimed in claim 28 , wherein the spaced unit cells are connected in series.
30. A membrane electrode assembly as claimed in claim 28 , further comprising wicking material located within the fuel chambers.
Priority Applications (1)
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US11/391,973 US20060172882A1 (en) | 2003-04-30 | 2006-03-29 | Membrane electrode assemblies and method for manufacture |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US10/428,171 US7049024B2 (en) | 2003-04-30 | 2003-04-30 | Membrane electrode assemblies and method for manufacture |
US11/391,973 US20060172882A1 (en) | 2003-04-30 | 2006-03-29 | Membrane electrode assemblies and method for manufacture |
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US10/428,171 Continuation US7049024B2 (en) | 2003-04-30 | 2003-04-30 | Membrane electrode assemblies and method for manufacture |
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US20060172882A1 true US20060172882A1 (en) | 2006-08-03 |
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US10/428,171 Expired - Lifetime US7049024B2 (en) | 2003-04-30 | 2003-04-30 | Membrane electrode assemblies and method for manufacture |
US11/391,973 Abandoned US20060172882A1 (en) | 2003-04-30 | 2006-03-29 | Membrane electrode assemblies and method for manufacture |
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US10/428,171 Expired - Lifetime US7049024B2 (en) | 2003-04-30 | 2003-04-30 | Membrane electrode assemblies and method for manufacture |
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US (2) | US7049024B2 (en) |
EP (1) | EP1473793B1 (en) |
JP (1) | JP4032042B2 (en) |
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TW (1) | TW200423464A (en) |
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Also Published As
Publication number | Publication date |
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US20040220048A1 (en) | 2004-11-04 |
JP4032042B2 (en) | 2008-01-16 |
EP1473793B1 (en) | 2009-07-08 |
EP1473793A3 (en) | 2006-07-19 |
DE602004021871D1 (en) | 2009-08-20 |
JP2004335466A (en) | 2004-11-25 |
EP1473793A2 (en) | 2004-11-03 |
US7049024B2 (en) | 2006-05-23 |
TW200423464A (en) | 2004-11-01 |
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