WO2003019704A1 - Fuel cell stack with passive air supply - Google Patents
Fuel cell stack with passive air supply Download PDFInfo
- Publication number
- WO2003019704A1 WO2003019704A1 PCT/US2002/028401 US0228401W WO03019704A1 WO 2003019704 A1 WO2003019704 A1 WO 2003019704A1 US 0228401 W US0228401 W US 0228401W WO 03019704 A1 WO03019704 A1 WO 03019704A1
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- WO
- WIPO (PCT)
- Prior art keywords
- fuel
- air
- flow field
- fuel cell
- stack
- Prior art date
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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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
- H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
-
- 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
- H01M8/0258—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant
- H01M8/026—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant characterised by grooves, e.g. their pitch or depth
-
- 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
-
- 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
- H01M8/2465—Details of groupings of fuel cells
- H01M8/2483—Details of groupings of fuel cells characterised by internal manifolds
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Definitions
- the present invention relates generally to fuel cell stacks using hydrogen or methanol fuel, and, more particularly, to fuel cell stacks having a passive air supply.
- PEFCs Polymer electrolyte fuel cells
- a fuel supply such as hydrogen or methanol
- an oxidant which may be air.
- Early fuel cells required systems that provided fuel cell cooling and a pressurized and humidified air supply. These systems did not enhance the portability of PEFCs.
- a passive air fuel cell system with hydrogen or methanol fuel can readily fulfill these requirements and offer significant advantage over the advanced batteries available today, especially in terms of the power density and energy capacity for long mission duration.
- the hydrogen/passive air fuel cell according to this invention is operated with ambient air naturally diffused to the fuel cell cathode. Since there are no pumps or other moving parts and energy consuming peripheral equipment involved in the system, system reliability and energy conversion efficiency are greatly enhanced. Also, because the air reactant transport to the electrode surface occurs by natural diffusion in the passive stack, an even reactant distribution among the cells can be more conveniently achieved than in a system using forced air feed.
- the control system can be greatly simplified or eliminated, and operation becomes more user friendly.
- the passive air power systems have potential as portable power sources of choice for both military and commercial markets, especially for low power applications, where the overall system specific energy density requirement, as high as a few thousands watts per kg, does not permit the added weight of complicated auxiliary equipment and control systems.
- the passive air fuel cell systems are much more like batteries in the sense of system simplicity and are more suitable for portable power applications.
- U.S. Patent 5,514,486 is directed to a passive ("air-breathing") portable PEFC where hydrogen fuel is supplied through a central annulus and air is supplied through diffusion along a radially directed porous flow field about the periphery of the device.
- the porous flow field acts to retain water reaction products in the cell to maintain hydration of the polymer electrolyte and to affect cooling of the cell.
- a drawback in the annular design is the limitation in the size of electrode area. As the electrode area is increased, the portion of the peripheral area from which oxygen from air diffuses readily to the electrode becomes small and stack performance suffers.
- the annular design provides greater energy than a conventional NiCad battery of similar size, but does not deliver power levels as high as NiCad batteries.
- the present invention provides a portable fuel cell stack that has a high power density and does not require auxiliary equipment for the supply of reactants, i.e., hydrogen or methanol and oxygen from air.
- reactants i.e., hydrogen or methanol and oxygen from air.
- a rectangular cell geometry and an open air flow field permit good access of air to the air cathode and easy release of water which is the fuel cell reaction product.
- the present invention includes a fuel cell stack having a plurality of polymer electrolyte fuel cells (PEFCs) where each PEFC includes a rectangular membrane electrode assembly (MEA) having a fuel flow field along a first axis and an air flow field along a second axis perpendicular to the first axis, where the fuel flow field is long relative to the air flow field.
- MEA membrane electrode assembly
- a cathode air flow field in each PEFC has air flow channels for air flow parallel to the second axis and that directly open to atmospheric air for air diffusion within the channels into contact with the MEA.
- FIGURE 1 is an exploded isometric view of a fuel cell according to one embodiment of the present invention.
- FIGURE 2 is an exploded isometric view of a fuel cell stack incorporating the fuel cells shown in FIGURE 1.
- FIGURE 3 graphically depicts the steady state performance of a six cell fuel cell stack having hydrogen feed and open to ambient air.
- FIGURE 4 graphically depicts polarization curves of individual cells in the fuel cell stack used to obtain the performance shown in FIGURE 3.
- FIGURE 5 graphically depicts the steady state performance of a six cell fuel cell stack having direct methanol feed and open to ambient air.
- the anode flow field is also provided with a perforated corrugated design.
- a uniform distribution of reactant and reaction products is obtained to maximize use of the fuel cell active electrode area.
- the cell rectangular design is a particular feature of the present invention.
- the MEA defines a long axis and a short axis perpendicular to the long axis.
- An anode flow field is oriented with hydrogen or methanol flow channels "fuel channels" parallel to the long axis.
- a cathode airflow field is oriented with air flow channels parallel to the short axis.
- the air flow channels are open to the atmosphere at the two ends of each channel so that air can diffuse into the cell from both sides along the air flow channels.
- Hydrogen or methanol is provided to the fuel channels through manifolds that are internal to the fuel cell stack. Hydrogen may be supplied from a pressurized container or from a metal hydride storage system; methanol may be supplied as an aqueous solution.
- the rectangular configuration provides a limited diffusion distance for air in the air flow channels so that adequate air is available along the MEA for reacting with fuel to provide a desired current density without incurring oxygen concentration polarization.
- the maximum rate of air diffusion flux per electrode area is related to the channel dimensions, i.e., the channel thickness and channel length.
- the length of the fuel flow field is then determined by total active electrode area required to provide the current and concomitant power output desired from the cell, i.e., the longer the fuel flow field, the greater total electrode area (with a fixed air channel length) and the total output current/power.
- the approach to optimize the configuration of the cathode and anode flow fields i.e., the length of the fuel channels, the length for air diffusion across the fuel channels, and the thickness of the air diffusion channels is based on (a) calculated estimates for the flow field thickness based on basic physical and electrochemical parameters and (b) optimizing around an estimate by experimentation.
- a thickness for the cathode flow filed is estimated by calculating the rate of supply of oxygen from air by diffusion along the rectangular opening defined by the overall thickness of the flow field and the length of the fuel channels.
- the rate of oxygen supply should react sufficient oxygen to produce the electrical current demanded from an active area of the cell defined by the lateral dimensions of the cell. If the length of the fuel channels (long axis of the cell) is designated d' , the length for air diffusion (short axis of the cell) (which is half the short axis dimension for two-sided air access), and the flow field thichkness by/ ⁇ , then the rate of oxygen supply needed by diffusion along the cathode is related to the current density J required from the fuel cell by:
- C° is the concentration of oxygen in air (8.73 x 10 "6 mol/cm 3 at 1 atm and
- the thickness of the cathode flow filed is then calculated from ⁇ qn. 1 to be:
- h given by ⁇ qn. 2 provides an initial estimate for the thickness of the cathode flow field required for effective oxygen supply through the edge of the stack, as shown in Figure 2.
- the actual rate of oxygen supply along the flow field for some specific geometry will vary somewhat as a function of the degree of openness of the flow field, as well as the cell temperature and the possible presence of liquid water in the flow field.
- a more precise optimized thickness can be defined for a specific stack by testing stack performance as a function of the thickness of the cathode flow field, i.e., varying the thickness in experimental stacks in, e.g., a range of 0.5x to 2x the estimated thickness.
- the minimum effective thickness of the cathode flow field hsted, identified experimentally as the minimum width providing the current demand at the same cell voltage (e.g., within 5-10 mV) as measured for a reference "face- breathing" cell, where the reference face-breathing cell is a single cell with the cathode opening directly to the air supply, i.e., the supply of air comes from a solid angle of 180°, and using the same MEA in the side-opening stack and operating under the same fuel feed conditions.
- the initial test results for operation in H 2 /passive air mode demonstrate the potential of this design concept.
- FIG. 1 shows the components of a unit cell within the 6-cell H 2 passive air stack.
- This cell consists of a membrane electrode assembly 20 having a membrane, anode backing, and cathode backing; anode flow field 24 made by corrugating a piece of perforated metal sheet; cathode flow field 14 made by corrugating a piece of perforated metal sheet; cathode side frame 16; anode side frame 22; anode side gasket 26; cathode side gasket 12; and bipolar plates 28.
- MEA 20 is rectangular in shape, having a long axis for hydrogen fuel flow and a short axis for air diffusion, where the long axis is perpendicular to the short axis.
- the length of the fuel flow field was 7.6 cm (long axis) and the length of the diffusion path was 2.6 cm, but neither of these dimensions has been optimized herein.
- the following detailed description of the components of the unit cell is meant to be exemplary and many different components might be used in place of the exemplary components, unless specifically noted.
- Membrane electrode assembly (MEA) 20 The membrane component of MEA 20 was made by painting Pt ink directly on to both sides of a polymer proton conducting membrane, such as a polymer electrolyte membrane, a National® 1 135 membrane (1 100 E.W. and 3.5 mil thick) in particular, over a vacuum table heated at 60°C.
- the Pt ink was made by mixing Pt black powder (30 m 2 g "1 , Johnson Matthey) catalyst with 10 times the amount of water by weight first, and then with 2.2 times the amount of 5 % N1200 E.W. ionomer solution (Solution Technology, Inc) by weight.
- the resulting composition of the dry ink is 90 % Pt black and 10 % of recast N1200 E.
- the electronic conducting phase (Pt) and protonic conducting phase (recast N1200 E. W. ionomer) form a thorough mixture so that the catalytic centers can be reached by reactants and connected to both electrode and membrane through the electronic and ionic conduction paths.
- Pt supported on carbon particles can have a larger number of platinum atoms on the surface, thus with more active sites, on a unity Pt weight basis. Since the densities of supported catalysts change with the platinum loading level on carbon, the suitable amount of recast ionomer in the catalyst ink should be adjusted accordingly.
- MEA 20 includes: Anode backing : E-tek 2.02 hydrophilic single sided carbon cloth backing (2.0 x 7.0 cm 2 ) was used to contact the anode side active area
- Cathode backing E-tek NC/DSA 2 hydrophobic carbon backing (2.0 x
- Anode flow field 24 The anode flow field (7.6 x 2.0 cm 2 ) was made from a corrugated and perforated 4 mil 316 L stainless steel sheet. The folds and troughs of the corrugation were oriented along the long side of the MEA to channel H 2 gas or methanol solution from the two manifolds into the active electrode area. The thickness of the flow field channels defined by the folds and troughs was 28 mil (about 0.7 mm) and has not been optimized herein.
- Cathode flow field 14 The cathode flow field (2.6 x 7.0 cm 2 ) was made from a corrugated and perforated 5 mil stainless steel sheet. The folds and troughs of the corrugation were oriented along the short side of the MEA to channel air from outside into the active electrode area. As with the anode field, the depth of the flow field channels defined by the folds and troughs is 28 mil and has not been optimized herein.
- Supporting frames 16, 22 One 8 mil thick supporting frame was placed on each side of the MEA.
- the frame contained two small rectangular shaped openings (0.150 x 1.85 cm 2 ) to match the fuel manifolds, and one large rectangular shaped opening (2.0 x 7.0 cm 2 ) to match the active electrode area.
- the supporting frames were made of G-10 fiber reinforced plastics. The purpose and function of the supporting frame are to (1 ) frame around the backing and match the backing thickness so as to achieve dimensional uniformity and sealing when the stack is assembled and compressed, (2) support the silicon gasket by bridging over the troughs of the corrugated channels.
- Anode side gasket 26 and cathode side gaskets 12 The gaskets were made from 32 mil thick 60 durometer silicon rubber sheet material. The compressed thickness of the gaskets in the assembled stack was 27 mil, and matched the thickness of the flow fields so as to achieve a good seal. Cathode side gaskets 12 were located parallel to airflow channels in cathode flow field 14 and did not cover the ends of the air flow channels. Anode side gasket 26 was formed as a frame around anode flow field 24 with side spacing to match the fuel manifold opening in anode side frame 22 and mating bipolar plate 29.
- Bipolar plates 28 Each of the bipolar plates 28 was made from a piece of 2 mil thick 316 L stainless steel sheet, and contained two small rectangular shaped openings (0.150 x 1.85 cm 2 ) to match the fuel manifolds.
- Figure 2 is an exploded isometric view of a fuel cell stack incorporating six unit cells, as shown in Figure 1. Each unit cell includes cathode side gasket 12; cathode flow field 14; MEA frame 20 with enclosed MEA 18; an assembly of anode side frame 22, anode flow field 24, and anode side gasket 26; and bipolar plates 28.
- the two bipolar plates 28 at the beginning and ending of the cell stack also serve as current collectors with current take-off tabs 38, 42.
- a fiber reinforced Teflon tape (not shown) was placed at the inner face of each endplate 32.
- Each fuel manifold 36 on each side of plates 28 introduce/remove fuel from the anode flow fields 24, which have flow channels perpendicular to manifold 36 and parallel to the long axis of the unit cell, as discussed above.
- cathode flow field 14 is oriented with the flow channels parallel to the short axis of MEA 20.
- the channels formed by the folds and troughs of flow field 14 are open to the atmosphere at the two ends of each channel so that air can diffuse into the channels along the cathode side of the MEA.
- the air diffusion length along the short axis of MEA 20 is relatively short so as to provide adequate oxygen flux availability throughout the diffusion length.
- the shorter the short axis, or the greater the air channel thickness the higher the oxygen flux reaching per active cathode electrode area.
- the unit fuel cells are sandwiched between end plates 32 and clamped using a plurality of bolts 46 with end nuts 48.
- an air filter 44 may be placed adjacent open air flow channel ends of cathode flow fields 14 (top and bottom of the stack) to keep particulate matter from forming flow obstructions in the flow channels.
- a suitable filter 44 is simply a porous polyethylene paper (15# SyntraTM 5507-AX, Lydall Manning Nonwovens, Lydall, Inc).
- a fuel connection 34 is provided on each end plate 32.
- the fuel connections 34 are oriented so that the connections are diagonally located on the assembled fuel cell stack.
- a preferred orientation places the outlet connection at a location lower than the inlet location so that the water reaction product can readily flow from the stack.
- Figure 3 depicts a steady state 6-cell H 2 /passive air stack polarization curve (filled symbols) and the corresponding stack power output (open symbols). Hydrogen was fed to the anode inlet at 0.76 atm with cathode flow fields open to the atmosphere at 0.76 atm. The performance shown by solid line was obtained when the cathode flow field planes and channels were in vertical position, and the performance shown by dashed line was obtained when the cathode flow field planes and channels were in horizontal position. The stack reached a steady temperature of 37°C when operated at 4.2 V or 0.7 V per cell for an extended period of time. The nearly identical performance curves show that the stack performance is insensitive to stack orientation.
- Figure 4 depicts polarization curves of the individual cells in the 6-cell H 2 /passive air stack at the steady state conditions shown for Figure 4.
- the individual cell performance at a current up to 0.8 A was relatively uniform across the stack. Cells in the center of the stack showed somewhat better performance than those close to the end plates, probably due to a higher cell temperature at the center of the stack.
- Table A depicts the performance of an experimental 6-cell stack of hydrogen fuel cells with passive air flow and dead-end hydrogen at zero-psig back pressure.
- the demonstrated performance of the 6-cell hydrogen/passive air stack compares favorably with that of a hydrogen /air-breathing fuel cell stack which has annular feed stack structure as described in U.S. Patents No. 5,595,834 and No. 5,514,486 as the state of art.
- the dimension of a projected 25 W (delivered at 0.5 V/cell with 40 cells) hydrogen-air stack with the maximum cell packing density is 6.4 cm in diameter and 8 cm long (not include endplates and bolts), or 257 cm 3 in volume.
- the stack according to the present invention will work at a much higher energy conversion point (61.5% vs. 42%) and still have a higher volumetric power density (135 W/L at 0.7 V /cell vs.
- Figure 5 depicts a steady state 6-cell direct methanol/passive air stack polarization curve (filled symbols) and the corresponding stack power output
- Table B depicts the performance of an experimental 6-cell stack of direct methanol (0.3 M methanol solution) fuel cells with passive air flow.
- Cell-stack is the complete stack without endplates, fitting and screws.
- a high level of water and methanol crossover through the polymer electrolyte membrane represents significant problems for the stack performance and for the water balance.
- the methanol crossover can be minimized to a large degree for a power system operated under a constant load by using an anode structure suitably designed, as taught by U.S. Patent Application S.N. 09/472,387, filed December 23, 1999, and incorporated herein by reference.
- Water balance between the anode and the cathode for a direct methanol fuel cell system may be maintained by utilizing the hydrophilic and hydrophobic properties of the anode and cathode backings.
- a static hydrodynamic pressure is established across the polymer electrolyte membrane, which pushes water from the cathode side to the anode side, and, thus, counters the water flux by electro-osmotic drag. Since the water flux produced by electro-osmotic drag is independent of the membrane thickness, while the water flux produced by hydrodynamic pressure is inversely proportional to the membrane thickness, a water balance can be more easily established with a thinner membrane.
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Abstract
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Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US31562701P | 2001-08-29 | 2001-08-29 | |
US60/315,627 | 2001-08-29 | ||
US10/119,892 US6986961B1 (en) | 2001-08-29 | 2002-04-10 | Fuel cell stack with passive air supply |
US10/119,892 | 2002-04-10 |
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WO2003019704A1 true WO2003019704A1 (en) | 2003-03-06 |
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PCT/US2002/028401 WO2003019704A1 (en) | 2001-08-29 | 2002-08-22 | Fuel cell stack with passive air supply |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2006068527A2 (en) * | 2004-12-21 | 2006-06-29 | Sre-Soluções Racionais De Energia, S.A. | Hydrogen- fuel cell stack with integrated cooling and air supply for use with a fixed pressure dead-ended supply configuration |
Citations (6)
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US5804326A (en) * | 1996-12-20 | 1998-09-08 | Ballard Power Systems Inc. | Integrated reactant and coolant fluid flow field layer for an electrochemical fuel cell |
US6255012B1 (en) * | 1999-11-19 | 2001-07-03 | The Regents Of The University Of California | Pleated metal bipolar assembly |
US6296963B1 (en) * | 1997-11-14 | 2001-10-02 | Mitsubishi Heavy Industries, Ltd. | Solid oxide electrolyte fuel cell |
US6299996B1 (en) * | 1999-09-24 | 2001-10-09 | Plug Power Inc. | Fuel cell system |
US6322915B1 (en) * | 1999-07-20 | 2001-11-27 | International Fuel Cells Llc | Humidification system for a fuel cell power plant |
US6413664B1 (en) * | 1999-12-23 | 2002-07-02 | Ballard Power Systems Inc. | Fuel cell separator plate with discrete fluid distribution features |
-
2002
- 2002-08-22 WO PCT/US2002/028401 patent/WO2003019704A1/en not_active Application Discontinuation
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5804326A (en) * | 1996-12-20 | 1998-09-08 | Ballard Power Systems Inc. | Integrated reactant and coolant fluid flow field layer for an electrochemical fuel cell |
US6296963B1 (en) * | 1997-11-14 | 2001-10-02 | Mitsubishi Heavy Industries, Ltd. | Solid oxide electrolyte fuel cell |
US6322915B1 (en) * | 1999-07-20 | 2001-11-27 | International Fuel Cells Llc | Humidification system for a fuel cell power plant |
US6299996B1 (en) * | 1999-09-24 | 2001-10-09 | Plug Power Inc. | Fuel cell system |
US6255012B1 (en) * | 1999-11-19 | 2001-07-03 | The Regents Of The University Of California | Pleated metal bipolar assembly |
US6413664B1 (en) * | 1999-12-23 | 2002-07-02 | Ballard Power Systems Inc. | Fuel cell separator plate with discrete fluid distribution features |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2006068527A2 (en) * | 2004-12-21 | 2006-06-29 | Sre-Soluções Racionais De Energia, S.A. | Hydrogen- fuel cell stack with integrated cooling and air supply for use with a fixed pressure dead-ended supply configuration |
WO2006068527A3 (en) * | 2004-12-21 | 2007-02-08 | Sre Solucoes Racionais De En S | Hydrogen- fuel cell stack with integrated cooling and air supply for use with a fixed pressure dead-ended supply configuration |
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