CA2332807A1 - Bipolar plates for electrochemical cells - Google Patents
Bipolar plates for electrochemical cells Download PDFInfo
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- CA2332807A1 CA2332807A1 CA002332807A CA2332807A CA2332807A1 CA 2332807 A1 CA2332807 A1 CA 2332807A1 CA 002332807 A CA002332807 A CA 002332807A CA 2332807 A CA2332807 A CA 2332807A CA 2332807 A1 CA2332807 A1 CA 2332807A1
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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
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04007—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids related to heat exchange
- H01M8/04067—Heat exchange or temperature measuring elements, thermal insulation, e.g. heat pipes, heat pumps, fins
- H01M8/04074—Heat exchange unit structures specially adapted for fuel cell
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/60—Constructional parts of cells
- C25B9/65—Means for supplying current; Electrode connections; Electric inter-cell connections
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/70—Assemblies comprising two or more 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
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0213—Gas-impermeable carbon-containing materials
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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
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0221—Organic resins; Organic polymers
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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
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0223—Composites
- H01M8/0226—Composites in the form of mixtures
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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
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0223—Composites
- H01M8/0228—Composites in the form of layered or coated products
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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
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0234—Carbonaceous material
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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
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0241—Composites
- H01M8/0245—Composites in the form of layered or coated products
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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
- 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
- H01M8/0232—Metals or alloys
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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
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04007—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids related to heat exchange
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
Abstract
A bipolar separator plate for two electrochemical cells connected in series, the plate having two layers of a porous electronically conductive material having positioned therebetween a solid layer of a polymeric material having dispersed therein at least 1 percent by weight of a conductive filler, where in the plate has an area resistivity of less than 1 ohm-cm2, and wherein the solid layer has a permeability of less than 50 .mu.Darcy (.mu.D).
Description
WO 99/60643 PC'f/US99110955 BIPOLAR PLATES FOR ELECTROCHEMICAL CELLS
This invention relates to electrochemical cells, and more particularly to components of such cells that have low permeability and are electronically conductive.
Electrochemical cells typically contain separator plates which are relatively impermeable to gases or liquid contained in the cell. Such plates are usually part of a gas or liquid distribution assembly. In fuel cells, for example, the separator plate is typically a graphite plate which has gas distribution channels machined into one of its surfaces.
However, such plates are expensive to produce. U.S. Patent No. 4,505,992 discloses a laminate for use as part of a fuel cE:ll assembly which comprises having a layer of a sealant material sandwiched between two porous carbon plates. However, the permeability and resistivity characteristics of such a composite may be less than desirable for certain applications.
Figure 1 illustrates a bipolar plate.
Figure 2 illustrates a bipolar plate having built-in cooling channels.
Figure 3 illustrates an assembly of components of a bipolar plate with cooling channels, prior to molding the assembly.
Figure 4 is an exploded schematic diagram of stack based on porous flow fields and containing the bipolar plate material of the present invention.
Figure 5 shows selected components of a fuel cell stack, including the (a) air delivery layer; (b) air flow field; (c) hydrogen delivery layer; and (d) hydrogen flow field.
In one aspect, this invention is a bipolar separator plate for two electrochemical cells connected in series, the plate comprising two layers of a porous electronically-conductive material having positioned therebetween a solid layer of a polymeric material having dispersed therein at least 1 percent by weight of a conductive filler, wherein the plate has an area resistivity of less than 1 ohm-cm2, and wherein the solid layer has a permeability of less than 50 wDarcy (~.D).
In another aspect, this invention is an electrochemical device having at least two electrochemical cells connected in series, each cell containing a gas or liquid material which is separated from a different gas or liquid material in an adjacent cell by two porous layers of electronically-conductive material having positioned therebetween a solid layer of a polymeric material having dispersed therein at least 1 percent by weight of a conductive filler, wherein the plate has an arE;a resistivity of less than 1 ohm-cm2, and wherein the solid layer has a permeability of less than 50 ~.D.
It has been discovered that the bipolar plate of the invention has desirable permeability, resistivity, and structural integrity characteristics for use in an electrochemical cell, particularly for cells in which vthe reactants on either side of the plate are pressurized.
These and other advantages of the invention will be apparent from the description which 1C follows.
Examples of suitable porous electronically-conductive materials include carbon paper, graphite paper, carbon felts, or other carbon-based composites, porous metal materials such as sintered metals, metal meshes, and metal screens, and solid, porous, electronically conductive polymer;> having a thickness of at least 1 mil. The optimum 15 thickness for the material will depend on the application, as well as the desired permeability and conductivity. Preferably, the material has a porosity of at least 20 percent, more preferably at least 40, most preferably at least 60 percent; but is preferably no greater than 90 percent, more preferably no greater than 85 percent, most preferably no greater than 80 percent.
This invention relates to electrochemical cells, and more particularly to components of such cells that have low permeability and are electronically conductive.
Electrochemical cells typically contain separator plates which are relatively impermeable to gases or liquid contained in the cell. Such plates are usually part of a gas or liquid distribution assembly. In fuel cells, for example, the separator plate is typically a graphite plate which has gas distribution channels machined into one of its surfaces.
However, such plates are expensive to produce. U.S. Patent No. 4,505,992 discloses a laminate for use as part of a fuel cE:ll assembly which comprises having a layer of a sealant material sandwiched between two porous carbon plates. However, the permeability and resistivity characteristics of such a composite may be less than desirable for certain applications.
Figure 1 illustrates a bipolar plate.
Figure 2 illustrates a bipolar plate having built-in cooling channels.
Figure 3 illustrates an assembly of components of a bipolar plate with cooling channels, prior to molding the assembly.
Figure 4 is an exploded schematic diagram of stack based on porous flow fields and containing the bipolar plate material of the present invention.
Figure 5 shows selected components of a fuel cell stack, including the (a) air delivery layer; (b) air flow field; (c) hydrogen delivery layer; and (d) hydrogen flow field.
In one aspect, this invention is a bipolar separator plate for two electrochemical cells connected in series, the plate comprising two layers of a porous electronically-conductive material having positioned therebetween a solid layer of a polymeric material having dispersed therein at least 1 percent by weight of a conductive filler, wherein the plate has an area resistivity of less than 1 ohm-cm2, and wherein the solid layer has a permeability of less than 50 wDarcy (~.D).
In another aspect, this invention is an electrochemical device having at least two electrochemical cells connected in series, each cell containing a gas or liquid material which is separated from a different gas or liquid material in an adjacent cell by two porous layers of electronically-conductive material having positioned therebetween a solid layer of a polymeric material having dispersed therein at least 1 percent by weight of a conductive filler, wherein the plate has an arE;a resistivity of less than 1 ohm-cm2, and wherein the solid layer has a permeability of less than 50 ~.D.
It has been discovered that the bipolar plate of the invention has desirable permeability, resistivity, and structural integrity characteristics for use in an electrochemical cell, particularly for cells in which vthe reactants on either side of the plate are pressurized.
These and other advantages of the invention will be apparent from the description which 1C follows.
Examples of suitable porous electronically-conductive materials include carbon paper, graphite paper, carbon felts, or other carbon-based composites, porous metal materials such as sintered metals, metal meshes, and metal screens, and solid, porous, electronically conductive polymer;> having a thickness of at least 1 mil. The optimum 15 thickness for the material will depend on the application, as well as the desired permeability and conductivity. Preferably, the material has a porosity of at least 20 percent, more preferably at least 40, most preferably at least 60 percent; but is preferably no greater than 90 percent, more preferably no greater than 85 percent, most preferably no greater than 80 percent.
2 C Suitable polymeric materials which contain the conductive filler include any thermoplastic or thermosetting polymer which is a solid at ambient conditions (about 23°C), stable under the operating conditions of the electrochemical cell, and can be mixed with a conductive filler and processed into the shape of a separator plate for use with electrochemical cells. Examples ,of such include polyolefins, polystyrenes, polyepoxides, 25 polyurethanes (including Isoplast~~M and PellethaneTM polyurethane resins, available from The Dow Chemical Company), pcdytetrafluoroethylenes, polyacrylates, polyethylene terephthalate, polyvinylchloride, p~olyvinylidene fluoride, vinyl ester resins (available from The Dow Chemical Company as DerakaneTM resins), acrylonitrile-butadiene-styrene copolymers, polyamides, polyestE;rs, linear polyimides, liquid crystal polymers, as well as 3 0 blends and copolymers thereof. Preferably, the polymer is polypropylene, syndiotactic polystyrene, IsopIastT"' polyurethane resin, polyvinylidene fluoride, a vinyl ester resin, or polytetrafluoroethylene.
Suitable conductive fillers include electronically-conductive grades of carbon black, carbon fibers, graphite, metal fibers and particles, and particles of intrinsically-conductive polymers. Suitable carbon fibers include those having a length of about 0.25 inch and a diameter of about 7 ~,m, as well a.s agglomerates of fibers having an aspect ratio of at least and a diameter in the range of 3.5 to 70 nm as described, for example, in WO
91/03057.
Suitable graphite particles have a size in the range of 20 to 500 nm and a surface area in the range of 1 to 100 m2/g. Examples of suitable carbon blacks include particles of carbon 1( having an average primary partic4e diameter of less than 125 nm, more preferably of less than 60 nm. The carbon black is preferably utilized as an aggregate or agglomerate of primary particles, the aggregate or agglomerate typically having a size of 5 to 10 times the primary particle size. Larger agglomerates, beads, or pellets of carbon particles may also be utilized as a starting material in the preparation of the composition, so long as they 1~~ disperse during the preparation or processing of the composition sufficiently to reach an average size in the cured compo:>ition of less than 10 microns, more preferably less than 5 microns, and most preferably less than 1.25 microns. Preferably, the conductive filler is a carbon fiber having an aspect ratNo of at least 5, more preferably at least 50, most preferably at least 100. However, the optimum aspect ratio of the fiber will depend on the mean pore 2 U size of the porous electronically-conductive material, with longer fibers being more suitable for use with larger mean pore sizE: materials.
The conductive filler is preferably employed in an amount, based on the weight of the polymeric material, of at least 1 percent, more preferably at least 10 percent, most preferably at least 20 percent; but preferably no greater than 90 percent, more preferably no 2 ~~ greater than 70 percent.
The bipolar plate may be made by any suitable process, but is preferably prepared by injection or compression molding a mixture of a thermoplastic polymer and a conductive carbon into the desired shape arrd size, and then combining the porous conductive layers with the molded layer by compression molding a multilayer composite of the molded layer 3 U positioned between two layers of the porous conductive material.
Alternatively, sheets of a filled thermoplastic material may be compression molded between layers of the porous WO 99/60643 PC'TNS99/10955 conductive material. In a third embodiment, a filled thermoplastic material may be injected between two layers of the porous conductive material in a mold, and then the resulting composite is compression molded.
The pressure and temperature of the process should be high enough to ensure good electrical contact between the conductive layer and the porous layers, and to increase the density of the solid layer and/or the electronically-conductive material, if necessary to achieve the desired permeability characteristics and/or better conductivity.
Preferably, the pressure and temperature is sufficient to cause a portion of the solid conductive layer to migrate into the pores of the porous layer in order to achieve better electrical contact 1G between the layers. As the polymer portion of the layer migrates into the porous material, the conductive carbon tends to stay between the two porous layers and the concentration of conductive carbon in the middle I<~yer increases accordingly, thereby increasing the conductivity of that layer. Although the degree of compaction of the composite may vary depending on the materials (such as, for example, the carbon paper thickness and porosity) 15 and the performance requirements for use in a particular type of electrochemical cell, the composite is preferably compressed under conditions sufficient to reduce its volume by 5 to 80 percent. Figure 1 shows a bipolar plate prepared by a compression molding process, having two layers of porous carbon paper (1 ) and a layer of a polymer containing a conductive filler (2). During the molding process, a portion of the polymer migrated into the 2 C porous carbon paper (3).
If a thermosetting polymer is used, the bipolar plate may be prepared by injecting the reactive monomeric components ~of a multi-part reactive thermosetting mixture (containing conductive filler) between two layers of the porous conductive material in a mold.
Alternatively, a latent-curable thermosetting polymer may be used in processes similar to 2 ~ those employed with thermoplastic polymers. The bipolar plate containing the uncured polymer may then be subjected to reaction conditions which cause the polymer to crosslink or cure.
The optimum thickness of the bipolar plate will depend on the types of electrochemical cell in which it is employed. For fuel cells, the thickness is preferably at 3 G least about 2 mils, more preferablly at least 5 mils, most preferably at least 10 mils; but is preferably no greater than 200 mils, more preferably no greater than 100 mils, most preferably no greater than 75 mil;;.
Permeability The permeability of the solid layer is less than 50 microdarcys (wD).
Preferably, the permeability is less than 20 p,D and is more preferably less than 10 wD. The permeability of the layer may be measured according to the following method: The solid material to be tested is mounted in a simple pressure cell equipped with rubber gaskets that prevent gas flow around the sample as well as to the outside of the cell. Pressurized air at 30 psig is supplied to one face of the sample while the air flow rate at atmospheric pressure is 1c~ measured using a soap bubble or other flow rate measuring device. The permeability of the solid material is calculated from the pressure and flow data using the Darcy equation for a compressible fluid:
2 p. L Qa Pe K=
z z A (Pb - Pa ) where K is the permeability in cm2 (K can also be expressed in Darcys; 1 Darcy =
1~> 0.99x10'8 cm2), w is the viscosity of the fluid at the measurement temperature in Pascal seconds, L is the length of the flow path in cm (the thickness of the solid material in this case), Qa is the flow rate at the outlet in cm3/s, Pe is the pressure at the outlet in pascals, A
is the area in cm2, and Pb is the pressure at the inlet in pascals.
If the electrochemical cell is a fuel cell, the bipolar plate preferably has a "leak rate"
2 c) of no greater than 3 cm/min, mona preferably no greater than 1 cmlmin, and most preferably no greater than 0.3 cm/min. The procedure for measuring the leak rate is as follows:
mount the sample in a pressure cell and apply 30 psig air to one side of the sample and measure the air flow rate (at 0 psig) out the other side. The leak rate is the flow rate (in cm3/min) divided by the area (in cmz) of the bipolar plate. ' 2 ~> Resistivi The area resistivity of the bipolar plate is preferably less than 0.1 S~2-cm2, more preferably less than 0.01 SZ-cm2, .and most preferably less than 0.003 SZ-cm2.
The area resistivity may be measured and calculated as follows: Resistance is measured by clamping a 4 cm2 bipolar plate between two (4 cm2) brass plates which serve as direct current (250 mA) carrying electrodes. The voltage across the thickness of the sample is measured via screws mounted in and electrically isolated from each brass plate. The ~> resistance is then calculated by diving the measured voltage by the current. The Area Resistivity = Rs, where R = resistance (S2) and s = area of bipolar plate being measured (i.e., area of brass plate) (cm2).
Coolin4 Channels In another embodiment of the invention, cooling channels may be built into the 1(~ bipolar plate, which are useful if the electrochemical cell generates heat and optimum performance is achieved if the device temperature is kept low. For example, during its regular operation an individual fuel cell or stack will generate heat. Built in cooling channels in the bipolar plates will help manage this heat by convection or by circulating cooling fluid through this channels (see Figure 2 for illustration).
2~> For fuel cell stacks of less than 1 kilowatt, it is expected that air driven by a fan through straight cooling channels would be sufficient. For higher wattage stacks, the cooling channels may need to contain a different heat-exchange fluid. Cooling channels may be fabricated using a small diameter (such as 1/16 inch) polytetrafluoroethylene tubing or small gauge (such as 18 gauge) stainless steel tubing. Further, the addition of cooling 20 channels may require the fabrication of thicker bipolar plates. After the fabrication of the bipolar plate with cooling channells, the tubing may be extracted from the bipolar plate, leaving built-in length-wise through channels in the plate, or may be left in place.
A preferred fabrication process is as follows: (1 ) Two carbon-filled thermoplastic plates are prepared; (2) A number of conduits are cut to lengths greater than the width of 2 ~> the desired bipolar plate; (3) Two carbon paper pieces are cut to fit the width and length of the mold chase; (4) Inside the chase, arrange the different components in the following order (as illustrated in Figure 3): Carbon paper layer, Carbon-reinforced thermoplastic plate, Conduits at regular parallel intervals covering the desired cooling area (To keep conduits in place, location plates which do not extend into the interior of the assembly and 3 t) do not become a part of it may be needed), Carbon-reinforced thermoplastic plate, Carbon paper layer; (5) Using a regular fabrication cycle, mold the arrangement prepared in step (4); and (6) Retrieve bipolar plate with cooling channels.
Bipolar Plates with Cooling_Flow Fi I s In another embodiment, an additional layer of porous electronically-conductive material may be positioned between two outer layers of porous electronically-conductive material. A solid layer of polymeric material is positioned between the center porous layer and each outer layer. The center' layer is thicker and selected so that it does not compress as easily as the outer layers of porous material during the fabrication process. The thicknesses of the center layers and the solid layers of polymeric material are selected so 1G that the center layer does not become completely filled with polymeric material during the molding process. This type of bipolar plate configuration leaves an open porous area in the middle of the bipolar plate, through which a cooling fluid may be circulated.
The following examples illustrate the invention, but are not intended to limit it in any way. Unless otherwise stated, all parts and percentages are given by weight.
1 ~~ Example 1 Three membrane and electrode assemblies ("MEAs") were prepared according to the method described in PCT publication No. WO 97/13287. The Pt catalyst loadings of the three cathode and three anode sides were 0.21, 0.19 and 0.18; and 0.14, 0.13, and 0.17 mg/cm2, respectively. The active (catalyzed) area of each of the three cells was 19.8 cm2.
2 U The MEAs were soaked in dilute sulfuric acid, then water, and loaded into the stack wet.
Porous cathode flow fields were constructed according to the method described in PCT publication No. WO 97/13287. Porous carbon paper having a porosity of 90 percent and 24 mils thick (available as SpectracarbTM paper from Spectracorp (Lawrence, MA)) was made hydrophilic by oxidation in .a medium comprising 0.006 M silver sulfate, 0.2. M sodium 2 ~~ persulfate and 0.5 M sulfuric acids at a temperature of 60°C for 1 hour. The porous anode flow fields were density 0.42 g/cm~, 14-mil thick porous carbon paper, also from Spectracorp. The edges of the flow fields were sealed with epoxy to provide a gas tight seal both internally and to the exllerior of the stack.
_7_ Air and hydrogen delivery layers were constructed from 3 layers of 10-mil thick GrafoiITM graphite paper by cutting out channels with a scalpel. When the stack was assembled, these layers cooperated with the bipolar plates and MEAs to form ducts that delivered reactant gases to the porous flow fields. These ducts were joined to internal manifolds that were formed from holes in the various elements when the stack was assembled.
End plates were constructed of 1/2-inch thick aluminum. Next to each end plate was placed a 73-mil thick layer of 316 alloy stainless steel to prevent corrosion of the inside face of the end plate.
Bipolar plates were constructed according to the present invention for use in the stack. Carbon fiber-filled nylon 66 (50 percent carbon fiber loading by weight, density 1.38 g/cm3, obtained from DSM EnginE:ering Plastics) was first dried at 80°F
for 16 hours in vacuum (29 mm Hg), then compression molded using a programmable compression molding machine. The desired amount of carbon fiber-filled nylon 66 (calculated as the 1~~ thickness times the length times the width of the chase, or mold, times the density of the carbon fiber-filled nylon 66) was placed in the chase, or mold, which was sandwiched between two KaptonTM slip sheets. This assembly was then further sandwiched between two thick smooth-finish metal sheets and placed in the compression-molding machine. After a 4-minute heat-soak stage wherein the mold platens of the compression mold were pre-2( heated to 540°F, closed, and compressed to a pressure of slightly above 0 psi, the pressure in the mold was increased to 500 Ib for 4 minutes, and then increased to 10,000 Ibf for 3 minutes, while maintaining the mold temperature at 540°F.
SpectracarbTM paper having a density of 0.50 g/cm3 and a thickness of 11.5 mils was placed on both sides of the carbon fiber-filled nylon 66 molded layer. This arrangement was 2 ~> placed in a 16-mil thick chase (mold) and returned to the compression-molding machine.
Molding cycles identical to those described above were applied, giving a final fabricated product 16 mils thick. This product was tested for electrical resistivity and gas permeability before use as a bipolar plate material in the stack.
The stack was assembled from the cathode end plate up, using 1/8-inch diameter 3 i) nylon 66 rods as guides to align the stack elements. These guides were left in place in the -g_ assembled stack. The order of stacking elements was as follows: aluminum anode end plate; stainless steel layer, hydrogen delivery layer, anode flow field; MEA
1; cathode flow field; air delivery layer; bipolar plate; hydrogen delivery layer; anode flow field; MEA 2;
cathode flaw field; air delivery layer; bipolar plate; hydrogen delivery layer; anode flow field;
MEA 3; cathode flow field; air delivery layer; stainless steel layer; and aluminum cathode end plate.
Once assembly was complete, the bolts were evenly tightened to 50 inch-pounds torque. The bolts were to be re-tightened over a period of hours to obtain uniform compression. Further tightening vvas required as the stack was heated to the operating temperature of 80°C. The operational thickness of this stack under full compression (minus the end plates and stainless steel layers) was about 299 mils.
The stack was evaluated using a fuel cell test stand manufactured by Fuel Cell Technologies, Inc. (Los Alamos, IWM). The test stand incorporated a 120 ampere Hewlett-Packard 605048 Electronic Load module with a 600 watt rating, as well as hardware to provide flow control of gas streams, heating and humidity for both cathode and anode gases, and back-pressure control for operation at pressures above atmospheric pressure.
During operation, the stack self-hf:ated to above the desired operating temperature of 80°C, but adequate cooling was provided by an external fan.
The stack was operated under the following conditions: cathode gas: air at 30 psig outlet pressure, 1970 standard cubic centimeters per minute (sccm) flow rate, and humidified at 88°C; and anode gas: hydrogen at 20 psig outlet pressure, 830 scan flow rate, and humidified at 100°C. After a 24-hour break-in period, the stack delivered 1.70 volts at 19.8 A (1 A/cm2), or about 34 watts.
Figure 4 is an exploded schematic diagram of stack based on porous flow fields and containing the bipolar plate material of the present invention. From left to right, the elements are: end plate, air delivery layer, cathode flow field, MEA, anode flaw field, hydrogen delivery layer, and bipolar plate.
Figure 5 shows selected stack components, as follows: (a) air delivery layer;
(b) air flow field; (c) hydrogen delivery layer; and (d) hydrogen flow field.
_g_ Examples 2-7 Carbon-containing solid layers were prepared using the method described in Example 1, using the following materials and molding parameters:
WO 99/60643 PC'fIUS99/10955 Table 1. Carbon-filled Thermoplastics CarbonLoad Plastic Form, Company, Drying Melting filler(% wt.) density material Vacuum Temp.
code (F) (g/cm ) Conditions Black 40 poly- pellets, RTP Co., no 450 propylene0.97-1.01 ESD-C-100 Fiber 40 poly- pellets, RTP Co., 110C, 610 carbonate1.36 RTP-387 16 hrs., 29 mm Hg Vac Fiber 50 nylon pellets, DSM Eng. 80F, 16 540 1.38 Plastics, hrs., J-1 /CF/50/EGmm Hg Vac Table 2. Materials and Molding Conditions Material Molding Stages PP & Carbon PC & Carbon Nyfon 66 &
Black Fiber Carbon Fiber Temperatu 450 610 540 re (F) Stage 1 Heat Soak: 3 3 4 (minutes) Time (minutE~s)5 10 4 Stage 2 Low-Pressure500 500 500 (Ibf) Time {minutEa)3 3 3 Stage 3 High-Pressure10000 10000 10000 (Ibf) Time to cool 20 20 20 mold to ambient temperature using a heat-transfer fluid (minutes) Notes: The chase (mold) is 8-rnils thick, 5.75 in. long, and 5.75 in, wide.
PP = polypropylene; PC = polyc:arbonate.
_11 _ WO 99/60643 PC'f/US99/10955 Bipolar plates were then Errepared using the above-described solid layers and the following carbon papers. The carbon papers were obtained from Spectracorp (Lawrence, MA) and Toray (Tokyo, Japan). In Comparative Examples 1 and 2, the carbon paper/plastic assemblies were compressed sufficiently to cause the fibers of the paper to touch each other within the bipolar plate, in order to achieve electrical contact between the layers and good conductivity.
Table: 3. Bipolar Plate Compositions Example Carbon paper, Fill Plastic Plate No. density (g/cm3), Thickness thickness (mil) (mil) Comp. Ex. Spectracorp, 0.50, none nylon 66 21.5 1 * 11.5 2 Toray (TGPH090), carbon nylon 66 23 0.50, 9 fiber 3** Spectracorp, 0.50, carbon nylon 66 16 11.5 fiber 4 Spectracorp, 0.50, carbon polypropylene20 11.5 black Spectracorp, 0.25, carbon nylon 66 12 8 fiber Comp. Ex. Spectracorp, 0.50, none polypropylene19.5 2 * 11.5 6 Spectracorp, 0.69, carbon nylon 66 44.5 18.5 fiber 7 Spectracorp, 0.67, carbon nylon 66 32.5 11.5 fiber * Comparative Example - not an example of the invention.
1() Below are the values for the product of through-plane resistivity for Examples 2-7.
Table 4 Example No. Area Resistivity (S2-cm2)Permeability (wD) Comp. Ex. 1* 0.0202 too high to measure 2 0.00018 0.14 3 0.0018 0.20 4 0.0042 2.5 5 0.00024 3.7 Comp. Ex. 2* 0.00074 15 6 0.0068 2.1 7 0.014 1.2 Examr~les 8-10 Three bipolar plates with cooling channels were assembled as illustrated in Figure 3, using polytetrafluoroethylene or steel tubing as a conduit material, except that carbon paper is used in Example 8. The chasE; (mold) thickness (See Figure 3) was double the plate thickness. The carbon paper usE;d was 11.5 mils thick and had a density of 0.50 g/cm3.
The assemblies were molded under the conditions described in Examples 1-7.
Table 5. Dimensions of Components for the Bipolar Plate with Cooling Channels Example No. Material Conduit Diameter Plate Thickness (mil) 8 carbon black 1/16 in. polytetrafluoroethylene63 &
polypropylE;ne 9 carbon fiber 1/16 in. polytetrafluoroethylene63 &
nylon 66 10 carbon fiber 18 gauge stainless steel42 &
nylon 66 Upon molding, the poiytetrafluoroethylene tubing did not collapse when placed in between the carbon black-polypropylene plates and was easily retrieved. The cooling holes that ran inside the plate were centered. The carbon-black polypropylene had a relatively 1'S low viscosity at its processing ternperatures, and the molten material easily conformed around the polytetrafluoroethylene tubing. However, due to the much greater viscosity of the carbon fiber-filled nylon 66 ai: its recommended processing temperature, the polytetrafluoroethylene tubing collapsed when trying to mold a plate out of this material.
When the stainless steel conduit, gauge 18, was employed to mold cooling channels 2 0 in a carbon-fiber nylon 66 bipolar plate, the tubing did not collapse. The metal tubing was not retrieved.
Suitable conductive fillers include electronically-conductive grades of carbon black, carbon fibers, graphite, metal fibers and particles, and particles of intrinsically-conductive polymers. Suitable carbon fibers include those having a length of about 0.25 inch and a diameter of about 7 ~,m, as well a.s agglomerates of fibers having an aspect ratio of at least and a diameter in the range of 3.5 to 70 nm as described, for example, in WO
91/03057.
Suitable graphite particles have a size in the range of 20 to 500 nm and a surface area in the range of 1 to 100 m2/g. Examples of suitable carbon blacks include particles of carbon 1( having an average primary partic4e diameter of less than 125 nm, more preferably of less than 60 nm. The carbon black is preferably utilized as an aggregate or agglomerate of primary particles, the aggregate or agglomerate typically having a size of 5 to 10 times the primary particle size. Larger agglomerates, beads, or pellets of carbon particles may also be utilized as a starting material in the preparation of the composition, so long as they 1~~ disperse during the preparation or processing of the composition sufficiently to reach an average size in the cured compo:>ition of less than 10 microns, more preferably less than 5 microns, and most preferably less than 1.25 microns. Preferably, the conductive filler is a carbon fiber having an aspect ratNo of at least 5, more preferably at least 50, most preferably at least 100. However, the optimum aspect ratio of the fiber will depend on the mean pore 2 U size of the porous electronically-conductive material, with longer fibers being more suitable for use with larger mean pore sizE: materials.
The conductive filler is preferably employed in an amount, based on the weight of the polymeric material, of at least 1 percent, more preferably at least 10 percent, most preferably at least 20 percent; but preferably no greater than 90 percent, more preferably no 2 ~~ greater than 70 percent.
The bipolar plate may be made by any suitable process, but is preferably prepared by injection or compression molding a mixture of a thermoplastic polymer and a conductive carbon into the desired shape arrd size, and then combining the porous conductive layers with the molded layer by compression molding a multilayer composite of the molded layer 3 U positioned between two layers of the porous conductive material.
Alternatively, sheets of a filled thermoplastic material may be compression molded between layers of the porous WO 99/60643 PC'TNS99/10955 conductive material. In a third embodiment, a filled thermoplastic material may be injected between two layers of the porous conductive material in a mold, and then the resulting composite is compression molded.
The pressure and temperature of the process should be high enough to ensure good electrical contact between the conductive layer and the porous layers, and to increase the density of the solid layer and/or the electronically-conductive material, if necessary to achieve the desired permeability characteristics and/or better conductivity.
Preferably, the pressure and temperature is sufficient to cause a portion of the solid conductive layer to migrate into the pores of the porous layer in order to achieve better electrical contact 1G between the layers. As the polymer portion of the layer migrates into the porous material, the conductive carbon tends to stay between the two porous layers and the concentration of conductive carbon in the middle I<~yer increases accordingly, thereby increasing the conductivity of that layer. Although the degree of compaction of the composite may vary depending on the materials (such as, for example, the carbon paper thickness and porosity) 15 and the performance requirements for use in a particular type of electrochemical cell, the composite is preferably compressed under conditions sufficient to reduce its volume by 5 to 80 percent. Figure 1 shows a bipolar plate prepared by a compression molding process, having two layers of porous carbon paper (1 ) and a layer of a polymer containing a conductive filler (2). During the molding process, a portion of the polymer migrated into the 2 C porous carbon paper (3).
If a thermosetting polymer is used, the bipolar plate may be prepared by injecting the reactive monomeric components ~of a multi-part reactive thermosetting mixture (containing conductive filler) between two layers of the porous conductive material in a mold.
Alternatively, a latent-curable thermosetting polymer may be used in processes similar to 2 ~ those employed with thermoplastic polymers. The bipolar plate containing the uncured polymer may then be subjected to reaction conditions which cause the polymer to crosslink or cure.
The optimum thickness of the bipolar plate will depend on the types of electrochemical cell in which it is employed. For fuel cells, the thickness is preferably at 3 G least about 2 mils, more preferablly at least 5 mils, most preferably at least 10 mils; but is preferably no greater than 200 mils, more preferably no greater than 100 mils, most preferably no greater than 75 mil;;.
Permeability The permeability of the solid layer is less than 50 microdarcys (wD).
Preferably, the permeability is less than 20 p,D and is more preferably less than 10 wD. The permeability of the layer may be measured according to the following method: The solid material to be tested is mounted in a simple pressure cell equipped with rubber gaskets that prevent gas flow around the sample as well as to the outside of the cell. Pressurized air at 30 psig is supplied to one face of the sample while the air flow rate at atmospheric pressure is 1c~ measured using a soap bubble or other flow rate measuring device. The permeability of the solid material is calculated from the pressure and flow data using the Darcy equation for a compressible fluid:
2 p. L Qa Pe K=
z z A (Pb - Pa ) where K is the permeability in cm2 (K can also be expressed in Darcys; 1 Darcy =
1~> 0.99x10'8 cm2), w is the viscosity of the fluid at the measurement temperature in Pascal seconds, L is the length of the flow path in cm (the thickness of the solid material in this case), Qa is the flow rate at the outlet in cm3/s, Pe is the pressure at the outlet in pascals, A
is the area in cm2, and Pb is the pressure at the inlet in pascals.
If the electrochemical cell is a fuel cell, the bipolar plate preferably has a "leak rate"
2 c) of no greater than 3 cm/min, mona preferably no greater than 1 cmlmin, and most preferably no greater than 0.3 cm/min. The procedure for measuring the leak rate is as follows:
mount the sample in a pressure cell and apply 30 psig air to one side of the sample and measure the air flow rate (at 0 psig) out the other side. The leak rate is the flow rate (in cm3/min) divided by the area (in cmz) of the bipolar plate. ' 2 ~> Resistivi The area resistivity of the bipolar plate is preferably less than 0.1 S~2-cm2, more preferably less than 0.01 SZ-cm2, .and most preferably less than 0.003 SZ-cm2.
The area resistivity may be measured and calculated as follows: Resistance is measured by clamping a 4 cm2 bipolar plate between two (4 cm2) brass plates which serve as direct current (250 mA) carrying electrodes. The voltage across the thickness of the sample is measured via screws mounted in and electrically isolated from each brass plate. The ~> resistance is then calculated by diving the measured voltage by the current. The Area Resistivity = Rs, where R = resistance (S2) and s = area of bipolar plate being measured (i.e., area of brass plate) (cm2).
Coolin4 Channels In another embodiment of the invention, cooling channels may be built into the 1(~ bipolar plate, which are useful if the electrochemical cell generates heat and optimum performance is achieved if the device temperature is kept low. For example, during its regular operation an individual fuel cell or stack will generate heat. Built in cooling channels in the bipolar plates will help manage this heat by convection or by circulating cooling fluid through this channels (see Figure 2 for illustration).
2~> For fuel cell stacks of less than 1 kilowatt, it is expected that air driven by a fan through straight cooling channels would be sufficient. For higher wattage stacks, the cooling channels may need to contain a different heat-exchange fluid. Cooling channels may be fabricated using a small diameter (such as 1/16 inch) polytetrafluoroethylene tubing or small gauge (such as 18 gauge) stainless steel tubing. Further, the addition of cooling 20 channels may require the fabrication of thicker bipolar plates. After the fabrication of the bipolar plate with cooling channells, the tubing may be extracted from the bipolar plate, leaving built-in length-wise through channels in the plate, or may be left in place.
A preferred fabrication process is as follows: (1 ) Two carbon-filled thermoplastic plates are prepared; (2) A number of conduits are cut to lengths greater than the width of 2 ~> the desired bipolar plate; (3) Two carbon paper pieces are cut to fit the width and length of the mold chase; (4) Inside the chase, arrange the different components in the following order (as illustrated in Figure 3): Carbon paper layer, Carbon-reinforced thermoplastic plate, Conduits at regular parallel intervals covering the desired cooling area (To keep conduits in place, location plates which do not extend into the interior of the assembly and 3 t) do not become a part of it may be needed), Carbon-reinforced thermoplastic plate, Carbon paper layer; (5) Using a regular fabrication cycle, mold the arrangement prepared in step (4); and (6) Retrieve bipolar plate with cooling channels.
Bipolar Plates with Cooling_Flow Fi I s In another embodiment, an additional layer of porous electronically-conductive material may be positioned between two outer layers of porous electronically-conductive material. A solid layer of polymeric material is positioned between the center porous layer and each outer layer. The center' layer is thicker and selected so that it does not compress as easily as the outer layers of porous material during the fabrication process. The thicknesses of the center layers and the solid layers of polymeric material are selected so 1G that the center layer does not become completely filled with polymeric material during the molding process. This type of bipolar plate configuration leaves an open porous area in the middle of the bipolar plate, through which a cooling fluid may be circulated.
The following examples illustrate the invention, but are not intended to limit it in any way. Unless otherwise stated, all parts and percentages are given by weight.
1 ~~ Example 1 Three membrane and electrode assemblies ("MEAs") were prepared according to the method described in PCT publication No. WO 97/13287. The Pt catalyst loadings of the three cathode and three anode sides were 0.21, 0.19 and 0.18; and 0.14, 0.13, and 0.17 mg/cm2, respectively. The active (catalyzed) area of each of the three cells was 19.8 cm2.
2 U The MEAs were soaked in dilute sulfuric acid, then water, and loaded into the stack wet.
Porous cathode flow fields were constructed according to the method described in PCT publication No. WO 97/13287. Porous carbon paper having a porosity of 90 percent and 24 mils thick (available as SpectracarbTM paper from Spectracorp (Lawrence, MA)) was made hydrophilic by oxidation in .a medium comprising 0.006 M silver sulfate, 0.2. M sodium 2 ~~ persulfate and 0.5 M sulfuric acids at a temperature of 60°C for 1 hour. The porous anode flow fields were density 0.42 g/cm~, 14-mil thick porous carbon paper, also from Spectracorp. The edges of the flow fields were sealed with epoxy to provide a gas tight seal both internally and to the exllerior of the stack.
_7_ Air and hydrogen delivery layers were constructed from 3 layers of 10-mil thick GrafoiITM graphite paper by cutting out channels with a scalpel. When the stack was assembled, these layers cooperated with the bipolar plates and MEAs to form ducts that delivered reactant gases to the porous flow fields. These ducts were joined to internal manifolds that were formed from holes in the various elements when the stack was assembled.
End plates were constructed of 1/2-inch thick aluminum. Next to each end plate was placed a 73-mil thick layer of 316 alloy stainless steel to prevent corrosion of the inside face of the end plate.
Bipolar plates were constructed according to the present invention for use in the stack. Carbon fiber-filled nylon 66 (50 percent carbon fiber loading by weight, density 1.38 g/cm3, obtained from DSM EnginE:ering Plastics) was first dried at 80°F
for 16 hours in vacuum (29 mm Hg), then compression molded using a programmable compression molding machine. The desired amount of carbon fiber-filled nylon 66 (calculated as the 1~~ thickness times the length times the width of the chase, or mold, times the density of the carbon fiber-filled nylon 66) was placed in the chase, or mold, which was sandwiched between two KaptonTM slip sheets. This assembly was then further sandwiched between two thick smooth-finish metal sheets and placed in the compression-molding machine. After a 4-minute heat-soak stage wherein the mold platens of the compression mold were pre-2( heated to 540°F, closed, and compressed to a pressure of slightly above 0 psi, the pressure in the mold was increased to 500 Ib for 4 minutes, and then increased to 10,000 Ibf for 3 minutes, while maintaining the mold temperature at 540°F.
SpectracarbTM paper having a density of 0.50 g/cm3 and a thickness of 11.5 mils was placed on both sides of the carbon fiber-filled nylon 66 molded layer. This arrangement was 2 ~> placed in a 16-mil thick chase (mold) and returned to the compression-molding machine.
Molding cycles identical to those described above were applied, giving a final fabricated product 16 mils thick. This product was tested for electrical resistivity and gas permeability before use as a bipolar plate material in the stack.
The stack was assembled from the cathode end plate up, using 1/8-inch diameter 3 i) nylon 66 rods as guides to align the stack elements. These guides were left in place in the -g_ assembled stack. The order of stacking elements was as follows: aluminum anode end plate; stainless steel layer, hydrogen delivery layer, anode flow field; MEA
1; cathode flow field; air delivery layer; bipolar plate; hydrogen delivery layer; anode flow field; MEA 2;
cathode flaw field; air delivery layer; bipolar plate; hydrogen delivery layer; anode flow field;
MEA 3; cathode flow field; air delivery layer; stainless steel layer; and aluminum cathode end plate.
Once assembly was complete, the bolts were evenly tightened to 50 inch-pounds torque. The bolts were to be re-tightened over a period of hours to obtain uniform compression. Further tightening vvas required as the stack was heated to the operating temperature of 80°C. The operational thickness of this stack under full compression (minus the end plates and stainless steel layers) was about 299 mils.
The stack was evaluated using a fuel cell test stand manufactured by Fuel Cell Technologies, Inc. (Los Alamos, IWM). The test stand incorporated a 120 ampere Hewlett-Packard 605048 Electronic Load module with a 600 watt rating, as well as hardware to provide flow control of gas streams, heating and humidity for both cathode and anode gases, and back-pressure control for operation at pressures above atmospheric pressure.
During operation, the stack self-hf:ated to above the desired operating temperature of 80°C, but adequate cooling was provided by an external fan.
The stack was operated under the following conditions: cathode gas: air at 30 psig outlet pressure, 1970 standard cubic centimeters per minute (sccm) flow rate, and humidified at 88°C; and anode gas: hydrogen at 20 psig outlet pressure, 830 scan flow rate, and humidified at 100°C. After a 24-hour break-in period, the stack delivered 1.70 volts at 19.8 A (1 A/cm2), or about 34 watts.
Figure 4 is an exploded schematic diagram of stack based on porous flow fields and containing the bipolar plate material of the present invention. From left to right, the elements are: end plate, air delivery layer, cathode flow field, MEA, anode flaw field, hydrogen delivery layer, and bipolar plate.
Figure 5 shows selected stack components, as follows: (a) air delivery layer;
(b) air flow field; (c) hydrogen delivery layer; and (d) hydrogen flow field.
_g_ Examples 2-7 Carbon-containing solid layers were prepared using the method described in Example 1, using the following materials and molding parameters:
WO 99/60643 PC'fIUS99/10955 Table 1. Carbon-filled Thermoplastics CarbonLoad Plastic Form, Company, Drying Melting filler(% wt.) density material Vacuum Temp.
code (F) (g/cm ) Conditions Black 40 poly- pellets, RTP Co., no 450 propylene0.97-1.01 ESD-C-100 Fiber 40 poly- pellets, RTP Co., 110C, 610 carbonate1.36 RTP-387 16 hrs., 29 mm Hg Vac Fiber 50 nylon pellets, DSM Eng. 80F, 16 540 1.38 Plastics, hrs., J-1 /CF/50/EGmm Hg Vac Table 2. Materials and Molding Conditions Material Molding Stages PP & Carbon PC & Carbon Nyfon 66 &
Black Fiber Carbon Fiber Temperatu 450 610 540 re (F) Stage 1 Heat Soak: 3 3 4 (minutes) Time (minutE~s)5 10 4 Stage 2 Low-Pressure500 500 500 (Ibf) Time {minutEa)3 3 3 Stage 3 High-Pressure10000 10000 10000 (Ibf) Time to cool 20 20 20 mold to ambient temperature using a heat-transfer fluid (minutes) Notes: The chase (mold) is 8-rnils thick, 5.75 in. long, and 5.75 in, wide.
PP = polypropylene; PC = polyc:arbonate.
_11 _ WO 99/60643 PC'f/US99/10955 Bipolar plates were then Errepared using the above-described solid layers and the following carbon papers. The carbon papers were obtained from Spectracorp (Lawrence, MA) and Toray (Tokyo, Japan). In Comparative Examples 1 and 2, the carbon paper/plastic assemblies were compressed sufficiently to cause the fibers of the paper to touch each other within the bipolar plate, in order to achieve electrical contact between the layers and good conductivity.
Table: 3. Bipolar Plate Compositions Example Carbon paper, Fill Plastic Plate No. density (g/cm3), Thickness thickness (mil) (mil) Comp. Ex. Spectracorp, 0.50, none nylon 66 21.5 1 * 11.5 2 Toray (TGPH090), carbon nylon 66 23 0.50, 9 fiber 3** Spectracorp, 0.50, carbon nylon 66 16 11.5 fiber 4 Spectracorp, 0.50, carbon polypropylene20 11.5 black Spectracorp, 0.25, carbon nylon 66 12 8 fiber Comp. Ex. Spectracorp, 0.50, none polypropylene19.5 2 * 11.5 6 Spectracorp, 0.69, carbon nylon 66 44.5 18.5 fiber 7 Spectracorp, 0.67, carbon nylon 66 32.5 11.5 fiber * Comparative Example - not an example of the invention.
1() Below are the values for the product of through-plane resistivity for Examples 2-7.
Table 4 Example No. Area Resistivity (S2-cm2)Permeability (wD) Comp. Ex. 1* 0.0202 too high to measure 2 0.00018 0.14 3 0.0018 0.20 4 0.0042 2.5 5 0.00024 3.7 Comp. Ex. 2* 0.00074 15 6 0.0068 2.1 7 0.014 1.2 Examr~les 8-10 Three bipolar plates with cooling channels were assembled as illustrated in Figure 3, using polytetrafluoroethylene or steel tubing as a conduit material, except that carbon paper is used in Example 8. The chasE; (mold) thickness (See Figure 3) was double the plate thickness. The carbon paper usE;d was 11.5 mils thick and had a density of 0.50 g/cm3.
The assemblies were molded under the conditions described in Examples 1-7.
Table 5. Dimensions of Components for the Bipolar Plate with Cooling Channels Example No. Material Conduit Diameter Plate Thickness (mil) 8 carbon black 1/16 in. polytetrafluoroethylene63 &
polypropylE;ne 9 carbon fiber 1/16 in. polytetrafluoroethylene63 &
nylon 66 10 carbon fiber 18 gauge stainless steel42 &
nylon 66 Upon molding, the poiytetrafluoroethylene tubing did not collapse when placed in between the carbon black-polypropylene plates and was easily retrieved. The cooling holes that ran inside the plate were centered. The carbon-black polypropylene had a relatively 1'S low viscosity at its processing ternperatures, and the molten material easily conformed around the polytetrafluoroethylene tubing. However, due to the much greater viscosity of the carbon fiber-filled nylon 66 ai: its recommended processing temperature, the polytetrafluoroethylene tubing collapsed when trying to mold a plate out of this material.
When the stainless steel conduit, gauge 18, was employed to mold cooling channels 2 0 in a carbon-fiber nylon 66 bipolar plate, the tubing did not collapse. The metal tubing was not retrieved.
Claims (19)
1. A bipolar separator plate for two electrochemical cells connected in series, the plate comprising two layers of a porous electronically-conductive material having positioned therebetween a solid layer of a polymeric material having dispersed therein at least 1 percent by weight of a conductive filler, wherein the plate has an area resistivity of less than 1 ohm-cm2, and wherein the solid layer has a permeability of less than 50 µDarcy (µD).
2. The separator plate of claim 1 wherein the conductive filler is used in an amount, based on the weight of the polymeric material, of at least 20 percent.
3. The separator plate of claim 1 wherein the conductive filler is used in an amount, based on the weight of the polymeric material, of at least 50 percent.
4. The separator plate of claim 1 wherein the conductive filler is carbon fiber having a diameter of 7 µm.
5. The separator plate of claim 1 which has a thickness of at least 10 mils.
6. The separator plate of claim 1 wherein the porous electronically-conductive material is carbon fiber paper having a porosity of at least 60 percent.
7. The separator plate of claim 1 wherein the polymeric material is a thermoplastic polyurethane.
8. The separator plate of claim 1 wherein the polymeric material is a polypropylene.
9. The separator plate of claim 1 wherein the polymeric material is a syndiotactic polystyrene.
10. The separator plate of claim 1 wherein the polymeric material is a vinyl ester resin.
11. The separator plate of claim 1 wherein the polymeric material is polyvinylidene fluoride.
12. The separator plate of claim 1 wherein the polymeric material is polytetrafluoroethylene.
13. The separator plate of claim 1 wherein the polymeric material is a polyepoxide.
14. A bipolar separator plate for two electrochemical cells connected in series, the plate comprising three layers of a porous electronically-conductive material having positioned between the first and second layer, and the second and third payer, a solid layer of a polymeric material having dispersed therein at least 1 percent by weight of a conductive filler, wherein the plate has an area resistivity of less than 1 ohm-cm2, and wherein the solid layer has a permeability of less than 50 µDarcy (µD).
15. An electrochemical device having at least two electrochemical cells connected in series, each cell containing a gas or liquid material which is separated from a different gas or liquid material in an adjacent cell by two porous layers of electronically-conductive material having positioned therebetween a solid layer of a polymeric material having dispersed therein at least 1 percent by weight of a conductive filler, wherein the plate has an area resistivity of less than 1 ohm-cm2, and wherein the solid layer has a permeability of less than 50 µD.
16. The electrochemical device of claim 15 wherein the conductive filler is used in an amount, based on the weight of the polymeric material, of at least 50 percent.
17. The electrochemical device of claim 15 wherein the conductive filler is carbon fiber having a diameter of 7 µm.
18. The electrochemical device of claim 15 which has a thickness of at least 20 mils.
19. The electrochemical device of claim 15 wherein the porous electronically-conductive material is a carbon fiber paper having a porosity of at least 70 percent.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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US09/082,931 US6103413A (en) | 1998-05-21 | 1998-05-21 | Bipolar plates for electrochemical cells |
US09/082,931 | 1998-05-21 | ||
PCT/US1999/010955 WO1999060643A1 (en) | 1998-05-21 | 1999-05-18 | Bipolar plates for electrochemical cells |
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CA2332807A1 true CA2332807A1 (en) | 1999-11-25 |
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CA002332807A Abandoned CA2332807A1 (en) | 1998-05-21 | 1999-05-18 | Bipolar plates for electrochemical cells |
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US (1) | US6103413A (en) |
EP (1) | EP1080509B1 (en) |
JP (1) | JP2002516467A (en) |
AT (1) | ATE221257T1 (en) |
CA (1) | CA2332807A1 (en) |
DE (1) | DE69902259T2 (en) |
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-
1998
- 1998-05-21 US US09/082,931 patent/US6103413A/en not_active Expired - Fee Related
-
1999
- 1999-05-18 DE DE69902259T patent/DE69902259T2/en not_active Expired - Fee Related
- 1999-05-18 CA CA002332807A patent/CA2332807A1/en not_active Abandoned
- 1999-05-18 JP JP2000550163A patent/JP2002516467A/en active Pending
- 1999-05-18 AT AT99921981T patent/ATE221257T1/en not_active IP Right Cessation
- 1999-05-18 MX MXPA00011427A patent/MXPA00011427A/en not_active Application Discontinuation
- 1999-05-18 EP EP99921981A patent/EP1080509B1/en not_active Expired - Lifetime
- 1999-05-18 WO PCT/US1999/010955 patent/WO1999060643A1/en active IP Right Grant
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EP1080509A1 (en) | 2001-03-07 |
DE69902259D1 (en) | 2002-08-29 |
JP2002516467A (en) | 2002-06-04 |
WO1999060643A1 (en) | 1999-11-25 |
EP1080509B1 (en) | 2002-07-24 |
MXPA00011427A (en) | 2004-09-06 |
ATE221257T1 (en) | 2002-08-15 |
US6103413A (en) | 2000-08-15 |
DE69902259T2 (en) | 2003-03-20 |
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