WO2004100301A1 - 直接形燃料電池システム - Google Patents
直接形燃料電池システム Download PDFInfo
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- WO2004100301A1 WO2004100301A1 PCT/JP2004/004477 JP2004004477W WO2004100301A1 WO 2004100301 A1 WO2004100301 A1 WO 2004100301A1 JP 2004004477 W JP2004004477 W JP 2004004477W WO 2004100301 A1 WO2004100301 A1 WO 2004100301A1
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- Prior art keywords
- fuel
- air
- cell system
- fuel cell
- direct
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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
- H01M8/2465—Details of groupings of fuel cells
- H01M8/247—Arrangements for tightening a stack, for accommodation of a stack in a tank or for assembling different tanks
- H01M8/2475—Enclosures, casings or containers of fuel cell stacks
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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
- H01M8/0258—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant
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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
- H01M8/0267—Collectors; Separators, e.g. bipolar separators; Interconnectors having heating or cooling means, e.g. heaters or coolant flow channels
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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
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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
- H01M8/04186—Arrangements for control of reactant parameters, e.g. pressure or concentration of liquid-charged or electrolyte-charged 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
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04223—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids during start-up or shut-down; Depolarisation or activation, e.g. purging; Means for short-circuiting defective fuel cells
- H01M8/04225—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids during start-up or shut-down; Depolarisation or activation, e.g. purging; Means for short-circuiting defective fuel cells during start-up
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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
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
- H01M8/0687—Reactant purification by the use of membranes or filters
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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
- H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
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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
- H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
- H01M8/2455—Grouping of fuel cells, e.g. stacking of fuel cells with liquid, solid or electrolyte-charged reactants
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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
- H01M8/2465—Details of groupings of 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
- H01M8/2465—Details of groupings of fuel cells
- H01M8/2483—Details of groupings of fuel cells characterised by internal manifolds
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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
- H01M8/2465—Details of groupings of fuel cells
- H01M8/2484—Details of groupings of fuel cells characterised by external manifolds
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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
- H01M8/04119—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with simultaneous supply or evacuation of electrolyte; Humidifying or dehumidifying
- H01M8/04156—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with simultaneous supply or evacuation of electrolyte; Humidifying or dehumidifying with product water removal
- H01M8/04164—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with simultaneous supply or evacuation of electrolyte; Humidifying or dehumidifying with product water removal by condensers, gas-liquid separators or filters
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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
Definitions
- the present invention relates to a direct fuel cell system using a liquid fuel fuel cell in which a fuel such as methanol, ethanol, isopropanol, or butanol is mixed with water and supplied directly to a fuel electrode.
- a fuel such as methanol, ethanol, isopropanol, or butanol is mixed with water and supplied directly to a fuel electrode.
- the present invention particularly relates to a direct fuel cell system in which fuel is naturally supplied to a liquid fuel fuel cell by convection or the like.
- Patent Document 1 JP 2003-100315 (E P 1296400A2)
- Patent Document 2 JP 2002-343378 A (U SP 20020172853A1)
- Patent Document 1 proposes a battery structure in which a plurality of monolithic cells are attached to the surface of a fuel tank.
- Patent Document 2 discloses a hollow fuel cell. A structure in which an air electrode is arranged outside the tank has been proposed. Summary of the Invention
- a basic object of the present invention is to simplify the supply of fuel in a direct fuel cell system, and in particular to eliminate the need for a fuel pump for supplying fuel from a fuel tank to a cell stack.
- An additional object of the present invention is to make it possible to control the direct fuel cell system to output an appropriate output according to a load request, and to prevent irreversible deterioration of the fuel cell.
- This is an additional object of the present invention is a liquid level of the fuel tank along with eliminating the need to adjust have use the Reberume one coater and a pump or the like, Ru near to facilitate the discharge of co 2 from the fuel tank.
- An additional object of the present invention is to facilitate starting of a direct fuel cell system.
- An additional object of the present invention is to enable the direct fuel cell system to operate even when installed at an angle from a horizontal plane.
- An additional object of the present invention is to make the direct fuel cell system compact by allowing excess water from the direct fuel cell system and water generated at the cathode to be recovered without a dedicated drain tank. Is to do.
- An additional problem with the present invention is:
- a secondary problem with the fuel cassette of the present invention is that
- the direct fuel cell system according to the present invention is a cell stack in which a plurality of unit cells having a fuel electrode on one surface of a proton conductive polymer solid electrolyte membrane and an air electrode on the other surface are connected in series via a separator.
- the cell stack In the fuel cell operated by liquid fuel, the cell stack is installed in the fuel tank so that at least a part of the cell stack is immersed below the liquid fuel level in the fuel tank, and the fuel electrode of the separator is A flow path for fuel supply is provided on the side surface, and both ends of the flow path are arranged below the liquid level of the liquid fuel to communicate with the liquid fuel, and the fuel in the fuel tank is naturally supplied to the fuel electrode, and the separator is provided.
- the air electrode side surface is provided with a flow path for air supply.
- an exhaust portion is provided at an upper portion of the fuel tank so that carbon dioxide generated at the fuel electrode is exhausted from the exhaust portion, and air outside the fuel tank is sent to the air electrode by a blower or a fan.
- a blower means both a blower and a fan.
- control unit controls the air supply amount of the blower or the fan according to the operating state of the fuel cell.
- the air supply amount of the blower or the fan is controlled so that the output voltage of the fuel cell is maintained at a predetermined value or more, and in particular, the air supply amount is increased by decreasing the output voltage.
- the cell stack is installed so as to be immersed in the fuel in the fuel tank, and the fuel is supplied to the fuel electrode by convection or the like, and the carbon dioxide generated at the fuel electrode is discharged to the upper exhaust part of the fuel tank. Exhaust from. This eliminates the need for a pump to supply fuel to the cell stack, provides a compact system, and eliminates the need for a gas-liquid separator for separating carbon dioxide from liquid fuel.
- an exhaust pipe for discharging exhaust gas from the outlet side of the air supply flow path of the separator to the outside of the fuel tank is provided, and heat exchange is performed on the exhaust gas from the exhaust pipe, and the liquid level of the fuel tank is changed. Depending on the level, one of the forces to drain the water recovered by heat exchange to the water tank and to return it to the fuel tank.
- the fuel and water in the fuel tank will be taken out of the system by the exhaust gas, and the liquid level in the fuel tank will drop. It is necessary to supply high-concentration methanol and water to make up for this. In addition, when water is completely recovered, the fuel level in the fuel tank rises, so it is necessary to frequently drain the fuel from the fuel tank. This is inconvenient, and care must be taken because formic acid and formaldehyde are contained in the remaining fuel.
- the liquid level in the fuel tank can be kept constant. This minimizes the need to refuel the fuel tank and eliminates the need to dump fuel directly from the fuel tank.
- an air supply pipe for supplying air from the blower or fan to the separator is provided, and a valve is provided for each of the exhaust pipe and the air supply pipe, and each valve is closed when the fuel cell is stopped, and the cell stack is provided. Keep the air supply channel airtight.
- the fuel will enter the air electrode side.
- a blower or fan it is necessary to discharge the fuel that has entered the air electrode side with a blower or fan, but this is difficult.
- the flow path is in a grid pattern, fuel is likely to remain in any place, and even if a flow path that is not on the grid is used, a blower or fan is required to have an excessive blowing capacity. If air and a large amount of fuel coexist in the cathode, the cathode is likely to heat up more than necessary.
- valve is closed when the fuel cell is stopped and the air supply channel of the cell stack is kept airtight, entry of fuel into the air electrode can be minimized and start-up is facilitated.
- an air pipe and a valve for bubbling air into the fuel in the fuel tank are provided from the bottom of the cell stack, and air is supplied to the fuel supply flow path of the cell stack during cold start. If both ends of the fuel supply flow path are immersed in the liquid fuel, air enters the fuel supply flow path, for example, by publishing from near the bottom of the cell stack.
- cold start means that the room temperature or liquid fuel temperature is 0 ° C or lower, or 10 ° C or lower, for example, but the specific temperature conditions are appropriately determined according to the characteristics of the fuel cell. Just do it.
- the air pipe is equipped with a valve, so the valve should be closed except when starting cold.
- a gas space remaining on the liquid surface is provided in the fuel tank, and a plurality of exhaust parts are provided at different positions in the horizontal plane at the upper part of the fuel tank, so that when the fuel tank is tilted, Make sure the exhaust is in contact with the gas space.
- the exhaust unit is, for example, a water-impermeable permeable membrane or a coiled air passage, and exhausts carbon dioxide from a gas space.
- the exhaust part may sink below the liquid level when the fuel tank is tilted. Then, it becomes difficult to discharge carbon dioxide from the exhaust part, and the fuel tank may be inadvertently pressurized, resulting in liquid leakage.
- a plurality of gas parts are provided, one of them remains on the liquid surface, and even if the fuel tank is tilted, carbon dioxide can be discharged.
- tilt the fuel tank means tilting slightly from horizontal, for example, ⁇ 15 ° or less from the horizontal, specifically ⁇ 10. In the following, it means to tilt ⁇ 5 ° or less in the narrowest range.
- a fuel supply flow path is two-dimensionally arranged on the fuel electrode side surface of the separator. More preferably, the separator is made horizontally long, and the horizontal length of the separator is made larger than its height.
- the upper fuel discharge end of some of the flow paths may come out above the liquid level. In this case, no fuel flow occurs in the flow path, and the flow path does not function.
- the flow path in which fuel does not flow can be minimized, and the operating range when the fuel tank is tilted can be expanded. Can be supplied to the pole.
- both ends of the air supply flow path may be connected to the atmosphere, and air may be introduced into the cell stack by natural ventilation.
- the entire cell stack is immersed in the liquid fuel.
- both ends of the air supply flow path and both ends of the fuel supply flow path are arranged on different surfaces of the cell stack, and particularly preferably, both ends of the fuel supply flow path are used when the cell stack is used.
- Both ends of the air supply channel are arranged on both sides of the cell stack on the upper and lower sides of the cell stack.
- the fuel tank doubles as a storage container for the cell stack.
- a liquid fuel supply port is provided in the fuel tank.
- the liquid fuel is, for example, an aqueous methanol solution.
- liquid fuel can be continuously supplied to the fuel electrode side by convection of the liquid fuel due to the movement.
- liquid fuel can be supplied by capillary action in addition to convection of liquid fuel.
- an opening that is open to the atmosphere may be provided in the fuel tank, or an internal manifold structure is provided in the cell stack and the internal manifold is provided. May be supplied to the air supply flow path from the air supply.
- the liquid fuel is a mixture of water and an organic solvent not added with an acid such as sulfuric acid, and particularly preferably an aqueous methanol solution without acid.
- an acid-free liquid fuel the conductivity of the liquid fuel is low, so that damage to electrodes and the like due to electric corrosion caused by an electric field generated by the cell stack can be prevented.
- a member such as activated carbon zeolite is brought into contact with fuel to adsorb or decompose an acid such as formic acid generated by a side reaction, and also adsorb or decompose harmful substances such as formaldehyde.
- an insulating member is provided so as to protrude from the edge of the cell stack, particularly preferably to protrude from the four side surfaces of the cell stack, to prevent a liquid junction and suppress damage to electrodes and the like.
- the insulating member is, for example, a packing provided between the separator and the electrode.
- the fuel tank is replenished with liquid fuel from the fuel cassette, and a fuel reservoir and a drainage reservoir are provided in the fuel cassette, and the water taken out together with the exhaust air from the air electrode of the fuel cell is drained. Collect in reservoir.
- concentration of the liquid fuel to be replenished does not necessarily have to be constant. In this way, methanol, isopropanol, dimethyl Since the water in the liquid fuel supplied together with the ether and the water generated at the air electrode can be collected in the fuel cassette, the drainage tank can be made unnecessary or small. If the fuel cassette is replaced, it is easy to use because it can replenish the fuel and treat wastewater such as generated water.
- air is supplied to the air electrode from a pump or a fan, and water is collected in a drainage reservoir of a fuel cassette by using pressure from a blower or a fan added to exhaust air from the air electrode. It is difficult to collect water simply by providing a drain in the fuel electrode. For example, it is conceivable to provide a drain pump or the like to feed the water into the drain. On the other hand, by using a blower or fan, and by providing a discharge air discharge structure in the drainage reservoir, the pressure of the blower or fan remaining at the outlet side of the air electrode, etc. Moisture can be pumped in.
- a part of the water collected in the drainage reservoir of the fuel cassette or the impurities contained in the exhausted air is evaporated by a chemical filter and then discharged to the outside.
- the chemical filter is, for example, activated carbon, and zeolite or silica gel may be used in addition to these.
- a suitable oxidation catalyst alone residual methanol, formic acid, formaldehyde, methyl formate, and the like in the recovered water or steam may be treated.
- the chemical filter is provided in the path for evaporating water in the embodiment, the chemical filter may be disposed in the drainage reservoir and immersed in the drainage. If a chemical filter is used, the collected impurities can be processed safely and the water can be easily recovered.
- a means for discharging the exhaust air from the drainage reservoir is provided.
- the drainage reservoir serves as a buffer for keeping the fuel tank liquid level constant, and the fuel tank liquid level can be easily maintained in a predetermined range.
- a gas-liquid separator for separating water from the exhaust air of the air electrode is provided, and the liquid water separated by the gas-liquid separator is collected in a drainage reservoir of the fuel cassette.
- the gas-liquid separator has a structure that can hold a certain amount of water.
- the exhaust air can be Although it may be possible to exhaust water other than water by introducing the liquid to the liquid drainage reservoir, it is necessary to separate the water and the exhaust air in the drainage reservoir.
- the temperature of the fuel tank rises due to the exhaust air, which complicates seals for preventing fuel leakage and fuel evaporation, especially for seals at connectors (connectors) for direct fuel cell systems.
- Even when the exhaust air from which water has been separated is not to be returned to the fuel tank or the like, it is preferable to exhaust it after removing methanol vapor by treating it with a chemical filter such as activated carbon.
- the fuel cell is submerged in the fuel of the fuel tank, a part of the water in the exhaust air from the air electrode is returned to the fuel tank through the gas-liquid separator, and the gas is stored in the fuel tank.
- An outlet is provided to discharge carbon dioxide from the fuel electrode.
- the present invention further provides a fuel cassette for a direct fuel cell system, comprising: a fuel reservoir connectable to the system; and a drainage reservoir for storing wastewater from the system.
- a discharge structure is provided for discharging water to the outside, and a part of the water collected in the drainage reservoir or impurities contained in the exhausted air is treated with a chemical filter and then evaporated.
- a dedicated drain tank can be eliminated or reduced in size.
- the fuel concentration in the fuel reservoir of the fuel cassette is, for example, 20 to 100 wt%, preferably 40 to 100 sec%.
- the fuel is methanol-water, and the methanol concentration in the fuel reservoir is, for example, 30 wt ° /.
- the fuel from the fuel tank contains methanol and water in a volume ratio of about 1: 2, and the molar ratio of both is about 1: 4. Oxidation of 1 mole of methanol gives
- the methanol concentration in the fuel tank can be kept constant.
- the methanol concentration in the fuel reservoir is 2 O wt. /.
- the methanol concentration in the fuel tank can be kept constant. In this way, the amount of water taken out from the air electrode is collected in the drainage tank and the amount collected in the fuel tank so that the fuel concentration in the fuel tank becomes constant according to the liquid fuel concentration in the fuel tank. It is preferred to determine the ratio.
- the space of the drainage tank after all the liquid fuel in the fuel cassette has been consumed is larger than the amount of drainage generated by the reaction of the liquid fuel with air, so that the space of the drainage tank is partially reduced to carbon dioxide discharged to the outside. Everything except the water can be stored in that space.
- a window is provided in the case of the fuel cassette so that the fuel reservoir can be viewed.
- an elastic bag or a flexible bag is provided in the fuel tank, and these bags are colored, or a movable partition is provided between the drainage tank and the fuel tank to open the bag or the partition. Make it visible from the window. Or make the bag transparent and color the fuel with pigments or pigments. In this case, since the proton conductive polymer solid electrolyte membrane does not transmit the dye or pigment, the drainage reservoir is not colored. In any case, the fuel remaining can be easily visually checked by color.
- a sliding guide for attaching and detaching the fuel cell to and from the direct fuel cell system is provided on the fuel set.
- the guide member of the direct fuel cell system and the guide of the fuel cassette are engaged and slid, so that the fuel cassette can be easily attached and detached.
- the fuel cassette is provided with projections and recesses for catching when detaching from the direct fuel cell system.
- the projections and recesses for hooking are ridges that catch the user's finger, depressions that press the belly of the user's finger, or patterns that have multiple projections and depressions.
- the fuel cassette is set in the direct fuel cell system. When doing so, make sure that the irregularities are exposed. In this way, the fuel cassette set in the direct fuel cell system can be easily Can be pulled out.
- FIG. 1 is a vertical sectional view of a main part of an embodiment of a direct fuel cell system in which air is supplied using a probe.
- Fig. 2 shows a front view (left side: fuel electrode side) and a rear view (right side: air electrode side) of the separator used in the example.
- FIG. 3 is a perspective view showing the structure of the end plate of the cell stack used in the example.
- Fig. 4 shows a front view (left side: fuel electrode side) and a rear view (right side: air electrode side) of the separator of the modified example.
- FIG. 5 is a diagram schematically showing a state of the upper portion of the tank when the direct fuel cell system of the embodiment is tilted in the vertical direction.
- FIG. 6 is a diagram schematically showing a modification of the direct fuel cell system.
- FIG. 7 is a diagram schematically illustrating publishing to the fuel electrode at the time of startup.
- FIG. 8 is a schematic diagram when a high-concentration methanol tank and a water tank are mounted in a system case.
- FIG. 9 is a side view of a modified direct fuel cell system.
- FIG. 10 is a diagram showing an example of a cell structure of a direct fuel cell system according to an embodiment in which air is supplied by natural ventilation.
- FIG. 11 is a diagram showing an example of the cell stack.
- FIG. 12 is a partially cutaway perspective view of the direct fuel cell system according to the embodiment.
- FIG. 13 (a) is a sectional view taken along the line AA of FIG. 12, and FIG. 13 (b) is a sectional view taken along the line BB of FIG.
- FIG. 14 schematically shows an embodiment of a direct fuel cell system using a fuel cassette.
- FIG. 15 is a sectional view of the fuel cassette of the embodiment.
- FIG. 16 is a sectional view of a fuel cassette according to a modification.
- FIG. 17 is a sectional view of a fuel cassette of another modification.
- FIG. 18 is a sectional view of a fuel cassette of still another modification.
- FIG. 19 is a cross-sectional view of a fuel cut of another modification.
- FIG. 20 is a sectional view of a fuel cassette of another modification.
- FIG. 21 is a diagram schematically showing that the direct fuel cell system and the fuel cassette of the embodiment are connected via a hollow needle.
- FIG. 22 is a diagram schematically showing that the direct fuel cell system and the fuel cassette of the embodiment are connected via a valve.
- FIG. 23 is a cross-sectional view showing a state where a fuel cassette is set in the direct fuel cell system.
- FIG. 24 is a diagram showing the guide of the fuel cassette to the direct fuel cell system.
- FIG. 25 is a diagram showing the guide of the fuel cassette to the direct fuel cell system.
- FIG. 26 is a perspective view showing a state in which the direct fuel cell system accommodating the fuel cassette of the embodiment is mounted on a personal computer.
- FIG. 27 is a perspective view of the fuel cassette of the embodiment.
- FIG. 28 is a perspective view of the fuel cassette and the direct fuel cell system of the embodiment.
- FIG. 29 is a sectional view of a direct fuel cell system accommodating the fuel cassette of the embodiment.
- FIG. 30 is a partially cutaway perspective view of the direct fuel cell system according to the fourth embodiment. Example
- reference numeral 2 denotes a direct fuel cell system in which a cell stack 4 composed of a liquid fuel type fuel cell is installed in a fuel tank 20.
- Reference numerals 5 and 6 denote end plates provided on both sides of the cell stack 4
- reference numeral 8 denotes an air supply pipe
- reference numeral 10 denotes an exhaust pipe
- reference numerals 12 to 14 denote valves.
- An air supply pipe 15 is connected to the air supply pipe 8 via a valve 14.
- a blower 16 supplies air to the air supply pipe 8.
- Reference numeral 18 denotes a coupling mat, which is provided below the bottom of the cell stack 4 and is connected to the air supply pipe 15 using, for example, a continuously permeable porous mat.
- Reference numeral 20 denotes a fuel tank, which is made of plastic, such as polypropylene, polyimide, or polyphenylene sulfide, which is impermeable to liquid fuel such as methanol. Contain methanol 17 fuel 22.
- the fuel is not limited to methanol and water, but may be isopropanol and butanol.
- Reference numeral 23 denotes a liquid level of methanol-water fuel (hereinafter referred to as “liquid”), and a gas space 24 is left above the liquid level 23 in the fuel tank 20, and a cell stack 4 is provided here. Make sure that exhaust air and carbon dioxide from the air electrode accumulate.
- Reference numerals 25 and 26 denote exhaust portions, which are located higher than the inner upper surface of the other portions of the fuel tank 20 and are in contact with the gas space 24.
- the exhaust portions 25 and 26 are preferably provided at a plurality of locations on the upper surface of the fuel tank 20, for example, in the embodiment, provided at two locations along the longitudinal center line of the upper surface of the fuel tank 20.
- a hydrophobic gas permeable membrane 27, 28 etc. is provided on the upper part of the exhaust part 25, 26 so that only gas can be discharged without passing fuel.
- a porous polytetrafluoroethylene membrane or the like may be used as long as it allows gas to pass therethrough without passing through liquid water.
- selectivity can be imparted to the gas permeability of the hydrophobic gas permeable membranes 27 and 28, those having low water vapor permeability and low permeability to alcohols, carboxylic acids, aldehydes, and ethers are preferable.
- mounting parts 30, 30 are provided, and end plates 5, 6 of the cell stack 4 are mounted so that the cell stack 4 can be installed.
- the end plates 5 and 6 are fitted into the grooves provided in the mounting portion 30, and after the fitting, hot-sealed with an adhesive, or provided with insulation and corrosion resistance to liquid fuel It is preferable to fasten with screws such as plastics and ports.
- Reference numerals 31 and 32 denote flow rectifiers, so that the fuel level 23 appears at a position slightly higher than the upper part of the flow rectifiers 31 and 32, and the flow rectifiers 31 and 32 are located at the upper part of the cell stack 4. The flow is regulated so that the liquid fuel flows from the outside to the outside.
- the liquid fuel which has passed through the cell stack 4 and has been heated to have a lower specific gravity, flows to a position distant from the cell stack 4 via the straightening plates 31 and 32, and is gradually cooled while being cooled. It sinks to the bottom of 20 and circulates to the bottom of cell stack 4.
- 3 4 is a temperature sensor, which is installed in the cell stack 4 ⁇ , etc., and is used to detect the state of the cell stack 4, and to detect the temperature from which it starts up during cold start, etc.
- Used for Reference numeral 35 denotes a methanol sensor, which is used to measure the methanol concentration in the liquid fuel 22, and can be installed at any position. Note that sensors 34 and 35 are not required. Is also good.
- 36 is a high concentration methanol tank, for example, methanol 50 wt. /. One water 50 wt ° /. High-concentration methanol fuel is stored, and high-concentration methanol fuel is supplied into the fuel tank 20 from a methanol pump 38 or the like.
- the standard concentration of the liquid fuel 22 is, for example, 3 to 5 wt% of methanol.
- the exhaust pipe 10 is cooled, for example, outside the valve 13, by cooling the exhaust gas through the heat exchanger 40, and is cooled by a check valve 44 provided below the drain 43 with a gas-liquid separation membrane.
- the water that has been filtered is discharged into the fuel tank 20 or the water tank 42 through the valve 45. Exhaust from which water has been removed is exhausted out of the system through an exhaust unit 46 provided with a water repellent film. Also fuel tank
- a liquid level sensor 48 is provided in 20 to measure the liquid level of the fuel in the fuel tank.
- the liquid level signal from the liquid level sensor 48 is input to the control unit 50, and the valve 45 is switched by the valve signal S.
- the liquid level is higher than the predetermined value, the water is supplied to the fuel tank 2. Drain into water tank 42 without returning to 0, otherwise return water to fuel tank 20.
- the liquid level sensor 48 obtains the height of the liquid surface using, for example, ultrasonic waves or light reflection, and the installation location is arbitrary.
- the heat exchanger 40 is, for example, one that releases heat to the surrounding air by a fan.
- the airflow may be a natural airflow, but may be cooled by, for example, an airflow from a fan.
- the heat exchanger 40 may be cooled by, for example, an airflow from a cooling fan of the CPU.
- control unit 50 is a control unit. 52 is a protection diode, which need not be provided.
- the control unit 50 operates the methanol pump 38 ′ according to the methanol concentration signal from the methanol sensor 35 to adjust the methanol concentration of the liquid fuel 22. Also temperature sensor
- the temperature signal from 34 starts, for example, in a cold start, specifically, when starting from a temperature of 10 ° C or less, a part of the air supply is bubbled from the bubbling mat 18 by the valve 14. This air is guided from the fuel flow path provided in the separator to the fuel electrode, and the fuel and the air publishing at the fuel electrode directly react to generate heat. The amount of publishing air is controlled by the fuel temperature.
- the control unit 50 monitors the output voltage of the cell stack 4, etc., and when other signals such as the magnitude of the load can be obtained from the load side, the output voltage is corrected with those signals, Monitor the status of cell stack 4.
- the direct fuel cell system 2 also has a secondary battery (not shown) for backup, which is used at the time of start-up and the like.
- Inversion is a phenomenon discovered by the inventors.
- the potential of the fuel electrode becomes more than +50 OmV or more with respect to the potential of the air electrode in the same single cell, for example, the Pt—Ru
- the electrode material of the fuel electrode is such that a catalyst containing Ru such as Pt-Ru is supported on C, a binder such as PTFE (polytetrafluoroethylene) is added, and a desired amount of proton conductivity is increased.
- the degree of hydrophobicity / hydrophilicity is controlled by adding a molecular solid electrolyte.
- the reason for adding Ru to the catalyst on the fuel electrode side is to prevent deterioration of characteristics due to CO adsorption when oxidizing fuel such as methanol.
- the electrode material of the air electrode is, for example, an electrode catalyst in which Pt is supported on C, to which a PPTFE binder and a proton conductive polymer solid electrolyte are added.
- Pt—Ru, Pt—Rh, and the like can be used as the electrode catalyst for the air electrode, in addition to Pt. Further, these electrode materials themselves are known.
- a Nafion membrane (Nafiori is a registered trademark of DuPont) or the like is used as a proton conductive polymer solid electrolyte membrane between the fuel electrode and the air electrode, and the membrane itself is well known.
- a permeable carbon sheet or the like is placed on the surface of the fuel electrode or air electrode opposite to the proton conductive polymer solid electrolyte membrane to control fuel and air supply and current collection.
- Cell stacks differ from hydrogen fuel cells in that the anode is exposed to the electrolyte.
- an acid such as formic acid is generated due to incomplete oxidation of methanol.
- the pH of the liquid fuel 22 becomes 3 Dropped to a degree.
- the liquid fuel 22 also contains formaldehyde and the like, it is preferable that the liquid fuel 22 is not exhausted from the fuel tank 20 but is circulated as much as possible so that formic acid, formaldehyde, etc. are not discharged out of the system.
- Liquid fuel is a weak electrolyte.In this state, if the potential of the fuel electrode becomes much more positive than that of the air electrode, the potential of the fuel electrode exceeds the elution potential of Ru, and Ru elutes into the fuel. Become. The inventor has found that this phenomenon is caused by the fact that when the potential of the fuel electrode becomes more than +50 OmV positive with respect to the potential of the air electrode, Ru is detected in the exhaust fuel, and cells that experience elution of-and Ru Confirmed that only a small output density was obtained even after the potential was returned to normal.
- a plurality of unit cells are connected in series. More preferably Instead of simply connecting the individual battery cells in series, instead of connecting about 2 to 4 single battery cells in parallel, multiple units are connected in series.
- a plurality of unit cells are connected in series, so that even in a unit cell in a poor state, a current according to the output current of the entire cell stack 4 flows. For this reason, a single cell that is in shortage of fuel or air is likely to have a particularly positive potential on the fuel electrode side, and if it is forcibly driven in this state, reversal will occur.
- the output voltage of the cell stack 4 is monitored by the control unit 50, and if the level of the load is known, the correction is added according to the level of the load. Control the air supply of the blower 16 so as to obtain it. Increasing the air supply volume makes it difficult for the poles to be generated in each single battery cell, thus preventing the poles. If the predetermined output voltage cannot be obtained even when the air supply amount is increased, the direct fuel cell system 2 is stopped. In addition, in order to prevent the pole reversal, it is conceivable to increase the methanol concentration in the liquid fuel 22. However, the control by the methanol pump 38 has a slow response and is not very effective in preventing the pole reversal.
- a circulation pump is provided in the upper part or lower part of the cell stack 4 in the fuel 22, and when the output voltage of the cell stack 4 drops, the pump is driven to accelerate the fuel circulation. May be.
- FIG. 2 shows the flow paths provided on the fuel electrode side surface 62 (left side) and the air electrode side surface 64 (right side) of the separator 60.
- the material of the separator 60 for example, carbon to which a resin is added is used, and in addition, a titanium plate, a stainless steel plate, or the like can be used.
- the separator 60 is horizontally long and has a width in the horizontal direction larger than the height, so that fuel supply by natural convection or the like is facilitated.
- a plurality of vertical flow paths 66 and preferably a plurality of horizontal flow paths 68 are provided on the fuel electrode side surface 62, and these are arranged in a grid pattern, in other words, two-dimensionally.
- the vertical flow path 66 may be inclined from the vertical direction, or the horizontal flow path 68 may be inclined from the horizontal direction.However, this increases the length of the flow path and decreases the fuel supply capacity. And preferably not.
- a plurality of vertical flow paths 72 and preferably a plurality of horizontal flow paths 70 are provided on the air electrode side surface 64 so that air supplied from the air supply hole 74 is guided to the exhaust hole 76 side.
- To Cell stack 4 is used in liquid electrolyte 22 with weak electrolyte, so it is necessary to prevent short circuit There is.
- an insulating resin coating 7 7 made of 1 "raw plastic is provided on the side surface of the separator 60, and a groove 8 8 is formed on the fuel electrode side surface 6 2 as an entrance / exit of the flow paths 66, 68. With a coating 7 7.
- reference numerals 79 and 80 denote bolts and nuts, which are made of synthetic resin such as ports and nuts to prevent short-circuits and improve corrosion resistance.
- 81 schematically shows each unit cell. Then, as described above, a plurality of single battery cells are connected in series via the separator to form a cell stack 4.
- a conductive material is used for the end plate 6 because the end plate 6 is intended to have a function as a current collecting terminal in addition to a function as a clamping plate.
- the configuration is shown in the upper right of Fig. 3.
- a carbon plate 82 made of carbon or carbon molded with a resin binder is used, and the surface of the plate is made of a conductive metal such as a precious metal such as gold plating or a perovskite.
- a conductive coating 84 is applied to increase conductivity, and a resin coating 86 is applied to the outside of the conductive coating 84 with an adhesive or the like to insulate the liquid fuel.
- the carbon plate 82 may be reinforced with carbon fiber or glass fiber to increase the strength.
- FIG. 4 shows a modified separator 100.
- the fuel electrode side surface 102 is provided with a plurality of vertical flow paths 105 and, for example, two horizontal flow paths 106 and 106 ′, and the air electrode side surface 104 is provided with, for example, A horizontal channel 107 is provided.
- Reference numeral 108 denotes a land provided in the flow channel 107, which has a height higher than that of the flow channel 107 and has a surface height in contact with the air electrode.
- Reference numeral 1109 denotes an air supply port, 110 denotes an exhaust port. These are provided, for example, on both left and right sides of the separator 100, and the upper and lower surfaces of the separator 100 are left for taking in liquid fuel.
- separator 60 of the embodiment and the separator 100 of the modified example have a length in the left-right direction larger than the vertical height, which is larger than the height in FIGS. Means to do. By doing so, the distance over which the liquid fuel must move due to the difference in specific gravity can be reduced, and fuel supply can be made easier.
- FIG. 5 shows a state in which the fuel tank 20 is operated while being tilted.
- fuel tank 20 It is conceivable in actual use that it is used at an angle of less than 5 ° or less than 10 ° from the horizontal plane.
- FIG. 5 schematically shows the position of the liquid surface 23 when the fuel tank 20 is used while being tilted from the horizontal plane.
- an exhaust portion 90 is provided only at one location, and if this portion is separated from the gas space 24 by the liquid level 23, the carbon dioxide does not flow into the exhaust portion 90.
- the exhaust portions 25 and 26 are provided at a plurality of places such as two places along the longitudinal direction of the fuel tank 20, especially at a plurality of places along the longitudinal center line of the upper surface of the fuel tank 20, Such an exhaust part remains on the liquid surface 23 and is connected to the gas space 24, so that the exhaust can be continued.
- the two exhaust portions 25 and 26 may be connected to each other and exhausted from the exhaust portion 92. In this case, however, the two exhaust portions 25 and 26 are substantially used.
- the vertical flow paths 66 and 105 in the separators 60 and 100 are also tilted from the vertical direction.
- the upper part of the vertical flow paths 66 and 105 in the vertical direction comes above the liquid level 23, the exhausted fuel cannot flow out from the liquid level 23, and does not function as a flow path.
- the horizontal flow passages 68, 106, 106 are provided, it is possible to minimize the part that cannot be discharged because of the exhaust emission and does not function as a flow passage.
- the provision of the exhaust portions 25 and 26 at two or more places, and the provision of the horizontal flow passages 68, 106, and 106 on the fuel electrode side surfaces 62 and 102 of the separator can reduce the inclination of the fuel tank 20. Increase tolerance.
- the range in which power can be normally generated even when the fuel tank 20 is tilted is, for example, 15 ° or less, preferably ⁇ 10 ° or less, and specifically ⁇ 5 ° or less.
- FIG. 6 shows a modified direct fuel cell system.
- Reference numeral 20 denotes the above-described fuel tank, and the illustration of the high-concentration methanol tank 36 and the water tank 42 is omitted.
- the blower 16 controls the air supply amount by a control unit 50 (not shown) according to the output voltage of the cell stack 4, and is the same as the embodiment of FIGS. 1 to 3 except for special points.
- 1 12, 114, and 116 are heat exchangers, and 118 is a cooling fan.
- the air from the blower 16 is heated by the heat exchanger 112 and supplied to the cell stack 4, and the air on the exhaust side exchanges heat with the liquid fuel 22 by heat exchange 14 to be cooled.
- Fig. 7 schematically shows the structure for publishing.Part of the air in the air line 8 is split from the valve 14 to the air line 15 and rises in the liquid fuel from the bubbling mat 18 to the cell stack. It enters the vertical flow path 6 of 4 and generates heat at the fuel electrode.
- the water tank 42 and the high-concentration methanol tank 36 are detachably attached to the outside of the fuel tank 20 so as to be integrated therewith.
- a high-concentration methanol tank 36 and a water tank 42 are installed inside the fuel tank 122, and the cell stack 4 and the liquid fuel 22 are placed in the gas space between them. Good to be accommodated.
- FIG. 9 shows a modified direct fuel cell system 132, which is the same as the direct fuel cell system 2 in FIG. 1 except for the points specifically indicated, and the same reference numerals indicate the same components.
- 1 34 is a housing
- 1 36 is a water separation tank, which separates water in the exhaust air by an appropriate method, and recovers the water to the fuel tank 20.
- water tank 42 may be mounted on the upper part of the housing 13 4, but this increases the height of the direct fuel cell system. In this modified example, water can be easily collected in the fuel tank 20 by using a water separation tank.
- FIG. 10 is a diagram showing an example of the cell structure of the direct fuel cell system according to the second embodiment
- FIG. 11 is a diagram showing an example of the cell stack.
- a pair of air electrodes 2 12 (not shown, fuel electrodes 2 13 are formed through an electrolyte 2 11 composed of a proton conductive polymer membrane)
- the joined electrolyte (which is joined to the opposite side of the electrolyte 211) and the fuel electrode 2 13 are joined to form an electrode-membrane assembly (hereinafter referred to as MEA) 210.
- MEA electrode-membrane assembly
- the two separator plates 222 are provided with two separator plates 220 so that air is supplied to the two sides and air supply channels 222 for discharging the reaction products from the cathode 221 are arranged.
- a 210 is pinched.
- the separator plate 220 has a fuel supply passage 22 on one side. 3 is provided, and a flow path 222 for supplying air is provided on the back surface thereof.
- the MEA 210 is laminated via the single plate 220 of the separator to obtain a cell stack 201 shown in FIG. Further, in the cell stack 201, a separator plate 220a provided with only the fuel supply flow path 221 and only an air supply flow path 224 are provided at the outermost part. Separator plate 222b is disposed.
- the separator plate 220 may be formed by laminating a separator plate 220a and a separator plate 220b such that each flow path is turned upside down. There are two types of boards.
- the cell stack 201 has a straight fuel supply flow path 22 1, 22 3 formed with an opening in the vertical direction, and a linear shape formed with an opening in the front-rear direction. And an air supply flow path 222 and 222.
- the liquid fuel is supplied from the upper and lower openings, the reaction product from the anode 2 13 is discharged from the upper opening, and the air is discharged from the front or rear opening (the front in FIG. 11).
- the reaction product is supplied and the reaction products from the cathode 2 12 side are discharged from the rear or front opening (rear in FIG. 11).
- each of the flow paths has a linear shape orthogonal to each other, but is not limited to this.
- the MEA210 was prepared as follows. In other words, among proton-conducting polymer electrolyte membranes, Nafion membrane (trade name: Nafion 117) manufactured by DuPont, which is generally used as a perfluorosulfonic acid-based electrolyte membrane, is used as the electrolyte 211.
- Nafion membrane trade name: Nafion 117
- DuPont which is generally used as a perfluorosulfonic acid-based electrolyte membrane
- a gas diffusion layer made of carbon paper impregnated with a PTFE solution and subjected to water repellent treatment, and an air electrode catalyst in which platinum fine particles are supported on carbon powder made of acetylene black, PTFE resin, and ophthalmic solution
- the catalyst paste obtained by mixing was applied and dried, and used as the air electrode 212.
- the same gas diffusion layer is coated with a catalyst paste obtained by mixing a fuel electrode catalyst in which platinum-ruthenium fine particles are supported on acetylene black carbon powder, a PTFE resin, and a naphion solution (isopropanol solvent).
- the dried fuel was used as fuel electrode 2 13.
- the catalyst having a platinum fine particle content of 40% by weight was used as the air electrode catalyst, it can be appropriately selected in the range of 10 to 70% by weight.
- the fuel electrode catalyst used had a platinum-ruthenium fine particle content of 40% by weight and a platinum: ruthenium weight ratio of 2: 1. However, the platinum-ruthenium fine particle content was 1%. 0 to 70 weight. /.
- the platinum: ruthenium weight ratio is in the range of 5: 1 to 1: 2. Can be selected as appropriate.
- the composition of each catalyst, perfluorosulfonic acid resin, and PTFE resin in the solution in which the air electrode catalyst and the fuel electrode catalyst are dispersed can be arbitrarily determined.
- the air electrode 2 12 and the fuel electrode 2 13 thus produced were joined to both surfaces of the electrolyte 211 by hot pressing to produce MEA.
- the liquid fuel is caused to flow through the fuel supply flow paths 221, 223. That is, as shown in FIG. 12, the fuel cell stack 201 is opened so that the fuel supply passages 22 1 and 22 3 are opened into the fuel tank 202 storing the liquid fuel.
- the fuel tank 202 is placed inside the fuel cell 202 so that the fuel tank 202 also serves as a storage container for the cell stack 201.
- the liquid fuel flows into the space 2 23 a formed by the fuel supply channel 2 23 as shown in FIG. Is supplied to the fuel electrode 2 13 (FIG. 10), and carbon dioxide as a reaction product is discharged from above.
- the liquid fuel can be continuously supplied to the anodes 2 13 by the convection of the liquid fuel by the movement. If a fuel tank is provided in this fuel tank 202, even if the concentration of the liquid fuel decreases due to the reaction, the system can be used continuously by replenishing the liquid fuel. it can.
- the discharged carbon dioxide becomes bubbles in the liquid fuel and accumulates in the upper part of the fuel tank 202, but may be exhausted by providing an exhaust port in the upper part of the fuel tank 202. If a water-repellent porous body such as Teflon (registered trademark) is provided in the exhaust port, leakage of liquid fuel from the exhaust port can be prevented.
- a water-repellent porous body such as Teflon (registered trademark) is provided in the exhaust port, leakage of liquid fuel from the exhaust port can be prevented.
- air is made to flow through the air supply channels '222, 224'. That is, as shown in FIG. 12, the air supply channels 2 2 ′ 2, 2 24 are opened to the atmosphere, and only the opening is subjected to resin bonding, packing seal, or the like, so that the liquid fuel is discharged.
- the cell stack 201 is placed in the fuel tank 202 so as not to leak outside.
- Fig. 13 (b) (a cross-sectional view taken along the line BB 'in Fig. 12)
- air flows into the space 224a formed by the air supply flow path 224.
- the water is supplied to the air electrode 2 12 and water as a reaction product is discharged.
- a water-repellent porous body such as Teflon (registered trademark) is provided in the opening, leakage of generated water can be prevented.
- the discharged water can be absorbed by a water absorbing body, or a separate collection cassette can be installed.
- a separate collection cassette can be installed.
- an external manifold structure is used without providing an open portion opened to the atmosphere in the fuel tank 202. It is also possible to provide air to the cell stack 201 in the fuel tank 202 through a pipe having the external manifold structure by using a pipe fan. In this way, leakage of the liquid fuel can be prevented only by applying resin bonding, packing seal, or the like to only the connection between the external manifold and the cell stack 201.
- air is not only supplied by natural diffusion or natural convection, but also forcedly circulated by a professional fan. It can also be done.
- a blower or a fan may be provided in the above-mentioned open part that is open to the atmosphere, and air may be supplied from this open part, or the separators 220, 220a, 22
- An internal manifold for circulating air may be provided in 0b, and air may be supplied from an air supply port communicating with the internal manifold.
- the depth of the air supply channel provided in each of the separators 220 and 220b is reduced to reduce the depth of each of the separators 220 and 22Ob. Can be made thinner. Therefore, a direct fuel cell system with the same output can be downsized, and a direct fuel cell system with the same dimensions can have a large capacity. Further, if a water-repellent porous body such as Teflon (registered trademark) is provided in the opening or the air supply port, leakage of water generated by the reaction can be prevented.
- Teflon registered trademark
- Example 3 14 to 29 show a third embodiment and its modification.
- 302 is a direct fuel cell system that supplies a liquid fuel such as methanol-water directly to the fuel electrode.
- Reference numeral 304 denotes a fuel cell stack, which is formed by laminating a plurality of MEAs each having a fuel electrode and an air electrode on both surfaces of a proton conductive polymer solid electrolyte membrane via a separator or the like.
- Numeral 306 denotes a fuel tank which stores liquid fuel such as methanol-water, and has a fuel cell stack 304 disposed therein, which is submerged in liquid fuel (below the liquid level).
- Numeral 308 denotes an air supply path
- numeral 310 denotes an air discharge path.
- the flow paths communicating with these are provided in the separator and MEA of the fuel cell stack 304, and the air electrode side of each separator is shown in the figure. There is no air supply groove.
- a fuel supply groove communicating from the lower side to the upper side of the fuel tank 303 is provided on the fuel electrode side of each separator, and the fuel electrode is connected to the fuel electrode by natural convection of the liquid fuel in the fuel tank 303. Supply fuel. Then, the exhaust fuel and carbon dioxide are discharged into the liquid fuel in the fuel tank 306 from the upper part of the fuel supply groove.
- Reference numeral 312 denotes a blower for supplying air
- reference numeral 3114 denotes a filter for removing dust in the air. The necessity of the filter can be freely selected.
- the air blown from the blower 3 12 into the air supply path 3 08 is supplied into the fuel cell stack 304, and the exhaust air enters the radiator 3 16 via the air discharge path 310 and is required.
- the air is cooled by the airflow from the fan 318 in accordance with the pressure, and is separated into exhaust air and water by the gas-liquid separator 320.
- the blower 312, the radiator 316, the fan 318, and the gas-liquid separator 320 may not be provided.
- the gas-liquid separator 320 has a gas-liquid separation membrane such as a porous high-molecular membrane, or a gas-liquid separator that separates mist-like water by colliding airflow with a baffle plate. It can be changed as appropriate within the range of known techniques. Further, the gas-liquid separator 320 may have a structure capable of maintaining the fuel tank 306 ⁇ at a constant liquid amount.
- the water recovery port 322 of the gas-liquid separator 322 is preferably provided below the liquid level of the fuel tank 306 so that water is discharged, for example, from near the bottom of the fuel tank. This is effective to ensure that the wastewater from the gas-liquid separator 320 / the exhaust air line 324 is pressurized. That is, a part of the pressure applied from the blower 3 12 is applied to the drain Z exhaust air line 3 24 and a part of the water separated by the gas-liquid separator 3 The liquid can be drained to 50 drainage reservoir 3 5 5 without using a liquid feed pump.
- Reference numeral 326 denotes a fuel pump which supplies liquid fuel such as methanol water in an elastic bag 352 (fuel reservoir) of a fuel cassette 350 to the fuel tank 303.
- the liquid fuel can be supplied to the fuel tank 306 by the contraction force of the elastic bag.
- the fuel pump 326 may be omitted.
- the liquid fuel is supplied to the fuel tank 306 by the pressure applied to the fuel cassette 350 through the drainage Z exhaust air line 324.
- 328 is a fuel supply line.
- Reference numeral 330 denotes a CPU (control processing unit), and reference numeral 3332 denotes a carbon dioxide outlet provided in a fuel tank 306.
- a water-repellent porous polymer membrane is used to form a fuel electrode.
- the carbon dioxide generated in the above is discharged outside.
- Reference numeral 3334 denotes a level meter, which measures the liquid level in the fuel tank 303, and reference numeral 336, a methanol sensor, which may be a sensor such as dimethyl ether or isopropanol, measures the concentration of fuel such as methanol.
- the CPU 340 controls the fan 318 using the output of the level meter 334.
- the degree of cooling in the radiator 316 changes, and the efficiency of the gas-liquid separator 320 changes accordingly, so that the liquid level position in the fuel tank 306 is within a predetermined range.
- the fuel pump 326 is controlled by a signal from the methanol sensor 336 to keep the fuel concentration within a predetermined range.
- the control of the liquid level in the fuel tank 306 will be described.
- the fan 318 is operated to cool the exhaust air by the radiator 316, thereby facilitating the separation of water in the gas-liquid separator 320.
- the generated water is recovered more in the fuel tank 306 to raise the liquid level.
- the fan 318 is stopped to raise the temperature of the exhaust air at the gas-liquid separator 320 and the amount of water returned to the fuel tank 306 Is reduced.
- a part of the separated water is collected in the drainage reservoir 355 of the fuel cassette 350 by the pressure of the air from the blower 312.
- the fuel cassette 350 is provided with an elastic bag 352 and a drainage reservoir 3555 so that the colored elastic bag 3552 can be removed from the opening window 354.
- Reference numeral 356 denotes a chemical filter such as a sheet-like activated carbon, which is formed in a case of the fuel cassette 350 and is provided in the air evaporating through a gas permeable membrane 358 such as a porous polymer membrane. , Methanol and formic acid, formaldehyde, ants Absorb impurities such as methyl acid.
- Fig. 15 to Fig. 20 show examples of fuel cassettes.
- 360 and 362 are a pair of connectors, of which 360 is a connector for supplying fuel from the elastic bag 352.
- Reference numerals 362 and 362 denote connectors for collecting exhaust fuel into the liquid reservoir 365.
- the elastic bag 3 52 is initially filled with fuel and is inflated, so if the connector 365 is directly connected to the connector on the fuel cell system 302 side The liquid fuel is supplied at the pressure of the elastic bag 352, so that the fuel pump 326 and the like can be eliminated.
- the space in which the elastic bag 352 contracts becomes a drainage reservoir 35
- the material of the elastic bag 352 is, for example, silicon rubber, petit rubber, latex rubber, or the like.
- polypropylene, polyethylene, PET, etc. are used for the case of the fuel cassette 350.
- the drainage reservoir 355 is filled with a water-absorbing resin, and collected. The water may be fixed.
- a flexible bag 372 that does not allow liquid fuel such as polypropylene, polyethylene, nylon, or fluorocarbon resin to pass through is used, and in other respects, the fuel in Fig. 15 is used. Same as cassette 350.
- a bellows bag 376 made of a fuel-impermeable polymer is used, and as the liquid fuel is delivered from the connector 360, the bellows bag 3 7 6 To shrink.
- a movable wall 380 is provided between the fuel reservoir 382 and the drain reservoir 355, and the suction force of the fuel pump and the drain reservoir 355 are provided.
- the movable wall 380 is moved to the connector 360 side by the pressure of the collected water.
- the fixed partition 3886 separates the drainage reservoir 3555 from the flexible bag 3772 and is collected in the drainage reservoir 3555. This prevents the liquid fuel in the flexible individual bag 372 from rising due to the temperature of the water, making it difficult to seal the connector 360.
- reference numeral 3886 denotes the fixed partition described above, and an elastic porous bag 352 is arranged on the connector 360 side of the fixed partition 3886.
- FIG. 21 shows a connector 360 ′ using the hollow needle 402.
- Reference numeral 390 denotes a case of the fuel cassette 350
- reference numeral 394 denotes a fitting concave portion
- reference numeral 396 denotes a sealing portion made of rubber or plastic
- reference numeral 398 denotes a needle cover.
- 400 is a connector on the direct fuel cell system side, and has a hollow needle 4
- the fuel cassette 350 and the direct fuel cell system are connected by passing 02 through the sealing portion 396.
- Fig. 22 shows a connector 360 "using a ball valve 412.
- 414 is a liquid-tight O-ring
- 416 is a panel that presses the pole valve 412 toward the opening 418
- 420 is a direct type fuel cell system.
- 422 is a mounting ring
- 423 is a pin
- pin 423 is fixed to connector 420 by mounting ring 422.
- a connector 360 may be provided on the direct fuel cell system side, and a connector 420 may be provided on the fuel cassette 350 side.
- the fuel supply connectors 360 in the case of FIGS. 21 and 22, the fuel supply connectors 360,.
- FIG. 23 shows the fuel cassette 350 set in the cassette area 454 of the direct fuel cell system.
- the fuel cassette 350 is housed in the cassette housing section 430 of the cassette area 454, and the end of the fuel cassette 350 on the outlet side is stopped, for example, from above and below.
- the stopper 432 includes a lock piece 434, a spring 436 for urging the lock piece 434 in a direction to push the lock piece 434 to the rear end of the fuel cassette 350, and an operation part 438 connected to the mouthpiece 434.
- the lock piece 434 protrude by the springs 436 to fix the connectors 360 ', 360' ', etc., and prevent liquid leakage from the connectors 360', 360 ", etc. Further, the lock pieces 434 are provided at the outlet. Because the side is curved and the inside is perpendicular to the wall of the cassette housing 430, the fuel cassette 3
- guide grooves 442 are provided at, for example, two places on the bottom surface, side surfaces, and top surface of the fuel cassette 350, and are engaged with the ridge guides 440 provided on the cassette housing portion 430.
- the fuel cassette 350 is securely guided and the connectors 360 ', 360'', etc. Connection can be ensured.
- the unevenness 444 is provided on the surface 404 and 391 of the fuel cassette 350 for catching when the fuel cassette 350 is removed from the cassette accommodating portion 430.
- the direct fuel cell system 302 is set in a personal computer 446 or the like and used as a portable power supply or the like, or used as an emergency or outdoor power supply.
- reference numeral 4488 denotes a sealing tape which seals the side of the fuel cassette 350 on which the connector is provided, to prevent fuel from leaking or evaporating before use.
- the fuel cassette 350 is located at a position corresponding to the outlet side of the cassette housing section 330 of the direct fuel cell system 302 (upper end of the rear end of the fuel cassette 350). Provide unevenness 4 4 4 Then, when removing the fuel cassette 350 from the cassette accommodating portion 4300, the user can easily take it out by hooking the user's finger or the like. Further, in FIG. 28, a colored elastic bag is visible in the window 354.
- the direct fuel cell system 302 includes a stack area 450, an auxiliary equipment area 450, and a cassette area 454.
- the above-mentioned fuel tank 303 is provided, and the fuel cell stack 304 is stored.
- the auxiliary machine area 4 52 is provided with the CPU blower 3 12, fuel pump 3 26, radiator 3 16, fan 3 18, etc. as shown in Fig. 29. Connector 4 5 5 so that it can be connected to a personal computer.
- the cassette area 454 is provided with an opening 456 shown in FIG. 28 so that air that has passed through the gas permeable membrane 358 of the fuel cassette 350 and the chemical filter 356 can be discharged.
- the chemical filter 356 may be provided on the opening 456 side, but is not preferable because the life of the filter is finite.
- Reference numeral 558 denotes a window through which the fuel bag 350 shown in FIG. 29 can be seen through the opening window 354 of the fuel cassette 350.
- reference numeral 400 denotes an evaporation hole provided in the case of the fuel cassette 350.
- Water generated in the direct fuel cell system can be collected in a fuel cassette and discarded, eliminating the need for a drainage tank, making it suitable for portable electronic devices such as personal computers and personal digital assistants.
- a suitable compact direct fuel cell system can be provided.
- Fuel can be easily supplied by the fuel cassette, and the water generated in the air electrode can be recovered, so that the liquid level in the fuel tank can be maintained within a predetermined range and the treatment of drainage becomes easy. .
- the generated formic acid and residual methanol are safe because they can be discarded together with the fuel cassette.
- a water-absorbing resin or the like may be set in the drainage reservoir to facilitate collection of the drainage in the drainage reservoir.
- the pressure of the air supply blower can be used for collecting the waste liquid, a drain pump is not required. When this pressure is applied to the elastic bag 352, etc., it can also be used for fuel supply.
- the operating conditions of the radiator can be controlled so that the liquid level of the fuel tank is maintained within a predetermined range.
- the fuel cassette can be easily attached and detached.
- the fuel cassette can be securely fixed to the cassette accommodating section, and the connection with the connector becomes more stable.
- the methanol concentration in the fuel tank is 20 ⁇ : 100 wt ° /. , Preferably 40 to: 100 wt ° /. Then, the amount of water that is supplied from the fuel reservoir and the amount of water generated at the air electrode can be collected in the drainage reservoir.
- the description of the elastic bag 3 52 also applies to the flexible bag 3 72 except for the elasticity.
- Known proton conductive polymer solid electrolyte membranes and their electrode materials may be appropriately used.
- the fuel cell stack may be separated from the fuel tank and separated, or the fuel may be directly supplied from the fuel reservoir of the fuel cassette to the fuel electrode without providing the fuel tank. In this case, for example, both the fuel discharged from the fuel electrode and the water from the air electrode are collected in a drainage reservoir.
- the fuel cassette is provided with three areas: a drain tank, a high-concentration fuel tank, and a fuel tank.
- the fuel tank is also used as a fuel tank, and high-concentration fuel is supplied from the high-concentration fuel tank to the fuel tank to increase the fuel concentration. May be maintained within a predetermined range, and fuel may be supplied directly from the fuel reservoir to the fuel electrode.
- the methanol concentration in the high-concentration fuel reservoir is, for example, 2 O wt%
- the fuel discharged from the fuel electrode is recovered in, for example, the fuel reservoir, and the water discharged from the air electrode is recovered in the water drainage reservoir.
- the methanol concentration in the tank can be kept almost constant.
- a water tank is provided in the fuel cassette and the level of the fuel tank drops when the direct fuel cell system is not operated for a long time, the water level in the water tank can be adjusted at the liquid level. .
- an acid such as sulfuric acid is not added to a liquid fuel such as methanol-water.
- a liquid fuel such as methanol-water.
- formic acid, propionic acid, formaldehyde, etc. are generated by the side reaction at the fuel electrode, and organic acids such as formic acid and propionic acid make the fuel electrically conductive, albeit slightly. If the liquid fuel becomes conductive, the electric field generated by the cell stack will cause electrical corrosion of the fuel electrode of the MEA. Therefore, activated carbon or zeolite is added to the fuel or placed in the fuel tank so as to be in contact with the liquid fuel to remove acids such as formic acid from the liquid fuel. This has the effect of eliminating harmful substances such as formaldehyde from liquid fuels. There is fruit.
- Liquid fuel methanol 1M-water
- methanol 1M-water liquid fuel with formic acid added to adjust the PH to 2 (formic acid concentration is about 1M)
- sulfuric acid and formic acid And a liquid fuel to which no was added.
- a carbonaceous separator was placed facing the fuel at a distance of 1 to 1 Ocm, 3 V or 6 V DC was applied between the separators, and the current flowing between the separators was observed. No current flowed in the liquid fuel containing neither formic acid nor sulfuric acid, and the current reached 30 to 100 times with 1 M sulfuric acid compared to PH 2 formic acid.
- FIG. 501 is a new cell stack
- 502 is a fuel tank
- 510 is a MEA
- 517 is an insulating packing, located between the MEA anode and separator, otherwise similar to the first embodiment etc. .
- the packing 517 can prevent the liquid junction. Insulating the bottom and side surfaces of the fuel supply groove and air supply groove of the separator with a synthetic resin can prevent deterioration of the MEA characteristics due to liquid junction or short circuit current.
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Fuel Cell (AREA)
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/555,601 US20070020497A1 (en) | 2003-05-07 | 2004-03-29 | Direct fuel cell system |
Applications Claiming Priority (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2003128656A JP4701585B2 (ja) | 2003-05-07 | 2003-05-07 | 直接形燃料電池 |
JP2003-128656 | 2003-05-07 | ||
JP2003201831A JP4894128B2 (ja) | 2003-07-25 | 2003-07-25 | 燃料電池システム |
JP2003-201831 | 2003-07-25 | ||
JP2003341123A JP4590848B2 (ja) | 2003-09-30 | 2003-09-30 | 直接液体燃料形燃料電池システムおよびその燃料カセット |
JP2003-341123 | 2003-09-30 | ||
JP2003-372070 | 2003-10-31 | ||
JP2003372070A JP4635428B2 (ja) | 2003-10-31 | 2003-10-31 | 直接液体供給形燃料電池 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2004100301A1 true WO2004100301A1 (ja) | 2004-11-18 |
Family
ID=33437159
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2004/004477 WO2004100301A1 (ja) | 2003-05-07 | 2004-03-29 | 直接形燃料電池システム |
Country Status (2)
Country | Link |
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US (1) | US20070020497A1 (ja) |
WO (1) | WO2004100301A1 (ja) |
Cited By (1)
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WO2011138392A1 (en) | 2010-05-06 | 2011-11-10 | Novartis Ag | Compositions and methods of use for therapeutic low density lipoprotein -related protein 6 (lrp6) antibodies |
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US8246817B2 (en) * | 2004-06-10 | 2012-08-21 | Ford Motor Company | Deionization filter for fuel cell vehicle coolant |
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JP2007335145A (ja) * | 2006-06-13 | 2007-12-27 | Matsushita Electric Ind Co Ltd | 燃料電池システム |
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KR20100078804A (ko) * | 2008-12-30 | 2010-07-08 | 삼성에스디아이 주식회사 | 연료순환구조를 갖는 연료전지시스템 및 그 구동 방법과 연료전지시스템을 포함하는 전자기기 |
US8480033B2 (en) | 2011-06-02 | 2013-07-09 | Lockheed Martin Corporation | Integral thermally insulated fuel bladder |
US9450265B2 (en) * | 2012-04-24 | 2016-09-20 | Audi Ag | Compact fuel cell system with fuel cell in fluid tank |
CN106299382B (zh) * | 2015-05-28 | 2018-11-09 | 清华大学 | 燃料电池系统 |
CN106299430B (zh) * | 2015-05-28 | 2018-10-02 | 清华大学 | 燃料电池的使用方法 |
CN106299383B (zh) * | 2015-05-28 | 2018-11-30 | 清华大学 | 燃料电池模组 |
CA2909013C (en) | 2015-10-14 | 2023-07-04 | Op-Hygiene Ip Gmbh | Direct isopropanol fuel cell |
JP6274197B2 (ja) * | 2015-12-21 | 2018-02-07 | トヨタ自動車株式会社 | 燃料電池及び燃料電池システム |
KR102184368B1 (ko) * | 2017-12-11 | 2020-11-30 | 삼성에스디아이 주식회사 | 배터리 팩 |
NL2022354B1 (en) * | 2019-01-08 | 2020-08-13 | Hyet Holding B V | Flow field plate and compressor comprising such plate |
US11728496B2 (en) * | 2021-03-09 | 2023-08-15 | GM Global Technology Operations LLC | Propulsion battery packs with integrated fuel tank mounting systems |
CN114312368A (zh) * | 2021-12-30 | 2022-04-12 | 潍柴动力股份有限公司 | 一种燃料电池系统及氢燃料电池公交车 |
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