WO2005020360A1 - 燃料電池システム、燃料電池システムの起動方法 - Google Patents
燃料電池システム、燃料電池システムの起動方法 Download PDFInfo
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- WO2005020360A1 WO2005020360A1 PCT/JP2004/012458 JP2004012458W WO2005020360A1 WO 2005020360 A1 WO2005020360 A1 WO 2005020360A1 JP 2004012458 W JP2004012458 W JP 2004012458W WO 2005020360 A1 WO2005020360 A1 WO 2005020360A1
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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
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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
- H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production 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
- H01M8/04223—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
- H01M8/04231—Purging of the 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
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
- H01M8/0432—Temperature; Ambient temperature
- H01M8/04365—Temperature; Ambient temperature of other components of a fuel cell or 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
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
- H01M8/0438—Pressure; Ambient pressure; Flow
- H01M8/04388—Pressure; Ambient pressure; Flow of anode reactants at the inlet or inside the fuel cell
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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
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
- H01M8/0438—Pressure; Ambient pressure; Flow
- H01M8/04395—Pressure; Ambient pressure; Flow of cathode reactants at the inlet or inside the fuel cell
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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
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
- H01M8/0438—Pressure; Ambient pressure; Flow
- H01M8/04425—Pressure; Ambient pressure; Flow at auxiliary devices, e.g. reformers, compressors, burners
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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
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
- H01M8/04537—Electric variables
- H01M8/04544—Voltage
- H01M8/04559—Voltage 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
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
- H01M8/04537—Electric variables
- H01M8/04634—Other electric variables, e.g. resistance or impedance
- H01M8/04649—Other electric variables, e.g. resistance or impedance 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
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
- H01M8/04746—Pressure; Flow
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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
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
- H01M8/04746—Pressure; Flow
- H01M8/04776—Pressure; Flow at auxiliary devices, e.g. reformer, compressor, burner
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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
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
- H01M8/04955—Shut-off or shut-down 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
- H01M8/10—Fuel cells with solid 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
- H01M8/10—Fuel cells with solid electrolytes
- H01M2008/1095—Fuel cells with polymeric electrolytes
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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 fuel cell system and a method for starting the same.
- FIGS. Fig. 1 shows the basic structure of a polymer electrolyte fuel cell (hereinafter referred to as PEFC) among conventional fuel cells.
- Fuel cells electrochemically react a fuel gas such as hydrogen and an oxygen-containing gas such as air by a gas diffusion electrode, and generate electricity and heat simultaneously.
- a polymer electrolyte membrane or the like that selectively transports hydrogen ions is used.
- a catalytic reaction layer 2 mainly composed of a carbon powder carrying a platinum-based metal catalyst is arranged in close contact. In the catalyst reaction layer, the reactions shown in (Chemical formula 1) and (Chemical formula 2) occur, and the reaction shown in (Chemical formula 3) occurs in the entire fuel cell.
- a fuel gas containing at least hydrogen undergoes a reaction represented by (Chemical Formula 1) (hereinafter, referred to as an anodic reaction), and hydrogen ions transferred through the electrolyte 1 are converted into an oxygen-containing gas (hereinafter, referred to as an anode gas).
- the reaction shown in (Chemical formula 2) (hereinafter referred to as the force sword reaction) in the catalytic reaction layer 2 to generate water, which generates electricity and heat.
- the hydrogen and oxygen react to generate water, the entire fuel cell can use electricity and heat.
- the side that participates in fuel gas such as hydrogen is referred to as the anode, a is indicated in the figure, and the side in which oxygen-containing gas such as air is involved is the cathode, and c is indicated in the figure.
- diffusion layers 3a and 3c having both gas permeability and conductivity are arranged on the outer surfaces of the catalyst reaction layers 2a and 2c in close contact with the catalyst reaction layers 2a and 2c.
- the diffusion layers 3a and 3c and the catalytic reaction layers 2a and 2c form electrodes 4a and 4c.
- Reference numeral 5 denotes an electrode electrolyte assembly (hereinafter, referred to as MEA), which is formed by the electrode 4 and the electrolyte 1.
- MEA electrode electrolyte assembly
- the MEA 5 mechanically fixes the MEA 5, connects the adjacent MEAs 5 electrically in series with each other, supplies a reaction gas to the electrodes, and removes gas generated by the reaction and excess gas.
- a pair of conductive separators 7a and 7c having gas passages 6a and 6c for carrying away on the surface in contact with MEA 5 are arranged.
- a basic fuel cell unit includes an electrolyte 1, a pair of catalytic reaction layers 2a and 2c, a pair of diffusion layers 3a and 3c, a pair of electrodes 4a and 4c, and a pair of separators 7a and 7c.
- this will be referred to as senoré).
- the separators 7a and 7c are in contact with the separators 7c and 7a of the adjacent cells on the side opposite to the MEA5.
- the cooling water passage 8 is provided on the side where the separators 7a and 7c are in contact, and the cooling water 9 flows here. Cooling water 9 transfers heat to adjust the temperature of MEA 5 via separators 7a and 7c.
- MEA gasket 10 seals ⁇ 5 and separator 7a or 7c, and separator gasket 11 seals separators 7a and 7c.
- Electrolyte 1 has a fixed charge, and hydrogen exists as a counter ion of the fixed charge. Electrolyte 1 is required to have a function to selectively transmit hydrogen ions. However, for that purpose, it is necessary that the electrolyte 1 retains moisture. When the electrolyte 1 contains water, the fixed charge fixed in the electrolyte 1 is ionized, and hydrogen, which is a counter ion of the fixed charge, is ionized and can move.
- the stack will be described with reference to FIG. Since the voltage of a fuel cell is usually as low as 0.75v, a high voltage is obtained by stacking a plurality of cells in series.
- the current collecting plate 21 is for extracting current from the stack to the outside, and the insulating plate 22 electrically insulates the cell from the outside.
- the end plates 23 fasten the stack of stacked cells and hold them mechanically.
- the outer housing 31 contains the fuel cell system.
- the gas purifying section 32 removes substances that have an adverse effect on the fuel cell from the fuel gas, and guides the fuel gas from the outside via the raw material gas pipe 33. Valves 3 4 control the flow of the feed gas.
- the fuel generator 35 generates a fuel gas containing at least hydrogen from the raw material gas. Fuel gas is led from the fuel generator 35 to the stack 38 via the fuel gas pipe 37.
- the blower 39 directs the oxidant gas through the intake pipe 40 to the stack 38.
- the exhaust pipe 42 discharges the oxidant gas discharged from the stack 38 to the outside of the fuel cell system.
- the fuel gas not used in the stack 38 flows again into the fuel generator 35 through the off-gas pipe 48.
- the gas from the off-gas pipe 48 is used for combustion and the like, and is used for an endothermic reaction for generating a fuel gas from a raw material gas.
- the power circuit section 43 takes out power from the fuel cell stack 38, and the control section 44 controls the gas, the power circuit section, and the like.
- the pump 45 flows water from the cooling water inlet pipe 46 to the water path of the fuel cell stack 38.
- the water flowing through the fuel cell stack 38 is transferred to the outside from the cooling water outlet pipe 47.
- the flow of water through the fuel cell stack 38 makes it possible to use the generated heat outside the fuel cell system while keeping the heated stack 38 at a constant temperature.
- Fuel cell system includes a fuel cell stack 38, a gas cleaning unit 32, a fuel generator 35, a power circuit unit 43, and a control unit 44.
- a home fuel cell system is composed of a fuel cell stack 38 and a fuel generator 35. It is necessary to ensure that the performance of the fuel cell system does not deteriorate and that the performance can be maintained for a long time.
- a raw material gas such as town gas containing methane
- electricity and quiet time heat consumption is stopped
- an operation method that operates during periods of high electricity and heat consumption is effective.
- the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a fuel cell system capable of appropriately coping with problems such as promotion of drying of an electrolyte membrane and local reactions, and stabilizing the performance of a fuel cell.
- An object of the present invention is to provide a starting method.
- a first aspect of the present invention provides a fuel cell that generates electric power from a fuel gas and an oxidant gas,
- Fuel gas supply means for supplying the fuel gas to the anode side of the fuel cell
- Oxidizing gas supply means for supplying the oxidizing gas to a power source side of the fuel cell
- Control means for controlling the fuel gas supply means, the oxidant gas supply means and the source gas supply means,
- the source gas supply unit sets at least the power source side of the fuel cell to the source gas.
- the fuel cell system is purged with
- the second invention is the fuel cell system according to the first invention, wherein the raw material gas supply means purges the anode side after purging the power source side in the fuel cell.
- a third invention provides a fuel gas pipe provided between the fuel gas supply means and a cathode side of the fuel cell,
- a fuel gas switch provided in the middle of the fuel gas pipe; a valve;
- An oxidizing gas pipe provided between the oxidizing gas supply means and the anode side of the fuel cell;
- An oxidizing gas opening / closing valve provided in the middle of the oxidizing gas piping; the source gas supply means; and the oxidizing gas piping between the oxidizing gas opening / closing valve and a power source side of the fuel cell.
- Source gas piping connected to a portion of
- a fuel cell system comprising a source gas on-off valve provided in the source gas pipe.
- a fourth invention provides a cathode-side discharge pipe for discharging off-gas discharged from a power source side of the fuel cell
- a cathode-side off-gas on-off valve provided in the middle of the cathode-side discharge pipe; The purging,
- a fuel cell system which is performed by opening and closing the source gas on-off valve for a predetermined period.
- the source gas supply means is connected to a part of the source gas pipe between the fuel gas on-off valve and the anode side of the fuel cell. Additional material gas piping,
- An additional source gas on-off valve provided in the middle of the additional source gas pipe, an anode side discharge pipe for discharging off-gas discharged from the anode side of the fuel cell,
- An anode-side off-gas on-off valve provided in the middle of the anode-side discharge pipe,
- a fuel cell system according to a fourth aspect of the present invention, wherein the additional source gas on-off valve is opened for a predetermined period.
- the oxidizing gas supply unit and the fuel gas supplying unit supply the fuel gas and the oxidizing gas to the fuel cell.
- the fuel cell system according to the fifth aspect of the present invention is performed by subsequently opening the oxidizing gas reclosing valve after opening the cathode-side off-gas on-off valve.
- the seventh invention provides a method for generating electric power from a fuel gas and an oxidizing gas.
- a fuel cell an oxidizing gas supply means for supplying an oxidizing gas to the fuel cell, and a fuel supply means for supplying the fuel gas to the fuel cell.
- At least a power source side of the fuel cell is purged with a raw material gas used to generate the fuel gas. How to start the system.
- An eighth aspect of the present invention is the start-up method of the fuel cell system according to the seventh aspect of the present invention, wherein after purging the force source side in the fuel cell, the anode side is purged.
- the present invention in the method for activating the fuel cell system according to the seventh aspect of the present invention, when starting the power generation of the fuel cell, before supplying the fuel gas and the oxidizing gas to the fuel cell, Further, the present invention is a program for controlling, by a computer, a step of purging at least a cathode side of the fuel cell with a source gas used to generate the fuel gas.
- a tenth aspect of the present invention is a recording medium carrying the program of the ninth aspect of the present invention, which is a recording medium that can be processed by a computer.
- FIG. 1 shows a partial structure of a unit cell of a polymer electrolyte fuel cell according to Embodiments 1 to 3 of the present invention and a conventional example. '
- FIG. 2 shows a polymer electrolyte fuel according to Embodiments 1 to 3 of the present invention and a conventional example.
- 1 shows a structure of a stack in which batteries are stacked.
- FIG. 3 is a configuration diagram showing a polymer electrolyte fuel cell system according to Embodiments 1 to 3 of the present invention.
- -FIG. 4 is a diagram showing a flowchart for explaining the operation of the polymer electrolyte fuel cell system according to Embodiment 1 of the present invention.
- FIG. 5 is a flowchart showing an operation of the polymer electrolyte fuel cell system according to Embodiment 2 of the present invention.
- FIG. 6 is a diagram showing a flowchart for explaining the operation of the polymer electrolyte fuel cell system according to Embodiment 3 of the present invention.
- FIG. 7 is a diagram showing a flowchart for explaining details of the stopping step 1 of the polymer electrolyte fuel cell system according to Embodiment 1 of the present invention.
- FIG. 8 is a configuration diagram showing a fuel cell system according to Embodiment 4 of the present invention.
- FIG. 9 is a configuration diagram showing a fuel cell system according to Embodiment 5 of the present invention.
- FIG. 10 is a cross-sectional view of a solid polymer electrolyte fuel cell provided with an electrolyte assembly (MEA; Membrane-Electrode Assembly).
- MEA Electrolyte assembly
- FIG. 11 is a block diagram showing a basic configuration of the fuel cell power generator.
- FIG. 12 is a block diagram showing a configuration of a fuel cell power generator according to Embodiment 6 of the present invention.
- FIG. 13 is a diagram of the first half of a flowchart illustrating a gas supply operation according to Embodiment 6 of the present invention.
- FIG. 14 is a diagram of the latter half of the flowchart for explaining the gas supply operation according to the sixth embodiment of the present invention.
- FIG. 15 is an AC impedance profile diagram of the fuel cell measured by varying the frequency applied to the fuel cell in the range of 0.1 Hz to lk Hz.
- FIG. 16 is a diagram showing the relationship between the relative humidity and the conductivity of the electrolyte membrane.
- FIG. 17 is a block diagram showing a configuration of a fuel cell power generator according to Embodiment 7 of the present invention.
- FIG. 18 is a diagram of the first half of a flowchart illustrating a gas supply operation according to Embodiment 7 of the present invention.
- FIG. 19 is a diagram of the latter half of the flowchart for explaining the gas supply operation according to the seventh embodiment of the present invention.
- FIG. 20 is a block diagram showing a configuration of a fuel cell power generator according to Embodiment 8 of the present invention.
- FIG. 21 is a diagram of the first half of a flowchart illustrating a gas supply operation according to Embodiment 8 of the present invention.
- FIG. 22 is a diagram of the latter half of a brochure illustrating a gas supply operation according to Embodiment 8 of the present invention.
- FIG. 24 is a diagram showing a configuration of a fuel cell system according to Embodiment 9 of the present invention.
- FIG. 25 is a diagram showing a transition of the average value of the internal resistance of the unit cell in the operation method of the fuel cell system according to Embodiment 9 of the present invention. _ .
- FIG. 26 is a diagram showing a transition of the battery temperature in the method of operating the fuel cell system according to Embodiment 9 of the present invention.
- FIG. 27 is a diagram showing transition of the amount of generated power in the operating method of the fuel cell system according to Embodiment 9 of the present invention.
- FIG. 28 is a diagram showing a transition of the average value of the voltage of the unit cell in the operation method of the fuel cell system according to Embodiment 9 of the present invention.
- FIG. 29 is a schematic vertical sectional view showing a part of the fuel cell stack in the fuel cell system according to Embodiment 9 of the present invention.
- FIG. 30 is a schematic cross-sectional view illustrating a structure of a part of a unit cell of the polymer electrolyte fuel cell according to Embodiment 10 of the present invention.
- FIG. 31 is a schematic diagram for explaining the structure of a stack in which polymer electrolyte fuel cells according to Embodiment 10 of the present invention are stacked.
- FIG. 32 is a schematic diagram of a fuel cell power generator according to Embodiment 10 of the present invention.
- FIG. 33 is a schematic diagram of a fuel cell power generator according to Embodiment 11 of the present invention.
- FIG. 34 is an explanatory diagram showing the relationship between the voltage change and the oxygen concentration in the start-stop operation of the fuel cell power generator according to Embodiment 10 of the present invention.
- FIG. 35 is an explanatory diagram showing a relationship between a voltage change and a potential change between the anode and the cathode in the start-stop operation of the fuel cell power generator according to Embodiment 11 of the present invention.
- FIG. 36 is an explanatory diagram showing a voltage change in the start / stop operation of the fuel cell power generator according to the comparative example of the present invention.
- FIG. 37 is an explanatory diagram showing the relationship between the number of times of starting and stopping of the fuel cell power generation device and the durability in the tenth embodiment, the eleventh embodiment, and the comparative example.
- FIG. 38 is a configuration diagram of a fuel cell system according to a conventional technique.
- FIG. 1 shows a basic configuration of a polymer electrolyte fuel cell as an example of a fuel cell according to Embodiment 1 of the present invention.
- a fuel cell electrochemically reacts a fuel gas containing at least hydrogen and an oxidizing gas containing oxygen such as air by a gas diffusion electrode, and generates electricity and heat simultaneously.
- a polymer electrolyte membrane or the like that selectively transports hydrogen ions is used.
- a catalytic reaction layer 2 mainly composed of a carbon powder carrying a platinum-based metal catalyst is closely arranged. Reactions represented by (Chemical formula 1) and (Chemical formula 2) occur in the catalytic reaction layers 2a and 2c.
- the fuel gas containing at least hydrogen undergoes the reaction shown in (Equation 1) (hereinafter, referred to as the anode reaction), and the hydrogen ions that have moved through the electrolyte 1 pass through the oxidant gas and the catalyst reaction layer 2 (Equation 2).
- the reaction shown below (hereinafter referred to as the force sword reaction) produces water, which in turn generates electricity and heat.
- the side that participates in fuel gas such as hydrogen is called the anode, and is denoted by a in the figure, the side that participates in oxidant gas such as air is called the force sword, and C is shown in the figure.
- diffusion layers 3a and 3c having both gas permeability and conductivity are arranged on the outer surfaces of the catalytic reaction layers 2a.
- the electrode 4a is composed of the diffusion layer 3a and the catalytic reaction layer 2a
- the electrode 4c is composed of the diffusion layer 3c and the catalytic reaction layer 2c.
- the membrane electrode assembly (hereinafter, referred to as MEA) 5 is formed by the electrodes 4 a and 4 c and the electrolyte 1.
- the MEA 5 mechanically fixes the MEA 5, electrically connects adjacent MEAs 5 in series with each other, supplies a reaction gas to the electrode, and generates gas or excess gas generated by the reaction.
- a pair of conductive separators 7a and 7c having gas flow paths 6a and 6c for carrying away gas on the surface in contact with MEA 5 are arranged.
- the basic fuel is composed of an electrolyte 1, a pair of catalytic reaction layers 2a and 2c, a pair of diffusion layers 3a and 3c, a pair of electrodes 4a and 4c, and a pair of separators 7a and 7c.
- a battery hereafter referred to as a cell.
- Separator 7a and 7c are on the side opposite to MEA 5, Separator 7c and 7a touch.
- a cooling water passage 8 is provided on the side where the separators 7a and 7c are in contact, and the cooling water 9 flows here. Cooling water 9 transfers heat to adjust the temperature of MEA 5 via separators 7a and 7c.
- MEA 5 and separator 7 a or 7 c are sealed with MEA gasket 10, and separators 7 a and 7 c are sealed with separator gasket 11.
- the electrolyte 1 has a fixed charge, and hydrogen ions are present as counter ions of the fixed charge. Electrolyte 1 is required to have a function of selectively permeating hydrogen ions. For this purpose, electrolyte 1 needs to retain moisture. When the electrolyte 1 contains water, the fixed charge fixed in the electrolyte 1 is ionized, and hydrogen, which is a counter ion of the fixed charge, can be ionized and move.
- FIG. 2 shows a stack of cells, called a stack. Since the voltage of a fuel cell is usually as low as 0.75 V, a plurality of cells are stacked in series to achieve a high voltage. A current is taken out from the stack to the outside from a pair of current collectors 21, the cell and the outside are electrically insulated by a pair of insulating plates 22, and a stack of cells is stacked by a pair of end plates 23. Fastened and held mechanically.
- FIG. 3 is a configuration diagram of the fuel cell system according to the embodiment of the present invention. The fuel cell system is housed in the outer casing 31.
- the source gas taken in from the outside through the source gas pipe 3 3 is purified by the gas purifier 3 2, which removes substances that have an adverse effect on the fuel cell, and then passed through the clean gas pipe 36 to the fuel generator 35. It is led to.
- An open / close valve 34 is provided in the source gas pipe 33 to control the flow of the source gas.
- the fuel generator 35 generates a fuel gas containing at least hydrogen from the raw material gas.
- Reference numeral 38 denotes a stack, which is a fuel cell stack shown in detail in FIGS. 1 and 2. Fuel gas is led from the fuel generator 35 to the anode side of the stack 38 via a fuel gas pipe 37.
- the air as the oxidizing gas passes through the intake pipe 40 from outside by the blower 39. Then, the gas is led to the cathode side of the stack 38 via an oxidizing gas pipe 40 a connected to the intake pipe 40 via the distribution valve 56.
- the oxidant gas not used in the stack 38 is discharged from the exhaust pipe 42 to the outside of the fuel cell system. Since the fuel cell needs moisture, the oxidizing gas flowing into the stack 38 is humidified by the humidifier 41.
- the fuel gas not used in the stack 38 flows into the fuel generator 35 again through the off-gas pipe 48.
- the gas from the off-gas pipe 48 is used for combustion and the like, and is used for an endothermic reaction for generating a fuel gas from a raw material gas.
- a distribution valve 60 is provided in the clean gas pipe 36, and a distribution valve 56 is also provided in the intake pipe 40. Distribution valve 60 and distribution valve 56 are connected to bypass pipe 55.
- a bypass pipe 61 is provided between the bypass pipe 55 and the fuel gas pipe between the stack 38 and the distribution valve 60, and an open / close valve 62 is provided in the bypass pipe 61. I have.
- the distribution valve 60 adjusts the amount of gas that flows into the fuel generator 35 and the amount of gas that flows through the bypass pipe 55 after the raw material gas purified by the gas cleaning section 32 and the distribution valve 5.
- the oxidizer gas 6 sent from the blower 39 and the purified thickener gas sent from the bypass pipe 55 are mixed at an arbitrary ratio. The mixed gas can be sent to the stack 38.
- An opening / closing valve 49 is provided in the fuel gas pipe 37 to shut off or control the flow of gas in the fuel gas supply path of the stack 38.
- the off-gas pipe 48 is provided with an on-off valve 54 for shutting off the flow of gas in the fuel gas discharge path of the stack 38.
- the on-off valve 57 is provided in the supply path of the oxidizing gas from the humidifier 41 to the stack 38, and shuts off or controls the flow of the gas in the supply path of the oxidizing gas of the stack 38.
- the on-off valve 58 is provided in the discharge path of the oxidizing gas from the stack 38, and shuts off or controls the flow of the gas in the discharge path of the oxidizing gas in the stack 38.
- a pressure gauge 59a is provided in the fuel gas supply path between the on-off valve 49 and the stack 38, and measures the pressure in the fuel gas supply path and the fuel gas path in the stack 38.
- Oxidizing gas supply for on-off valve 5 7 and stack 3 8 A pressure gauge 59 b is provided in the path, and the pressure of the oxidizing gas supply path and the pressure of the oxidizing gas path in the stack 38 are measured.
- the voltage of the fuel cell stack 38 is measured by the voltage measuring section 52, and the electric power is taken out by the power circuit section 43.It is provided in each pipe of raw material gas, fuel gas, oxidizing gas, off gas, and cooling water
- the controlled valves, the respective on-off valves and the power circuit are controlled by the controller 44.
- Water is flowed from the cooling water inlet pipe 46 to the water path of the fuel cell stack 38 by the pump 45, and the water flowing through the fuel cell 38 is transported outside from the cooling water outlet pipe 47.
- the flow of water through the fuel cell stack 38 makes it possible to use the generated heat outside the fuel cell system while keeping the heated stack 38 at a constant temperature.
- the fuel cell system includes a fuel cell stack 38, a gas cleaning unit 32, a fuel generator 35, a power circuit unit 43, and a control unit 44.
- the basic operation of the fuel cell system having the above configuration will be described.
- the valve 34 is opened, and the source gas flows from the source gas pipe 33 into the gas purification section 32.
- a hydrocarbon gas such as natural gas or propane gas can be used.
- 13 A of city gas which is a mixed gas of methane, ethane, propane, and butane gas is used. .
- Neo is used especially for removing gas odorants such as TBM (tertiary butyl mercaptan), DMS (dimethyl sulfide), and THT (tetrahydrothiophene).
- gas odorants such as TBM (tertiary butyl mercaptan), DMS (dimethyl sulfide), and THT (tetrahydrothiophene).
- Sulfur compounds, such as odorants are adsorbed on the fuel cell catalyst and become a catalyst poison, inhibiting the reaction.
- hydrogen is generated by the reaction shown in (Chemical formula 9) and the like.
- the simultaneously generated carbon monoxide is reduced to less than 10 ppm by a shift reaction as shown in (Chemical formula 10) and a selective oxidation reaction of carbon monoxide as shown in (Chemical formula 11). Removed.
- a fuel gas containing hydrogen and moisture is generated and flows into the fuel cell stack 38 through the fuel gas pipe 37.
- the oxidizing gas passes through the humidifier 41 by the blower 39 and then flows into the stack 38.
- the exhaust gas of the oxidizing gas is discharged to the outside through the exhaust pipe 42.
- the humidifier 41 a humidifier in which oxidizing gas flows into warm water or a humidifier in which water is blown into oxidizing gas can be used.
- a total heat exchange type is used.
- water and heat in the exhaust gas pass through the humidifier 41, they are transferred from the intake pipe 40 to the oxidizing gas serving as a raw material. After the cooling water flows from the cooling water inlet pipe 46 to the water path of the fuel cell stack 38 by the pump 45, the water is transported outside from the cooling water outlet pipe 47.
- the cooling water inlet pipe 45 and the cooling water outlet pipe 47 are connected to equipment for storing or using heat, such as a normal water heater.
- the heat generated in the fuel cell stack 38 can be extracted and used for hot water supply.
- the voltage is measured by the voltage measurement unit 52, and when the control unit 44 determines that the power generation is sufficiently performed, the power is extracted by the power circuit unit 43.
- the power circuit unit 43 converts the DC power taken out of the stack 38 into AC power, and is connected to a power line used in a home or the like by a so-called system link.
- An oxygen-containing gas such as air flows through the gas passage 6C, and a fuel gas containing hydrogen flows through the gas passage 6a.
- Hydrogen in the fuel gas diffuses through the diffusion layer 3a and reaches the catalytic reaction layer 2a.
- hydrogen is divided into hydrogen ions and electrons. The electrons are transferred to the cathode through an external circuit.
- Hydrogen ions permeate the electrolyte 1 and move to the cathode side to reach the catalytic reaction layer 2C.
- Oxygen in the oxidant gas such as air diffuses through the diffusion layer 3 C and reaches the catalytic reaction layer 2 C.
- oxygen reacts with electrons to form oxygen ions
- oxygen ions react with hydrogen ions to generate water.
- the oxygen-containing gas and the fuel gas react around the MEA 5 to generate water, and electrons flow.
- heat is generated during the reaction, and the temperature of MEA 5 increases.
- water generated by the reaction is carried out by flowing water through the cooling water paths 8a and 8c. In other words, heat and current (electricity) are generated.
- it is important to control the humidity of the gas introduced and the amount of water generated by the reaction.
- Exhaust gas which is not used in the stack 38, is transferred to the outside after transferring heat and moisture to the oxidant gas sent from the blower 39 through the humidifier 41. Is discharged.
- Off-gas which is a fuel gas that has not been used in the stack 38, flows into the fuel generator 35 again through the off-gas pipe 48. The gas from the off-gas pipe 48 is used for combustion in the fuel generator 35.
- the reaction to generate fuel gas from the source gas is an endothermic reaction as shown in (Chemical formula 6), and is used as heat required for the reaction.
- the power circuit 43 draws DC power from the stack 38 after the fuel cell starts generating power.
- the control unit 44 controls the other parts of the fuel cell system so as to keep the control of the other parts optimal. If you want to stop the operation of the fuel cell, distributing valves 56 and 60 Then, the raw material gas purified by the gas purification section 32 is poured into the stack 38.
- ME A 5 in FIG. 1 was created as follows. That is, acetylene black (denka black, manufactured by Denki Kagaku Kogyo Co., Ltd., particle size: 35 nm), which is a carbon powder, was converted to an aqueous dispersion of polytetrafluoroethylene (PTFE) (Dynamic Co., Ltd., manufactured by Daikin Industries, Ltd.). 1) to prepare a water-repellent ink containing 20% by weight of PTFE as a dry weight. This ink is applied and impregnated on carbon paper (TGPH060H manufactured by Toray Industries, Inc.) as a base material of a gas diffusion layer, and is heat-treated at 30,0 ° C. using a hot air drier to obtain a gas diffusion layer. A layer (about 200 ⁇ ) was formed.
- PTFE polytetrafluoroethylene
- a catalyst (50 wt.%) Obtained by supporting a Pt catalyst on carbon powder Ketjen Black (Ketjen B lack £. Ketjen Black International Co., Ltd., particle size 3011111). 1 :) 66 parts by weight, 33 parts by weight of perfluorocarbon sulfonic acid ionomer (5% by weight Nafion dispersion liquid manufactured by A1 Drich, USA) which is a hydrogen ion conductive material and a binder (Dry weight of polymer), and the resulting mixture was molded to form a catalyst layer (10 to 20 ⁇ m).
- the gas diffusion layer and the catalyst layer obtained as described above were joined to both sides of a polymer electrolyte membrane (Nafion 112 membrane of DuPont, USA) to produce MEA5.
- a polymer electrolyte membrane Nafion 112 membrane of DuPont, USA
- a conductive separator made of a graphite plate impregnated with phenol resin, having an outer dimension of 20 cmX 32 cmX 1.3 mm and having a gas flow path and a cooling water flow path of 0.5 mm depth Plate 7 was used.
- the source gas purified by the gas purifying unit 32 is used as the inert gas. Since the main component of the source gas is methane gas, the polymer electrolyte fuel cell used in the present embodiment has almost no reactivity and can be treated as an inert gas.
- the temperature of the water in the cooling water inlet piping 46 with a hot water storage tank attached is 70 ° C, and the cooling water outlet piping 4
- the pump 45 was adjusted so that the temperature of the water in 7 became 75 ° C.
- the power generation of the stack 38 is stopped, and then the on-off valve 49 is closed to stop the supply of the fuel gas to the stack 38, or the supply of the fuel gas to the stack is stopped.
- the probe 39 is stopped, all the purified fuel gas flows through the bypass pipe 55 through the distribution valve 60, and the gas flowing into the stack 38 through the distribution valve 57 flows from the bypass pipe 55. Adjust so that gas is all.
- the oxidizing gas is replaced with a raw material gas as an inert gas. It is.
- FIG. 7 shows a more specific flowchart of (stopping step 1).
- control is performed so that electric power from the stack 38 is not supplied to the external addition (not shown) (S1), and then the on-off valve is set so that fuel gas is not supplied to the stack 38 any more.
- Close 49 S2.
- the opening / closing valve 51 is closed (S3).
- the on-off valve 57 is closed so that the oxidizing gas is no longer supplied to the stack 38 (S4).
- the distribution valves 60 and 56 are switched, and the raw material gas piping 33 is switched from the clean gas piping 36 to the bypass pipe 55 and the oxidizing gas piping 40a, and then the on-off valve 57 is opened ( S 5).
- the raw material gas that has passed through the gas cleaning section 32 is supplied to the power source side of the stack 38, and the oxidizing gas in the stack 38 is purged by this raw material gas.
- the control unit 44 measures the supply amount of the supplied source gas (S6), and determines whether or not the supply amount is equal to or larger than a predetermined value (S7).
- the supply of the source gas is continued until this value is reached, and when it is determined that the value is equal to or greater than the value, the on-off valve 57 is closed (S8), and thereafter the on-off valve 58 is closed (S9).
- the pump 45 is stopped to stop the circulation of the cooling water to the stack 38 (S10).
- the supply amount of the source gas to be replaced was set to 2 to 5 times the volume to be replaced. This is based on the following calculation. .
- the volume to be replaced is V (L)
- the flow rate of the gas to be replaced is V (L / min)
- the initial concentration of the target component of the oxidizing gas is c.
- the concentration after time t (min) is c
- the concentration change dc in the product V during the short time dt is replaced during the short time dt as shown in (Equation 1) It is equal to the amount of the target component pushed out by the gas. (Number 1)
- V ⁇ t / V indicates how many times the volume of the gas to be replaced is larger than the volume to be replaced. A factor of 2 replaces 86% or more, and a factor of 5 replaces 99.3% or more. If the volume of the replacement gas is less than twice, the amount of the oxidizing gas remaining increases, and if it exceeds five times, the replacement gas is wasted.
- the supply of fuel gas is stopped earlier or at the same time as the supply of oxidant gas, so the power generation efficiency per fuel energy can be increased without wasting fuel gas. You can.
- stop process 1 After the above (stop process 1) is completed, the process proceeds to (stop process 2). That is, the valve 34 is closed, and the supply of the source gas is stopped.
- the extraction of the current from the stack 38 may be the same as the stop of the blower 39 in the (stop process 1) as described above, but the power circuit 43 may be controlled at a predetermined voltage.
- the catalytic reaction layer 2a when the voltage per unit cell of the stack 38 is 0.5 V or more, the current is extracted by the power circuit unit 43, and when the voltage is less than 0.5 V, the current is not extracted. If stopped in (stopping step 2), the catalytic reaction layer 2a will be filled with a gas containing hydrogen, and the potential will be 0V (ratio of hydrogen electrode).
- the catalyst reaction layer 2c is filled with a raw material gas that is an inert gas. However, since hydrogen diffuses through the electrolyte 1, the potential is 0 V (ratio of hydrogen electrode). Therefore, both electrodes can be stopped without becoming a high potential at which oxidation or dissolution occurs, so that the deterioration is small and the performance can be maintained for a long time.
- the on-off valve 34 is opened and the raw material gas is sealed again.
- the source gas is added to the fuel gas, the hydrogen concentration decreases, but the entry of high-potential gases such as oxygen has been eliminated.
- the potentials at 4a and 4c can be kept low. As a result, not only deterioration due to electrode oxidation and dissolution can be suppressed, but also damage to the constituent materials of the stack 38 due to pressure changes can be prevented, so that high performance can be maintained for a long time.
- the pressure gauges 59a and 59b are used to directly measure the pressure in the stack 38. However, a thermometer that measures the temperature in the stack 38, etc. The measurement obtained by this means The internal pressure of the stack 38 may be obtained indirectly based on the value.
- the raw material gas purified by the gas purifying section 32 is used as the inert gas. This is convenient because it uses a source gas and can be created without special equipment, but the same effect can be obtained even if a nitrogen gas cylinder or the like is installed and an inert gas such as nitrogen gas is used. .
- the raw material gas as the inert gas is humidified by the humidifier 41 provided in the passage of the oxidizing gas and the fuel gas. By providing the humidifier 41 in a common passage for the oxidizing gas and the fuel gas, different gases can be humidified by one humidifier, which is more effective.
- the source gas as an inert gas was humidified.
- bypass pipe 61 and the on-off valve 62 may be omitted, and the stop step 3 may be omitted, and the stop step 3 may be performed as a method of sealing the source gas only on the force source side. .
- the oxidizing gas in the stack 38 is replaced by the raw material gas as an inert gas while the fuel gas flows through the stack 38. After a predetermined time (stopping process 2), move on.
- (stopping process 2) the on-off valves 57 and 58 are closed, and a raw material gas as an inert gas is sealed inside the stack 38.
- hydrogen is also supplied because fuel gas is supplied. Since the source gas is sealed, hydrogen that has diffused the electrolyte 1 from the fuel gas and moved to the source gas side stays near the catalytic reaction layer 2c. As a result, the potential of the electrode 4c can be quickly and surely lowered, so that the deterioration of the electrode can be more reliably suppressed.
- (Stopping step 2) may be performed for a predetermined period of time, but in this embodiment, after the voltage per unit cell of the stack becomes equal to or less than 0.4, the procedure proceeds to (Stopping step 3). did.
- the electrode 4a is always at 0 V, so that the cell voltage is equal to the potential of the electrode 4c.
- the electrode 4c becomes 0.4 IV, it can be said that the potential of the electrode 4c has definitely decreased due to the diffused hydrogen, and the fuel gas can be used without excess and deficiency, thereby increasing the power generation efficiency per energy. It is.
- the on-off valves 49, 5, and 1 are closed, and the fuel gas is sealed in the stack 38.
- the fuel gas and the source gas are supplied to the on-off valve 49 Since the gas is enclosed in the stack 38 by closing the valves 51 and 51, no gas flows in and out due to convection in the state of (stopping step 3), and the potential of the electrodes 4a and 4c can be kept low. Since the deterioration is less due to oxidation and dissolution, the performance can be maintained for a longer period of time.
- the raw material gas that has passed through the clean gas pipe 36 is sent to the fuel generator 35.However, by selecting a configuration that does not cause a reaction in the fuel generator 35 or a certain time so that the temperature is maintained, the raw material gas is used as fuel. It can be passed through a generator 35.
- the on-off valves 49 and 51 are slightly opened, and the sealed fuel gas is slightly replaced with the raw material gas.
- the gas concentration of oxygen or the like which has invaded from the outside by diffusion or the like during the encapsulation can be reduced, and the potential rise of the electrodes 4a and 4c can be suppressed for a long period of time. Deterioration due to oxidation or dissolution of a and 4c can be suppressed, and the performance can be maintained for a long time.
- the bypass pipe 61 and the on-off valve 62 may be omitted.
- Embodiment 3 The operation of the fuel cell system according to Embodiment 3 will be described below, and an embodiment of the method for stopping the fuel cell system according to the present invention will be described with reference to the flowchart shown in FIG.
- the basic configuration and operation are the same as those of the first or second embodiment, except that the bypass pipe 61 and the on-off valve 62 are omitted.
- the detailed operation method is shown below.
- the basic conditions for power generation and heat generation (operating process) are the same as in the first embodiment.
- the current drawn from the stack 38 in the power circuit 43 is controlled by the controller 4-4 according to the level of power consumption at home or the like. When the power generated from the fuel cell system is no longer consumed, the current drawn from the stack 38 decreases, and the voltage increases.
- the electrode 4c will be oxidized and dissolved, so go to (Stopping step 1). In other words, when the voltage exceeds the open circuit voltage of 0.88 V, it is possible to eliminate the ⁇ ! Rotation and maintain the performance for a long time.
- shutdown step 1 is the same as in the first embodiment.
- the blower 39 is stopped, and the fuel gas purified by the distribution valve 60 is supplied to either the bypass pipe 55 or the clean gas pipe 36.
- the gas flowing into the stack 38 by the distribution valve 57 is adjusted so that all the gas from the bypass pipe 55 is exhausted.
- the oxidizing gas in the stack 38 is replaced with the raw material gas as an inert gas while the fuel gas flows through the stack 38.
- stop process 2 After a certain period of time (stopping process 2), move on. In (stop process 2), the on-off valves 49 and 51 are closed while the source gas is flowing even after the purge is completed, and the fuel gas is sealed in the stack 38. As a result, the use of fuel gas can be reduced.
- Stop process 3 The on-off valves 57 and 58 are closed, and the raw material gas as an inert gas is sealed inside the stack 38. In the stack 38, the hydrogen that diffuses the electrolyte 1 from the fuel gas and moves to the source gas side stays near the catalytic reaction layer 2c. As a result, the potential of the electrode 4c can be reliably reduced, so that deterioration of the electrode can be reliably suppressed.
- (Stopping process 4) monitors changes in the pressure gauges 59a and 59b. Since the on-off valves 49, 51, 57, and 58 are closed, the temperature of the stack 38 drops, etc. The volume of the feed gas decreases, and the inside of the stack 38 becomes negative pressure. If the pressure inside the stack 38 becomes negative, not only gas such as air easily enters, but also the electrolyte 1 and various gaskets may be damaged.
- the opening / closing valve 49 or 57 is opened and the raw material gas is added.
- the operation is performed when the pressure changes by 5 KPa.
- the operation of flowing the source gas to the stopped stack 38 is the same as in the second embodiment.
- the on-off valve 49 or 57 is opened, and the gas is filled again.
- the source gas is added to the fuel gas, the hydrogen concentration decreases.
- the potentials of the electrodes 4a and 4c can be kept low. As a result, not only deterioration due to electrode oxidation and dissolution can be suppressed, but also damage to the constituent materials of the stack 38 due to pressure change can be prevented, so that high performance can be maintained for a long time.
- the pressure in the stack 38 is directly measured by the pressure gauges 59a and 59b.However, a means such as a thermometer for measuring the temperature in the stack 38 is used. May be provided, and the internal pressure of the stack 38 may be obtained indirectly based on the measurement value obtained thereby. That is, if the difference ⁇ ⁇ from the temperature T 1 after the purge on the power source side is completed to the temperature T 2 at the time of measurement decreases by about 5 ° C, it is considered that the pressure has decreased, and the on-off valve 49 or 57 Is opened, and the raw material gas is sealed in the stack 38.
- the stack 38 corresponds to the fuel cell of the present invention
- the fuel gas pipe 37 corresponds to the fuel gas pipe of the present invention
- the on-off valve 49 corresponds to the fuel cell of the present invention.
- These correspond to fuel gas on-off valves, and these are the fuels of the present invention.
- It constitutes gas supply means.
- the oxidizing gas pipe 40a corresponds to the oxidizing gas pipe of the present invention
- the on-off valve 57 corresponds to the oxidizing gas on-off valve of the present invention, and these constitute the oxidizing gas supply means of the present invention.
- the source gas pipes 33 and the bypass pipe 55 correspond to the source gas pipe of the present invention
- the distribution valves 56 and 60 correspond to the source gas on-off valve of the present invention. Equivalent to means.
- the control section 44 corresponds to the control means of the present invention.
- the off-gas pipe 48 corresponds to the anode-side exhaust pipe of the present invention
- the on-off valve 51 corresponds to the anode-side off-gas on-off valve of the present invention
- the exhaust pipe 42 corresponds to the cathode-side exhaust pipe of the present invention.
- On-off valve 58 corresponds to the anode-side off-gas on-off valve of the present invention.
- the bypass pipe 61 corresponds to the additional material gas pipe of the present invention
- the on-off valve 62 corresponds to the additional material gas on-off valve of the present invention.
- the first to third embodiments may also correspond to the following embodiments of the invention.
- a fuel cell including a pair of separators having a gas flow path for supplying and discharging the fuel cell; a fuel generator for generating a fuel gas to be supplied to the fuel cell from the raw material gas;
- a fuel cell system comprising: a gas purifier that removes fuel from a fuel cell; a power circuit that extracts power from the fuel cell; a voltage measuring unit that measures the voltage of the fuel cell; and a controller that controls the gas, power circuit, and the like.
- the fuel cell When the fuel cell is stopped, the supply of the fuel gas and the oxidizing gas is stopped, and the oxidizing gas inside the fuel cell is partially or entirely replaced with a gas inert to the fuel cell.
- the anode electrode When the fuel cell system is stopped, there is no or little oxygen inside the stopped fuel cell, so the anode electrode has a hydrogen potential (about 0 V with respect to the hydrogen electrode), and the cathode electrode also has an anode.
- the hydrogen diffuses from the hydrogen to the potential of hydrogen, Since the potentials of both electrodes can be kept low, a decrease in performance due to shutdown can be suppressed.
- the fuel cell system according to the first invention is provided with a shut-off valve in a supply path and a discharge path of a fuel gas and an oxidizing gas, and the fuel gas and the oxidizing agent are stopped when the fuel cell is stopped. Stop the gas supply, replace part or all of the oxidizing gas inside the fuel cell with a gas that is inert to the fuel cell, close the shutoff valve, and turn off the fuel gas and the fuel cell.
- the fuel cell system of the first invention or the second invention is provided with a humidifier in a passage for the oxidizing gas and the raw material gas, and the humidified oxidizing gas and the raw material gas are provided.
- the fuel cell system is capable of supplying fuel gas to the fuel cell, and the oxidizing gas is used as an inert gas that replaces part or all of the fuel gas.
- the humidified raw material gas can be flowed into the fuel cell, preventing the polymer electrolyte membrane from drying, preventing performance degradation due to drying of the polymer electrolyte membrane that occurs during shutdown. It can be suppressed.
- a polymer electrolyte membrane a pair of electrodes sandwiching the polymer electrolyte membrane, and a fuel gas containing at least hydrogen supplied and discharged to one of the electrodes, and an oxidizing gas containing oxygen to the other.
- Fuel cell including a pair of separators having gas flow paths for supplying and discharging fuel, a fuel generator for generating fuel gas to be supplied to the fuel cell from the raw material gas, and a raw material containing components that adversely affect the fuel cell
- a gas purifier that removes gas from the gas and power from the fuel cell
- a fuel cell system having a power circuit section for outputting a voltage, a voltage measurement section for measuring the voltage of the fuel cell, and a control section for controlling a gas power circuit section, etc., when the fuel cell is stopped, the voltage of the fuel cell becomes 0.
- the operation of the fuel cell system is stopped in which the supply of the fuel gas and the oxidizing gas is stopped and the oxidizing gas in the fuel cell is partially or entirely replaced with an inert gas to the fuel cell.
- the potential of each electrode of the fuel cell can always be 0.88 V or less (based on the elementary electrode), so that oxidation and dissolution of the catalyst such as Pt can be prevented, and Can be maintained for a long time.
- a polymer electrolyte membrane a pair of electrodes sandwiching the polymer electrolyte membrane, supply and discharge of a fuel gas containing at least hydrogen to one of the electrodes, and an oxidant gas containing oxygen to the other.
- Fuel cell including a pair of separators having gas flow paths for supplying and discharging fuel, a fuel generator for generating fuel gas to be supplied to the fuel cell from the raw material gas, and a raw material containing components that adversely affect the fuel cell
- a fuel cell including a gas purifying unit for removing gas, a power circuit unit for extracting electric power from the fuel cell, a voltage measuring unit for measuring a voltage of the fuel cell, and a control unit for controlling a gas-power circuit unit and the like.
- the anode electrode is filled with hydrogen and the potential is about 0 V (based on the hydrogen electrode). Even if the pressure is reduced or the oxidizing gas is supplied by the primary inertia, the potential of the force electrode is reduced to about 0 (based on the hydrogen electrode) by the hydrogen diffused from the anode after the replacement with the inert gas. Since V is reached, performance can be suppressed even if the operation is stopped. Also, the fuel gas is called oxidant gas. By shutting down first, the amount of hydrogen not used for power generation can be minimized, and a fuel cell system with higher power generation efficiency per energy can be realized.
- a polymer electrolyte membrane, a pair of electrodes sandwiching the polymer electrolyte membrane, a fuel gas containing at least hydrogen is supplied to one of the electrodes, and the other is oxidant containing oxygen.
- a fuel cell including a pair of separators having gas flow paths for supplying and discharging gas, a fuel generator for generating fuel gas to be supplied to the fuel cell from a raw material gas, and a component that adversely affects the fuel cell.
- a fuel having a gas purifying unit for removing from a source gas, a power circuit unit for extracting electric power from a fuel cell, a voltage measuring unit for measuring a voltage of the fuel cell, and a control unit for controlling a gas-power circuit unit and the like.
- the supply of the oxidizing gas is stopped after the supply of the oxidizing gas is stopped, and the oxidizing gas inside the fuel cell is a gas that is partially or completely inert to the fuel cell.
- the hydrogen flows to the anode at least for the first time when the oxidant gas is replaced with an inert gas, so that oxygen is removed from the power sword.
- the potential of the anode electrode is not changed at all even if it diffuses into the cathode (based on the hydrogen electrode). A voltage of about 0 V is maintained, and a sufficient amount of hydrogen diffuses into the power source. Since the voltage can be reliably reduced to about OV (based on the hydrogen electrode), the performance of the cathode electrode can be reliably improved, so that the performance can be suppressed even if the operation is stopped.
- a polymer electrolyte membrane a pair of electrodes sandwiching the polymer electrolyte membrane, a fuel gas containing at least hydrogen supplied and discharged to one of the electrodes, and an oxidizing gas containing oxygen to the other.
- a pair of separators having gas flow paths for supplying and discharging fuel, a fuel gas and oxidizing gas supply path, a fuel cell equipped with a shutoff valve in the discharge path, and a supply of raw material gas to the fuel cell Generator that generates fuel gas to be discharged, a gas purifier that removes components that have an adverse effect on the fuel cell from the source gas, a power circuit that extracts power from the fuel cell, and a voltage that measures the voltage of the fuel tank
- a fuel cell system that has a measurement unit and a control unit that controls the gas, power circuit, etc., when the fuel cell is stopped, the fuel gas stops being supplied, and then the shut-off valve supplies the fuel gas into the fuel cell.
- the fuel cell system operates by injecting the inert gas into the fuel gas filling section and the inert gas filling section. Even if the internal pressure becomes negative pressure due to the reaction between hydrogen and hydrogen and the internal pressure becomes negative or the pressure between the anode and the power source becomes different, inert gas is injected into the fuel gas and inert gas charging sections. By injecting, the internal pressure can eliminate the negative pressure or the pressure difference between the anode and the cathode, so that the stress applied to the polymer electrolyte membrane etc.
- the sealing gas can be replaced by the inert gas by opening the shutoff valve of the discharge path of the fuel gas or the oxidizing gas. Even if oxygen in the air gradually invades through the gasket / separator material while the fuel cell is stopped, it can be discharged outside the fuel cell.
- a polymer electrolyte membrane a pair of electrodes sandwiching the polymer electrolyte membrane, a fuel gas containing at least hydrogen supplied and discharged to one of the electrodes, and an oxidizing gas containing oxygen contained in the other.
- a pair of separators having gas flow paths for supplying and discharging fuel, a fuel cell equipped with shut-off valves in the fuel gas and oxidizing gas supply and discharge paths, and a fuel gas to be supplied to the fuel cell from the raw material gas
- Fuel generator and components that have an adverse effect on the fuel cell A gas purifier that removes gas from the raw material gas, a power circuit that extracts power from the fuel cell, a voltage measuring unit that measures the voltage of the fuel cell, a pressure measuring unit that measures the pressure inside the fuel cell, In a fuel cell system that has a control unit that controls the gas, power circuit, etc., when the fuel cell is stopped, the supply of the fuel gas is stopped, and then the fuel gas is sealed inside the fuel cell with a shut-off valve and oxidized.
- the operation method of the fuel cell system shall be to inject the inert gas into the fuel gas inlet and the inert gas inlet or open the shut-off valve and open the space inside the fuel cell to the outside.
- the internal pressure can be reduced to a negative pressure or the pressure difference between the anode and the cathode. Since such a stress can be eliminated, a decrease in performance can be suppressed even when the operation is stopped. Furthermore, when the inert gas is injected, the sealing gas can be replaced by the inert gas by opening the shut-off valve of the fuel gas or oxidizing gas discharge path, and the gasket / separator material can be replaced while the fuel cell is stopped. Even if oxygen in the air gradually invades through the fuel cell, it can be discharged outside the fuel cell.
- a pair of separators having gas flow paths for supplying and discharging gas, a fuel cell equipped with a shut-off valve in the supply path and discharge path of fuel gas and oxidizing gas, and supplying fuel gas from raw material gas to the fuel cell
- Controls a fuel generator that generates fuel gas to be discharged, a gas purifier that removes components that have an adverse effect on the fuel cell from the source gas, a power circuit that extracts power from the fuel cell, and a gas and power circuit.
- a fuel cell system with a control unit when the fuel cell is stopped, the supply of fuel gas is stopped, then the fuel gas is sealed inside the fuel cell by a shutoff valve, and the supply of oxidant gas is stopped.
- the anode electrode can be reliably maintained at about 0 V (based on the hydrogen electrode), the voltage can detect the potential of the force source, and the potential of the force source can be maintained until the potential reaches a predetermined potential.
- Inactive It is possible to replace the gas, it can suppress a decrease in performance even if the stop.
- any one of the first to ninth aspects is used as an inert gas for the fuel cell, a component gas having an adverse effect on the fuel cell,
- the oxidizing gas can be easily replaced with an inert gas without having a special device such as a cylinder.
- the performance can be prevented from deteriorating.
- FIG. 8 is a configuration diagram of a fuel cell system according to Embodiment 4 of the present invention.
- the fuel cell system according to the fourth embodiment of the present invention includes a polymer electrolyte fuel cell 81 that generates electric power using a fuel gas and an oxidant gas, and a hydrogen gas that is reformed by adding water to a raw material gas.
- Generator 8 that generates fuel gas rich in water
- water supply means 8 3 that supplies water to fuel generator 8 2.
- combustor 8 that burns fuel gas discharged from fuel cell 8 1.
- a blower 85 for supplying air as an oxidant gas to the cathode of the fuel cell 81 an air supply means 86 for purging, and a fuel generator 8
- a fuel gas supply channel that supplies the fluid sent from the fuel cell 2 to the anode of the fuel cell 81, and supplies the exhausted combustion gas to the combustor by passing the fluid sent from the fuel generator 82 through the fuel cell.
- the raw material is not limited to natural gas, but is a compound composed of at least carbon and hydrogen exemplified by city gas, hydrocarbons such as methane and propane, and alcohols such as methane and ethanol. Any material may be used as long as it contains.
- the liquid raw material such as alcohol is preferably a vaporized raw material gas.
- the flow path switching means 88 forms a bypass flow path and is set to supply the fluid sent from the fuel generator 82 to the bypass pipe 87, the fuel gas is supplied to the fuel cell 81. Since the inlet side is in the closed state, the flow path switching means 88 and the on-off valve 89 constitute the anode closing means 8 12.
- the internal configuration of the fuel cell 81 is the same as that shown in FIGS.
- the fuel generator 82 is maintained at a temperature of about 64 ° C. to generate hydrogen-rich fuel gas from natural gas and water, and the fuel gas flows through the supply passage. It is sent to the fuel cell 81 via the formed flow path switching means 88.
- the fuel cell 81 power was generated using hydrogen in the fuel gas and oxygen in the air supplied from the blower 85 via the open power sword closing means, and was not consumed by power generation
- the residual fuel gas passes through the open / close valve 8 9 and the combustor 8 4
- stop the blower 8 5 to fuel cells 8 1 force Sword
- the supply of air to the fuel cell is stopped, and before the voltage of the fuel cell 81 becomes the open circuit voltage, the raw material power source supplying means 810 starts supplying the raw material to the power source of the fuel cell 81.
- the power source closing means 811 is closed, and the raw material power source supply means 810 transfers the raw material to the power source of the fuel cell 81. Stop supplying to the sword.
- the flow path switching means 88 is switched to the bypass pipe 87 side to form a bypass flow path and close the on-off valve 89 to seal the fuel gas present at the anode of the fuel cell 81. Then, the supply of the raw material to the fuel generator 82 is stopped.
- the supply of water to the fuel generator 82 by the water supply means 83 is continued.
- the water supplied to the fuel generator 82 becomes steam by the heat of the fuel generator 82, and pushes out the hydrogen-rich fuel gas remaining in the fuel generator 82, thereby causing the flow path switching means 88, the pipe pipe 8 It burns in the combustor 8 4 via 7.
- the combustion in the combustor 84 stops because the amount of hydrogen-rich fuel gas gradually decreases, but the generation of steam is continued by the residual heat of the fuel generator 82.
- the amount of water vapor generated by the fuel generator 82 reaches an amount enough to drive out the hydrogen-rich fuel gas in the fuel generator 82; and the temperature of the fuel generator 82 reaches about 400 ° C.
- the supply of water by the water supply means 83 is stopped and air is supplied by the air supply means for purging 86 to push out the water vapor in the fuel generator 82 and to switch the flow path 88,
- the gas is discharged from the combustor 84 via the bypass pipe 87.
- the purge air supply means 86 stops the air supply and completes the fuel cell system stop processing.
- the above-mentioned temperature of 400 ° C. means that the catalyst used in the fuel generator 82 is The temperature is set with a certain safety factor in mind so that the catalyst does not oxidize when exposed to air at high temperatures and does not cause performance degradation. Therefore, it is natural that the temperature changes depending on the setting of the safety factor, and the temperature should naturally be set differently for different types of catalysts.
- the flow path switching means 88 burns the raw material through the fuel generator 82, the flow path switching means 88, and the bypass pipe 87 while forming the bypass flow path. It is supplied to the vessel 84 and burns. At the same time, the water supply means 3 supplies water to the fuel generator 82. Then, the fuel generator 82 is heated to about 64 ° C. by the burner 84, and is converted from the raw material into a fuel gas rich in hydrogen.
- the temperature of the carbon monoxide removing section (not shown) included in the fuel generator 82 is stabilized, and the concentration of carbon monoxide contained in the fuel gas does not deteriorate the anode electrode of the fuel cell 81 (approximately 2 (0 ppm), the on-off valve 89 is opened, the flow path switching means 88 is switched to the fuel gas supply flow path side, and the fuel gas is switched to the flow path switching means 88, the fuel cell 81, the on-off valve It is supplied to combustor 84 via 8 9.
- the force sword closing means 8 1 1 is set to the open state, the blower 8 5 starts supplying air to the force sword of the fuel cell 8 1, and starts power generation by the fuel cell 8 1.
- the flow path switching unit 88 forms a bypass flow path and opens and closes the valve 89.
- the fuel cell 1 can be stopped safely without air flowing into the cathode of the fuel cell 1. It will not be exposed to oxidizing atmospheres where there is rust.
- the raw material power sword supply means 810 supplies the raw material to the cathode of the fuel cell 1 to drive out the air of the power sword and then stops. Even if gas diffusion to the anode occurs, air does not enter the anode, so the anode potential Is kept low, the elution of the anode catalyst is eliminated, and the durability of the fuel cell system is not reduced.
- the cathode catalyst is not eluted due to the high cathode potential, and the durability of the fuel cell system is reduced. Do not invite.
- the raw material supplied to the power sword of the fuel cell 81 by the raw material cathode supply means 8 10 is sealed, so that even if the stop period is long, Air does not reach the fuel cell 81 from outside, and there is no concern that the durability of the fuel cell system will be reduced, even during long-term shutdown.
- the fuel generator 82 pushes out the internal fuel gas with water vapor first, and after the temperature drops sufficiently, drives out the water vapor with air, so there is no danger of flammable gas staying inside at high temperatures.
- water does not accumulate inside when stopped, so that water does not accumulate in the piping at the next start-up, and the supply of fuel gas does not become unstable.
- the flow path switching means 88 is switched to the fuel gas supply flow path side, and the on-off valve 89 is opened to burn the fuel gas sealed in the fuel cell 1.
- the fuel gas sealed in the fuel cell 81 is not released to the outside, and there is no danger of the fuel gas being discharged to the outside.
- FIG. 9 is a configuration diagram of a fuel cell system according to Embodiment 5 of the present invention.
- the same components as those in the conventional example or the fourth embodiment of the present invention are given the same numbers. '
- the fuel cell system according to a fifth embodiment of the present invention differs from the raw material further comprising a raw material anode supply means 8 1 3 supplied to the anode of the fuel cell 1 in the fourth embodiment.
- the operation of the fuel system according to the present embodiment having the above-described configuration will be described below, and an embodiment of the method for stopping the fuel cell system according to the present invention will be described.
- the fuel generator 82 is maintained at a temperature of about 64 ° C. to generate hydrogen-rich fuel gas from natural gas and water, and the fuel gas flows through the supply passage. It is sent to the fuel cell 81 via the formed flow path switching means 88. In the fuel cell 81, power is generated using hydrogen in the fuel gas and oxygen in the air supplied from the blower 85 through the open power sword closing means, and is consumed by the power generation. The remaining residual fuel gas is sent to a combustor 84 via an open / close valve 89 in an open state and burned, and is used as a heat source for maintaining the temperature of the fuel generator 82.
- the raw material power source supply means 810 starts supplying the raw material to the power source of the fuel cell 81.
- the canode closing means 811 is closed, and the raw material cathode supply means 810 supplies the raw material to the power source of the fuel cell 81. To stop.
- the flow path switching means 88 is switched to the bypass pipe 87 side to form a bypass flow path and keep the on-off valve 89 open, and the anode closing means 81 2 To the anode.
- the on-off valve 89 is closed, and the raw material anode supply means 81 3 supplies the raw material to the anode of the fuel cell 81. Stop.
- the supply of the raw material to the fuel generator 82 is stopped, and the supply of water to the fuel generator 82 by the water supply means 83 is continued.
- the water supplied to the fuel generator 82 becomes steam by the heat of the fuel generator 82, and pushes out the hydrogen-rich fuel gas remaining in the fuel generator 82, and the flow path switching means 88, the pipe pipe 8 Fire via 7 Burn in 84.
- the combustion in the combustor 84 stops because the amount of hydrogen-rich fuel gas gradually decreases, but the generation of steam is continued by the residual heat of the fuel generator 82.
- the amount of water vapor generated by the fuel generator 82 reaches a sufficient amount to expel the hydrogen-rich fuel gas in the fuel generator 2 and the temperature of the fuel generator 82 reaches approximately 400 ° C.
- the supply of water by the water supply means 8 3 is stopped and air is supplied by the purge air supply means 86 to push out the water vapor in the fuel generator 82 and to switch the flow path 8 8.
- the purging air supply means 86 stops the air supply and completes the stop generation of the fuel cell system.
- the above-mentioned temperature of 400 ° C is based on the assumption that the catalyst used in the fuel generator 82 contains ruthenium as a main component. It is a temperature set with a certain safety factor in mind so as not to cause it. Therefore, it is natural that the temperature changes depending on the setting of the safety factor, and the temperature should naturally be set differently for different types of catalysts.
- the flow path switching means 88 feeds the raw material through the fuel generator 82, the flow path switching means 88, and the bypass pipe 87 while forming the bypass flow path. Supply to 4 for combustion.
- the water supply means 83 supplies water to the fuel generator 82.
- the combustor 84 heats the fuel generator 82 to about 640 ° C. and converts the raw material into a hydrogen-rich fuel gas.
- the temperature of the carbon monoxide removing section (not shown) included in the fuel generator 82 is stabilized, and the concentration of carbon monoxide contained in the fuel gas does not deteriorate the anode voltage of the fuel cell 1 (about 2 (0 ppm), the on-off valve 89 is opened, the flow path switching means 8 is switched to the fuel gas supply flow path side, and the fuel gas is switched
- the fuel is supplied to the combustor 84 via the stage 88, the fuel cell 81, and the on-off valve 89.
- the force sword closing means 8 1 1 is set to the open state, the blower 8 5 starts supplying air to the force sword of the fuel cell 8 1, and starts power generation by the fuel cell 8 1.
- the anode closing means 812 supplies the raw material to the anode of the fuel cell 81, and the raw material almost completely removes the fuel gas in the anode of the fuel cell 81.
- the on-off valve 89 when closing and filling the raw material, even if nitrogen is not used, the fuel cell 1 can be stopped safely without inflow of air into the power source of the fuel cell 1. Is not exposed to an oxidizing atmosphere in the presence of oxygen.
- the raw material power supply means 8100 first supplies the raw material to the cathode of the fuel cell 81, expels the cathode air, and then stops, so that the fuel cell 81 is a solid polymer type. Even if gas is diffused from the power source to the anode through the solid polymer electrolyte membrane, no air is mixed into the anode, so that the durability of the fuel cell system does not decrease.
- the cathode air discharge operation using the above-described raw material is started before the fuel cell 81 reaches the open circuit voltage, a high potential difference is generated between the power source and the anode of the fuel cell 1 and the weakness is generated. The elution of electrodes due to the loss of current does not occur, and the durability of the fuel cell system is not reduced.
- the raw material supplied to the power sword of the fuel cell 81 by the raw material cathode supply means 8 10 is sealed, so that even if the stop period is long, Air does not reach the fuel cell 81 from outside, and there is no concern that the durability of the fuel cell system will be reduced, even during long-term shutdown.
- the fuel generator 82 first pushes out the internal fuel gas with water vapor, and after the temperature drops sufficiently, drives out the water vapor with air.Therefore, there is no danger of keeping the combustible gas inside under high temperature conditions. In order to prevent water from staying inside when stopped, Water will not be trapped in the piping at the next start-up, and the supply of fuel gas will not be unstable. Then, at the time of startup, after starting combustion in the combustor 84, the flow path switching means 88 forms a fuel gas supply flow path, opens the on-off valve 89, and burns the fuel gas sealed in the fuel cell 1. By burning the fuel in the fuel cell 84, the fuel gas sealed in the fuel cell 81 is not released to the outside, and there is no danger of fuel gas being discharged to the outside.
- the fuel cell 81 corresponds to the fuel cell of the present invention
- the fuel generator 82 corresponds to the fuel generator of the present invention
- the pipe connecting the fuel generator 82 and the fuel cell 81 corresponds to the fuel gas pipe of the present invention
- the flow path switching means corresponds to the fuel gas on-off valve of the present invention. It constitutes fuel gas supply means.
- the on-off valve on the inlet side of the force sword closing means 8 11 1 corresponds to the oxidizing gas on-off valve of the present invention
- the pipe connecting this to the fuel cell corresponds to the oxidizing gas pipe of the present invention.
- the raw material power supply means corresponds to the raw material gas on-off valve of the present invention
- the pipe connecting this to the fuel cell 81 corresponds to the raw gas pipe of the present invention. It constitutes gas supply means.
- the on-off valve 89 on the fuel gas outlet side of the anode closing means 8 12 corresponds to the anode-side off-gas on-off valve of the present invention, and the pipe connecting this to the fuel cell is the anode-side exhaust pipe of the present invention.
- the on-off valve 89 on the air outlet side of the cathode closing means 81 1 corresponds to the power source side off-gas opening / closing valve of the present invention, and the pipe connecting this to the fuel cell is the power source side exhaust gas of the present invention.
- the bypass pipe 87 corresponds to the bypass means of the present invention, and the combustor 84 corresponds to the combustor of the present invention.
- the raw material anode supply means 8 13 is used as the additional raw material gas on-off valve of the present invention. Then, by using the piping connecting the raw material anode supply means 8 13 and the fuel cell 81 as the additional raw material gas piping of the present invention, the stopping process 3 of the first embodiment in the configuration of the fourth and fifth embodiments can be performed. May be performed.
- Embodiments 4 and 5 above also correspond to the following embodiments of the invention. That is, as a first invention, a fuel cell that generates electric power from a fuel gas containing hydrogen and an oxidizing gas, a fuel generator that generates the fuel gas from a raw material, and a purge that supplies air to the fuel generator Air supply means, raw material cathode supply means for supplying raw material to the cathode of the fuel cell, bypass means for bypassing the fuel cell on a fuel gas path from the fuel generation means to the fuel cell, and fuel generation Switching means for switching a path of gas discharged from the fuel cell to the fuel gas path or bypass means; and anode closing means for closing an inlet and an outlet of an anode of the fuel cell.
- the raw material cathode supply means supplies the raw material to the fuel cell of the fuel cell, and the anode closing means supplies the anode.
- a fuel cell system wherein the air supply is supplied by the purge air supply means after the water is supplied by the water supply means. May be.
- a fuel cell for generating electric power from a fuel gas containing hydrogen and an oxidizing gas
- a fuel generator for generating the fuel gas from a raw material
- purge air supply means for supplying air to the fuel generator
- raw material power supply means for supplying raw material to the cathode of the fuel cell
- raw material anode for supplying raw material to the anode of the fuel cell
- a supply means for bypassing the fuel cell on a fuel gas path from the fuel generation means to the fuel cell, and a path for gas discharged from the fuel generator to the fuel gas path or the bypass means.
- the raw material power supply means supplies the raw material to the cathode of the fuel cell, and the raw material anode supply means supplies the raw material to the anode of the fuel cell.
- the fuel cell system is further characterized in that the water is supplied by the water supply means and then the air is supplied by the purge air supply means. Good.
- the fuel cell according to the first or second invention is characterized in that a stop operation of the fuel cell is started at the latest before the voltage of the fuel cell reaches the open circuit voltage. It may be a battery system.
- the raw material anode supply means starts supplying the raw material to the anode of the fuel cell after the raw material cathode supply means starts supplying the raw material to the cathode of the fuel cell.
- the fuel cell system according to the second aspect of the present invention is characterized in that
- the fuel cell further includes anode closing means for closing an inlet and an outlet of an anode of the fuel cell, wherein the anode closing means is configured such that the material anode supply means is an anode of the fuel cell.
- the fuel cell system according to any one of the second to fourth inventions, wherein after supplying the raw material to the fuel cell, the inlet and the outlet of the anode of the fuel cell are closed.
- a fuel cell comprising cathode closing means for closing an inlet and an outlet of a power source of the fuel cell, wherein the power source closing means supplies the raw material to the cathode of the fuel cell by the raw material power source supplying means. Thereafter, the fuel cell system according to any one of the first to fifth inventions, wherein the inlet and the outlet of the cathode of the fuel cell are closed.
- a fuel cell comprising at least one of a raw material, a residual fuel discharged from the anode of the fuel cell, and a fuel supplied from the fuel generator via the bypass means. Equipped with a combustor, when the device is started, the said The fuel cell system according to any one of the first, fifth and sixth aspects, wherein the anode closing means opens an inlet and an outlet of an anode of the fuel cell after combustion is started in the combustor. It may be.
- Fuel cells supply fuel gas such as hydrogen gas to the anode and oxidant gas such as air to the power source.
- the electrolyte membrane a polymer electrolyte membrane that selectively transports hydrogen ions is used.
- the porous catalytic reaction layers disposed on both sides of the electrolyte membrane mainly include a carbon powder supporting a platinum-based metal catalyst.
- the reaction of the following formula (12) occurs in the catalytic reaction layer of the anode, and the reaction of the following formula (13) occurs in the catalytic reaction layer of the force sword.
- the following equation (14) occurs.
- the hydrogen ions generated by the reaction of the formula (12) are transported from the anode to the cathode via the electrolyte membrane, and from the anode to the cathode via an external circuit. Electrons are moved to one side, and in a force source, oxygen gas, hydrogen ions, and electrons react as shown in equation (13) to generate water and to obtain heat of reaction due to catalytic reaction.
- the function of selectively transporting hydrogen ions is required in the electrolyte membrane.
- water contained in the electrolyte membrane is used as a movement path to transfer hydrogen ions from the anode to the force source. It is thought that ionic conductivity that can be transported appears.
- FIG 10 shows a solid polymer electrolyte with an electrolyte assembly (MEA; Membrane-Electrode Assembly).
- a cross-sectional view of a degraded fuel cell is shown.
- An anode 1 1 4a and a force sword 1 1 4c are sandwiched between both sides of a polymer electrolyte membrane 1 1 1 made of perfluorocarbon sulfonic acid having hydrogen conductivity so as to sandwich the electrolyte membrane 1 1 1.
- the suffix a of the reference number indicates the one related to the anode 111a on the side that participates in the fuel gas such as hydrogen gas
- the suffix c indicates the force source 114 that is involved in the oxidant gas such as air. The ones related to c are shown.
- a noble metal such as platinum on porous carbon.
- Catalyst reaction layer 1 1 2 c (hereinafter, catalyst reaction layer 1 1 2c), and the second layer film, which is laminated in close contact with the outer surfaces of the catalytic reaction layers 112a and 112c, is a gas for the anode 114a having both gas permeability and electric conductivity.
- a diffusion layer 113a (hereinafter referred to as a gas diffusion layer 113a) and a gas diffusion layer 113c of a cathode 114c (hereinafter referred to as a gas diffusion layer 113c).
- the MEA 117 is composed of an electrolyte membrane 111, an anode 114a, and a power source 114c.
- the MEA 117 is mechanically fixed, and the MEAs 117 adjacent to each other are provided. They are electrically connected in series.
- a conductive separator plate ⁇ i 6 a (hereinafter referred to as a conductive separator plate 1 16 a) for the anode 114 a is disposed in contact with the outer surface of the anode 114 a and the power source 114 c
- a conductive separator plate 1 16 c (hereinafter, referred to as a conductive separator plate 1 16 c) for the force source 114 c is disposed in contact with the outer surface of the base plate.
- reaction gas is supplied to the anode 114a and the force sword 114c to carry away the reaction product gas after the reaction and the excess reaction gas that has not contributed to the reaction (depth: 0.5).
- 18c) is formed on the conductive separator plates 1 ⁇ ⁇ ⁇ ⁇ ⁇ 6a, 1 16c on the contact surface with the MEA 117.
- a fuel cell (single cell) 20 composed of MEA 117 and separator plates 1 16 a and 1 16 c is formed.
- the fuel cell 121 for example, about 160 cells of the fuel cell 120 are stacked; more specifically, the conductive separator plate 1 16 of one of the fuel cells 120 is stacked.
- the fuel cells 120 are stacked such that the outer surface of a and the outer surface of the conductive separator plate 116c of the other fuel cell 120 face each other and are in contact with each other.
- a groove (depth: 0.5 mm) formed in the conductive separator plate 116a is provided on the contact surface between the conductive separator plate 116a and the adjacent conductive separator 116c.
- a cooling water passage 19 is provided which is composed of 119 a and a groove (depth: 0.5 mm) 119 c formed in the conductive separator plate 116 c.
- the temperature of the conductive separator plates 1 16a and 1 16c is adjusted by the cooling water flowing inside the cooling water passage 1 19, and the temperature of the conductive separators 1 16a and 1 16c is adjusted through these conductive separators 1 16a and 1 16c. This allows the temperature adjustment of ME A117.
- conductive separator plates 116a and 116c for example, graphite plates having an outer size of 20 cmX 32 cmX 1.3 mm and impregnated with a phenol resin are used.
- the MEA gasket 1 15a (hereinafter referred to as MEA) on the side of the annular rubber anode 114a.
- Gasket 1 15a) and MEA gasket 1 15c (hereinafter referred to as MEA gasket 1 15c) on the side of cathode 114c, and conductive separator plates 1 16a, 1 16
- MEA gaskets 115a and 115c prevent gas mixing and gas leakage of the gas flowing through the gas flow paths 118a and 118c.
- manifold holes (not shown) for cooling water flow, fuel gas flow, and oxidant gas flow are formed. ing.
- FIG. 11 is a block diagram showing a basic configuration of a fuel cell power generation device.
- the fuel cell power generator 1100 mainly supplies the raw material gas to the fuel generator 123.
- Control unit 127 to control control, circuit unit 125 to extract power generated by fuel cell 121, and measuring unit 126 to measure voltage (generation voltage) of this circuit unit 125 It is composed of
- the fuel cell power generator 1100 includes a first switching valve 12 9 and first, second, and third shut-off valves 13 0, 13 1, and 13 2 described in detail below. It is installed and controlled by the control unit 127. Note that a dotted line in FIG. 11 indicates a control signal.
- the fuel gas performance deteriorating substances contained in the source gas are removed.
- the cleaning source gas is supplied to the fuel generators 123 via the cleaning device.
- the gas cleaning section 22 p since the city gas 13 A containing methane gas, ethane gas, propane gas and butane gas is used as the raw material gas, the gas cleaning section 22 p In this way, odorants such as tertiary tyl mercaptan (TBM) and dimethyl sulfide (DMS) contained in city gas 13 A, as well as impurities such as tetrahydrothiophine (THT) are adsorbed and removed.
- water is supplied into the fuel generator 23 from the second water supply means 175 (for example, a water supply pump).
- a hydrogen gas-rich fuel gas (reformed gas) is generated from the raw material gas and the steam in the reforming section 123 e of the fuel generator 123 by a reforming reaction.
- the fuel gas supplied from the fuel generator 123 is passed through the fuel gas supply pipe 16 1 and the anode side inlet 121 a by the first switching valve 129, and then is supplied to the fuel gas supply pipe.
- the fuel is supplied to the anode side inlet 121 a of the fuel cell 121 via the fuel cell 121, and is used at the anode 114 a for the reaction of the formula (1).
- the first switching valve 12 9 is disposed in the fuel gas supply pipe 16 1 between the anode inlet 12 a and the fuel generator 12 3.
- the fuel gas not used for the power generation reaction in the fuel cell 121 is sent out from the anode side outlet 121b through the anode exhaust pipe 147. It is led to the outside of the fuel cell 1 21 through the first shut-off valve 130 in the open state.
- the first shut-off valve 130 is arranged in the anode exhaust pipe 147 between the anode-side outlets 1 2 1 b and the water removing section 1 33.
- the remaining fuel gas led to the outside passes through the second check valve 148 (the second check valve 148 is in a direction allowing flow) in the middle of the anode exhaust pipe 147,
- the check valve 14 1 prevents backflow in the direction of the first connection pipe 164.
- the remaining fuel gas is removed from the water by a water removal unit 133 disposed in the anode exhaust pipe 147, and then is sent to a combustion unit (not shown) of the fuel generator 123. Sent and burned inside the combustion section. The heat generated by this combustion is used as heat for an endothermic reaction such as a reforming reaction.
- the oxidizing gas (air) supplied from the blower 128 as an oxidizing gas supply means to the humidifier 124 via the oxidizing gas supply pipe 162 is supplied to the humidifier 1
- the acid After being humidified in 2 4, the acid passes through the second shutoff valve 1 3 1 in the open state.
- the second shut-off valve 13 1 is disposed in the middle of the oxidizing gas supply pipe 16 2 between the humidifier 124 and the cathode side inlet 121 c.
- the water required for humidification is supplied from the first water supply means 174 (for example, a water supply pump) to the inside of the humidifier 124, and the heat required for humidification is calculated as shown in Fig. 11
- the fuel is supplied to the humidifier 124 from the fuel generator 123 shown by a double line.
- the humidified oxidizer gas supplied to the fuel cell 1 21 the one that was not used for the power generation reaction in the fuel cell 1 2 1 was opened from the cathode side outlet 1 2 1 d.
- the fuel gas is led to the outside of the fuel cell 1 2 1 through 3 2, and the remaining oxidizing gas is returned to the humidifier 1 24 again through the power source exhaust pipe 1 60 and contained in the refluxing oxidizing gas. Water and heat are given to the fresh oxidant gas sent from the blower 128 inside the humidifier 124.
- the third shut-off valve 13 2 is arranged in the cathode exhaust pipe 160 between the power source side outlet 121 d and the humidifier 124. Further, as the humidifying section 124, a total heat exchange humidifier 134 using an ion exchange membrane and a hot water humidifier 135 are used in combination.
- the switching operation of one switching valve 12 9 and the opening and closing operation of the first, second and third shut-off valves 13 0, 13 1 and 13 2 depend on the detection signals (for example, temperature signals) of various devices. It is controlled by the control unit 127 based on this, and appropriate DSS operation is performed.
- the output terminal 17 2 a of the anode 1 14 a (hereinafter, the output terminal 17 2 a) and the output terminal 17 2 c of the cathode 1 14 c (hereinafter referred to as the output terminal 172 c) is connected to the circuit section 125, and the circuit section 125 is connected to the fuel cell 1 2 1
- the electric power generated inside is taken out, and the generated voltage of the circuit section 125 is monitored by the measuring section 126.
- the fuel gas delivered from the reforming section 123 e CO shift section 123 f which removes part of the carbon monoxide gas (CO gas) contained by the shift reaction, and the CO gas concentration in the fuel gas delivered from the CO shift section 123 f Is provided with a CO removal unit 123 g that can reduce the pressure to 10 ppm or less.
- CO gas concentration By reducing the CO gas concentration to a predetermined concentration level or less, the poisoning of platinum contained in the anode 114a by the CO gas in the operating temperature range of the fuel cell 121 can be prevented, and deterioration of the catalyst activity can be avoided.
- CO 114 poisoning such as platinum-lutetium is used for the anode 114a to take measures against CO gas poisoning in the catalyst material.
- this CO gas is oxidized to carbon dioxide, and its concentration is reduced to about 5000 ppm (see equation (5)).
- CO gas can also be removed by oxidation in the CO removal section 123 g downstream of the conversion section 123 f, but the CO removal section 123 g oxidizes not only CO gas but also useful hydrogen gas. Therefore, it is desirable to reduce the CO gas concentration as much as possible in the CO shift section 123f.
- the operation of the fuel cell power generator 100 at the start of startup will be described. If the temperature of the fuel generator 123 (reforming section 123 e) is 640 ° C or lower, the fuel generator 123 (reforming section 123 e) performs the reforming reaction of equation (4). Does not occur. For this reason, at the start of startup, the gas delivered from the fuel gas is not guided to the anode side inlet 121 a, but the fuel gas supply pipe 16 is operated by the switching operation of the first switching valve 129.
- the operation of the fuel cell power generator 1100 when starting and stopping is described.
- the first switching valve 1 29 is operated to connect the fuel gas supply pipe 1 6 1 to the anode exhaust pipe 1 4 7 and the fuel gas supply pipe 1 6 1 and the anode side.
- the first, second and third shutoff valves 130, 131, and 132 are closed, respectively. This After the start and stop, the fuel gas can be sealed in the anode 114a of the fuel cell 121, and the oxidant gas can be sealed in the power source 14c of the fuel cell 121.
- the operation of the gas supply system of the basic structure of the fuel cell power generator has been outlined above for normal operation (during power generation), start-up, and operation shutdown.
- fuel cell power generators for example, household fuel cell power generators
- the fuel gas that humidifies the inside of the fuel cell during the transition period from the fuel cell shutdown period to the power generation period By exposing the fuel cell to the atmosphere of the fuel cell, it is possible to dry the electrolyte membrane when the fuel cell is shut down, and to carry out local combustion of the fuel cell due to oxygen gas contamination caused by long-term storage. Can solve important issues.
- the humidification of the source gas refers to maintaining the atmosphere of the source gas such that the dew point of the source gas is equal to or higher than the operating temperature of the fuel cell.
- FIG. 12 is a block diagram showing the configuration of the fuel cell power generator according to Embodiment 1, and FIGS. 13 and 14 show the gas supply operation of the fuel cell power generator of FIG. It is a flowchart figure explaining.
- the configurations of the instrument 17 3, the circuit section 125, the measuring section 126 and the control section 127 are the same as those described in the basic configuration (see Fig. 10 and Fig. 11).
- the fuel cell power generation device described below is not suitable for introducing the humidified raw material gas into the fuel cell 122, such as a switching valve, a shutoff valve, and a mass flow meter.
- the basic configuration differs from the basic configuration in that the input sensors of the control unit 127 are as follows. Here, the description will focus on the points of change of the input sensors such as the pipe switching valve, the shutoff valve, and the mass flow meter. .
- the mass flow meter 17 4a of the node 11 14a for measuring the gas flow rate (hereinafter referred to as the mass flow meter 1) 7 0a) is arranged in the middle of the fuel gas supply pipe 16 1 just after the outlet of the fuel generator 1 23.
- the first switching valve 12 9 downstream of the mass flow meter 17 0 a and upstream of the anode 1 2 1 a of the fuel cell 12 1 extends from the fuel generator 12 3. It is located in the middle of the fuel gas supply pipe 16 1 communicating with the inlet 1 2 1 a.
- the first switching valve 12 9 is connected to the anode exhaust pipe 1 4 7 through the first connecting pipe 16 4 in which the first check valve 14 Passed.
- the connection between the first connecting pipe 164 and the anode exhaust pipe 147 is located between the water removing section 133 and the second check valve 148.
- a second switching valve 14 2 is disposed in the middle of the anode exhaust pipe 1 4 7 extending from the anode outlet side 1 2 1 b to the fuel generator 1 2 3, and on the downstream side of the second switching valve 1 4 2
- a first shutoff valve 130 and a second check valve 148 are arranged in this order in the middle of the anode exhaust pipe 144. .
- a second shutoff valve 13 1 and a third switching valve 14 3 are provided in this order.
- a fourth switching valve 144 and a third shutoff valve 132 are arranged in this order in the cathode exhaust pipe 160 extending from the power source side outlet 121d to the humidifier 122. Is provided.
- the third switching valve 144 is connected to the middle of the anode exhaust pipe 144 via the first circulation pipe 144, and the fourth switching valve 144 is connected to the second of The second switching valve 144 is connected to the second switching valve 142 via the circulation pipe 144.
- the connection between the first circulation pipe 144 and the anode exhaust pipe 144 is located between the water removal unit 133 and the second check valve 148.
- the temperature detection means preferably a thermocouple of a Pt resistor for detecting the temperature inside the fuel cell 121 is near the center of the fuel cell 21 as shown in Fig. 12. It is embedded in the conductive separator plate 116c of the force source 114c in the fuel cell 120 (see Fig. 10).
- an impedance measuring device 173 connected to the output terminals 172a and 172c is used. Is provided.
- the circuit section 125 is connected to the output terminals 172a and 172c, and the electric power generated inside the fuel cell 121 in the circuit section 125 is taken out.
- the voltage of 125 (power generation voltage) is monitored by the measuring unit 126.
- the output signal of the mass flow meter 170a, the output signal of the temperature detecting means 171 (via the measuring section 126) and the output signals of the output terminals 1772a and 172c (impedance) ) Is input to the control unit 127.
- the flow rate of the raw material gas is monitored by the control unit 127 based on the output signal of the mass flow meter 170a, and the output signal of the temperature detection unit 171 is processed by the measurement unit 126.
- the internal temperature of the fuel cell 1 2 1 is monitored by the control unit 1 2 7 based on the output signal of the output terminals 1 7 2 a and 1 7 2 c based on the processing signal processed by the impedance measuring instrument 1 7 3
- the membrane resistance of the electrolyte membrane 111 is monitored by the controller 127.
- the switching operation of the first, second, third, and fourth switching valves 122, 144, 144, 144, and the first and second switching valves to be described below are performed by the control unit 127.
- the opening and closing operations of the third and third shutoff valves 130, 131, and 1332 are controlled.
- the fuel cell power generator 1100 After stopping the fuel cell power generator 1100, the fuel cell power generator 1100 is stored for a long time by keeping the inside of the fuel cell 121 filled and sealed with the raw material gas.
- the switching valve and the shutoff valve are operated as follows for stopping and storing the fuel cell power generator 1100 (step S401).
- the first shutoff valve 1 30 connected to the second switching valve 142 and the second shutoff valve 1 31 connected to the third switching valve 143 and the third shutoff valve 1 connected to the fourth switching valve 144 Close 32 each.
- the first switching valve 129 is operated to connect the fuel gas supply pipe 161 with the anode exhaust pipe 147, while disconnecting the fuel gas supply pipe 161 from the anode inlet 121a.
- the second switching valve 142 is operated to make the anode side outlet 121 b communicate with the first shutoff valve 130, while the anode side outlet 121 b is shut off from the second circulation pipe 146.
- the third switching valve 143 is operated to make the cathode side inlet 121 c communicate with the second shutoff valve 131, while the power: node side inlet 121 c is cut off from the first circulation pipe 145.
- the fourth switching valve 144 is operated to make the power source side outlet 121 d communicate with the third shutoff valve 132, while the power source side outlet 121 d is cut off from the second circulation pipe 146.
- the inside of the fuel cell 21 is maintained at a temperature lower than the operating temperature of the fuel cell (70 ° C.), and is usually kept near room temperature (about 20 to 30).
- the removal of impurities in the raw material gas is ⁇ : It is an essential cleaning process.
- methane gas, propane gas, putangas ⁇ it is desirable to use any one of the above gases.
- step S403 the temperature inside the fuel cell 121 is raised to the operating temperature (70 ° C.) (step S403).
- a heater (not shown) or hot water stored in a cogeneration water heater (not shown) of the fuel cell power generation device 110 is used.
- the internal temperature of the fuel cell 12 1 is monitored by the control unit 27 based on the detection signal of the temperature detecting means 17 1. You.
- step S 4 04 it is determined whether or not the internal temperature of the fuel cell 12 1 has reached the operating temperature (70 ° C.) or more (step S 4 04). In the case of No), the temperature increasing operation of S403 is continued, and when the temperature reaches 70 ° C or more (Yes in S.404), the process proceeds to the next step.
- step S405 the switching valve and the shutoff valve are operated as follows.
- the third shutoff valves 1 3 2 to be connected are closed respectively.
- the first switching valve 129 is operated to make the fuel gas supply pipe 161 communicate with the anode exhaust pipe 147, while the fuel gas supply pipe 161 is cut off from the anode side inlet 121a.
- the second switching valve 142 is operated to make the anode side outlet 121 b communicate with the first shutoff valve 130, while the anode side outlet 121 b is cut off from the second circulation pipe 146.
- the third switching valve 143 is operated to make the force side inlet 121 c communicate with the second shutoff valve 131, while the cathode side inlet 121 c is shut off from the first circulation pipe 145.
- the fourth switching valve 144 is operated to make the power source side outlet 1.21 d communicate with the third shutoff valve 132, while the power source side outlet 121 d is cut off from the second circulation pipe 146. .
- the gas discharged from the fuel generator 123 and flowing through the fuel gas supply pipe 161 is supplied to the first connection pipe 164 (the first check valve 141 allows the flow) and the anode exhaust pipe 147 to generate the fuel. Refluxed to the combustion section of vessel 123 and burned inside the combustion section.
- a predetermined temperature range (a temperature range in which CO gas is not generated from the raw material gas and water vapor in the fuel generator 123 (reforming section 123e) and the carbon is not deposited in the raw material gas) is obtained.
- the fuel generator 123 is preheated (step S406).
- the specific range of the temperature rise temperature of the fuel generator 123 is 300 ° C or lower for the following reasons. From the viewpoint of heating and humidifying the source gas most efficiently, the range of the heating temperature is preferably 250 ° C. or more. -When the temperature of the fuel generator 23 exceeds 640 ° C, the reforming reaction of the fuel generator 123 (reforming unit 123e) generates hydrogen gas from the raw material gas and steam, and the hydrogen gas If the inside of the fuel cell 21 is purged, there is a possibility that local combustion will occur inside the fuel cell 21 due to hydrogen gas at the start of power generation.
- the temperature of the fuel generator 123 (reforming section 123e) is 640 ° C or lower, no hydrogen gas is generated due to the reforming reaction, but the fuel is generated within the range of 500 ° C or higher and 6.40 ° C or lower.
- the raw material gas is carbonized in the generator 123 (reforming section 123e) to deposit carbon from the raw material gas, and the temperature of the fuel generator 123 (reforming section 123e) is 500 ° C or more. It is not preferable to keep the temperature at this temperature.
- the temperature of the fuel generator 123 (reforming section 123 e) is 300 ° C or less, the catalyst poisoning of ME A 117 in the fuel generator 123 (reforming section 123 e).
- the carbon monoxide gas having the following is not generated from the raw material gas and the steam.
- the temperature of the fuel generator 123 (reforming section 123e) at 300 ° C or lower and use the raw material gas humidified in this temperature range west as the purge gas. It is.
- the temperature of the fuel generator 123 (reforming section 123e) is monitored by the control section 127 based on the detection signal of the reforming temperature measuring section (not shown), and the temperature of the fuel generator 123 (reforming section 123e) is monitored. Appropriate temperature raising operation of the quality part 123 e) is achieved.
- step S407 it is determined whether or not the temperature of the fuel generator 123 (reforming section 123e) has risen to the range of 250 ° C. to 300 ° C. (step S407).
- step S 4.07, No the preheating operation of the fuel generator 123 in S 406 was continued, and the temperature was raised to the range of 250 ° C. to 300 ° C. (Y s in S 407). move on.
- the inside of the fuel generator 123 is maintained so that the dew point of the raw material gas supplied from the raw material gas supply means 122 can be maintained at the operating temperature (70 ° C) or higher of the fuel cell 121.
- the source gas is shifted to a state where it can be humidified (step S408).
- the temperature of the fuel generator 123 has already been raised to around 300 ° C, and the water required for humidification can be supplied from the second water supply means 175 to the fuel generator 123.
- Raw material inside vessel 1 23 It is possible to humidify the gas.
- the switching valve and the shutoff valve are operated as follows to supply the humidified raw material gas (step S409).
- the third shut-off valves 1 3 2 connected to are closed.
- the first switching valve 12 9 is operated to operate the fuel gas supply pipe 16
- the second switching valve 14 2 is operated to shut off the anode side outlet 1 2 1 b from the first shutoff valve 13 0, while the anode side outlet 1 2 1 b is connected to the second circulation pipe 1. 4 Connect with 6. Further, the third switching valve 14 3 is operated to move the power source side inlet 1 2 1 c to the second shutoff valve.
- the cathode side inlet 1 2 1 c is communicated with the first circulation pipe 1 4 5 while shutting off 1 3 1. Further, the fourth switching valve 144 is operated to shut off the power source side outlet 1 2 1 d from the third shutoff valve 1 32, while the power source side outlet 1 2
- the humidified raw material gas sent out from the fuel generator 123 humidifies a part of the fuel cell 121 and is guided to the outside as follows.
- a purging process is performed to replace the inside of the chamber with the atmosphere of the humidified raw material gas (step S410).
- the raw material gas supplied from the raw material gas supply means 122 is purified in the gas cleaning section 122, and then sent to the fuel generator 123 via the raw gas supply pipe 163. It is humidified inside the fuel generator 123. Thereafter, the humidified raw material gas is sent out from the fuel generator 123 and flows into the fuel cell 122 from the anode side inlet 121 a of the fuel cell 121 via the fuel gas supply pipe 161. After the anode 114a is exposed to the atmosphere of the humidified raw material gas, the humidified raw material gas It is sent out from the fan side outlet 1 2 1 d and flows out of the fuel cell 1 2 1.
- the humidified raw material gas is switched in the direction of the second circulation pipe 144 by the second switching valve 144, passes through the second circulation pipe 144, and is switched to the fourth switching valve.
- the direction is switched in the direction of the fuel cell cathode side outlet 121 d by means of 144, and the fuel flows into the fuel cell 122 again again.
- the cathode 114c is exposed to the atmosphere of the humidified raw material gas, and the raw material gas is sent out from the power source side inlet 121c and flows out again outside the fuel cell 121.
- the raw material gas is switched in direction by the third switching valve 144 and flows in the direction of the first circulation pipe 145 to reach the anode exhaust pipe 147.
- the raw material gas that has reached the anode exhaust pipe 1 47 is prevented from backflow by the first and second check valves 14 1 and 14 48, and is guided to the body of the water removal unit 13 3.
- water is removed from the humidified raw material gas in the water removing section 133, it is sent to the combustion section of the fuel generator 123.
- the humidified raw material gas is supplied to the anode inlet 12 1 a and anode outlet 12 1 b of the fuel cell 12 1, the power source outlet 12 1 d and the power source 12 as shown by the thick dotted line in FIG. After passing through the side inlets 1 2 1 c in order, it flows around the fuel cell 1 2 1 in an annular shape to reach the anode exhaust pipe 1 4 7.
- the fuel gas supplied to the combustion section is burned inside the combustion section, and the heat generated by this combustion is used for heating the fuel generators 123.
- the total supply amount of the humidifying raw material gas must be at least three times the gas fillable volume of the internal space of the fuel cell 12 1. For example, if the gas fillable volume is about 1.0 L, flow rate 1. 5 LZ min at with approximately 5 minutes, may be supplied Re this in the fuel cell 1 2 1, the total feed rate by the control unit 1 2 7 based on the output signal of the lifting Rometa 0 a Monitored.
- the inside of the fuel cell 1 2 1 can be exposed to the humidified raw material gas, and the dried electrolyte membrane 1 1 1 of the fuel cell 1 2 1 can be humidified during stopped storage, and the fuel cell 1 2 1 can be temporarily stopped during storage.
- oxygen gas is mixed into the fuel cell, local combustion with fuel gas generated by the oxygen gas can be prevented.
- the humidified raw material gas is introduced into the fuel cell 12 1 during the transition period from the stop period of the fuel cell 12 1 to the power generation period, the inside of the fuel cell 12 1 There is no exposure in the atmosphere of the humidified raw material gas, and the water repellency of the fuel cell electrode is not impaired.
- both the anodes 114a and the power swords 114c can be humidified by a single humidified raw material gas supply path indicated by a thick dotted line in FIG. Piping can be simplified.
- step S411 After sufficiently supplying the humidified raw material gas to the inside of the fuel cell 121, the switching valve and the shut-off valve are operated as follows (step S411), and the fuel cell generator 110 By promoting the heating of the generator 123, the internal temperature of the fuel generator 123 (reforming unit 123 e) is raised to the temperature (approx. Immediately raise the temperature to
- the first shut-off valve 13 0 connected to the second switching valve 14 2 and the second shut-off valve 13 1 connected to the third switching valve 14 3 and the fourth shut-off valve 14 4 Close the third shutoff valves 1 3 2 to be connected.
- the first switching valve 12 9 is operated to operate the fuel gas supply pipe 16 1 is connected to the anode exhaust pipe 147, while the fuel gas supply pipe 16 1 is disconnected from the anode inlet 121a.
- the second switching valve 142 is operated to make the anode side outlet 121 b communicate with the first shutoff valve 130, while the anode side outlet 121 b is cut off from the second circulation pipe 146.
- the third switching valve 143 is operated to make the cathode side inlet 121 c communicate with the second shutoff valve 131, while the power source side inlet 121 c is shut off from the first circulation pipe 145.
- the fourth switching valve 144 is operated to make the power source side outlet 121 d communicate with the third shutoff valve 132, while shutting off the cathode side outlet 121 d ⁇ the second circulation pipe 146.
- the gas delivered from the fuel generator 123 to the fuel gas supply pipe 1.61 is supplied to the first connection pipe 164 (the first check valve 141 allows the flow) and the anode exhaust pipe 147 to generate the fuel. It is returned to the combustion part of the vessel 123 and burned inside the combustion part.
- the fuel generator 123 is heated to a predetermined temperature (a temperature range in which hydrogen gas is generated from the raw material gas and steam by the reforming reaction; 640. C or more) (step S412).
- step S 413 it is determined whether or not the temperature of the fuel generator 123 (reforming section 123 e) has risen to 640 ° C. or higher. If No in 3), the heating operation of S412 is continued, and when the temperature reaches 640 ° C or more (Yes in S413), the process proceeds to the next step.
- the internal temperature of the fuel cell 121 is checked, and the conductivity of the electrolyte membrane 11 of the fuel cell 21 is checked. It is determined whether the power generation of the device '1100 can be started. As a first confirmation operation, it is determined whether or not the internal temperature of the fuel cell 121 is equal to or higher than the operating temperature (70 ° C.) (step S 414), and if the temperature rise is insufficient (No in S 414) Re-execute the temperature rise operation of S404 After the temperature is increased (Yes in S414), the process proceeds to the next step.
- the horizontal axis represents the actual resistance component Z 'and the vertical axis represents the reactance component Z ", and the frequency of the AC current applied to the fuel cell 12 1 (electrode area: 144 cm 2 ) is set to 0.
- the AC impedance profile of the fuel cell 1 21 measured in the range of l Hz to l kHz is shown (impedance measurement by the AC method). Intersects the horizontal axis ( ⁇ ') at an alternating current at a frequency of 1 kHz, it is estimated that the impedance at an alternating current at a frequency of 1 kHz indicates the resistance R s of the electrolyte membrane 111.
- Figure 15 is a schematic diagram of a so-called Cole-Colelot in which the AC impedance is measured. In this case, the intersection of the semicircle and the horizontal axis has the smaller resistance value ( Figure 1). R s) shown in 5 is the membrane resistance of the electrolyte membrane 1 1 Means.
- the impedance measuring device '17 Apply the measurement AC voltage (1 kHz) from 3.
- the electric conductivity of the electrolyte membrane 111 can be estimated based on the AC impedance of the electrolyte membrane 111 of the fuel cell 121 obtained in this manner.
- the fuel cell 120 is exchanged by applying an AC voltage (1 kHz) to each of the 110 cells, for example.
- the flow impedance is measured, and the conductivity of the electrolyte membrane 11 is calculated from the measured value and the thickness and the area of the electrolyte membrane 11.
- Figure 16 shows that when the temperature of the electrolyte membrane 11 is maintained at 80 ° C, the horizontal axis indicates the polymer electrolyte membrane (the Nafion 112 electrolyte membrane of DuPont, USA; The relative humidity of 50 m) is taken, and the vertical axis is the conductivity of the electrolyte membrane. The correlation between the two is shown.How the conductivity of the electrolyte membrane depends on the relative humidity of the electrolyte membrane It is for explaining.
- the power generation start time of the fuel cell having the stop period and the power generation period is determined based on the conductivity of the electrolyte membrane of the fuel cell. It is possible to predict and improve the reliability of the determination of the power generation start time of the fuel cell power generator.
- the first switching valve 1 2 9 is operated to disconnect the fuel gas supply pipe 16 1 from the anode exhaust pipe 1 4 7, while the fuel gas supply pipe 16 1 is connected to the anode side inlet 1 2 1 a
- the second switching valve 14 2 is operated to connect the anode-side outlet 12 1 b to the first shut-off valve 13 30, while the node-side outlet 12 21 b is connected to the second circulation pipe 14. Cut off from 6.
- the third switching valve 14 3 is operated to connect the cathode inlet 1 2 1 c with the second shutoff valve 13 1, while the cathode inlet 1 2 1 c is connected to the first circulation pipe 1 4 Cut off from 5.
- the fourth switching valve 144 is operated to connect the power source side outlet 1 2 1 d with the third shutoff valve 13 2, while the power source side outlet 1 2 1 d is connected to the second circulation pipe 1. 4 Cut off from 6.
- the hydrogen gas-rich fuel gas delivered from the fuel generator 123 through the fuel gas supply pipe 161 is supplied to the anode side inlet of the fuel cell 121.
- the remaining fuel gas sent from the anode-side outlet 1 2 1 b and not consumed by the anode 1 14 a is supplied to the fuel cell 1 2 1 through the anode exhaust pipe 1 4 Reflux to generator 123.
- the humidified air (humidified oxidant gas) sent from the humidifier 123 via the oxidant gas supply pipe 162 is introduced into the cathode side inlet 121c of the fuel cell 121, and The remaining oxidant gas sent out from the power source side outlet 121d and not consumed by the power source 114c is humidified by the fuel cell 122 through the power source exhaust pipe 160. Reflux to 24.
- the fuel gas is supplied to the anode 114a, the oxidant gas is supplied to the cathode 114c, and hydrogen ions and electrons are generated inside the fuel cell 121, and the output terminal 170 A current can be taken out to the circuit section 125 through a and 172c, and the generated voltage is monitored in the measuring section 126.
- FIG. 17 is a block diagram showing a configuration of the fuel cell power generator according to Embodiment 7.
- Fuel cell 1 2 1, First water supply 1 7 4, Second water supply 1 7 5, Raw gas supply 1 2 2, Fuel generator 1 2 3, Humidifier 1 2 4, Impedance measurement
- the configurations of the measuring device 173, the circuit portion 125, the measuring portion 126, and the control portion 127 are the same as those described in the sixth embodiment.
- Embodiment 7 differs from Embodiment 6 in that the arrangement of the piping for introducing the humidified raw material gas into the fuel cell 121, the switching valve, the shutoff valve, and the mass flow meter is changed as follows. This is different from Fig. 12), and the explanation here focuses on the changes in the piping, switching valve, shutoff valve and mass flow meter.
- the first circulating pipe 145 extending between the third switching valve 143 shown in FIG. 12 and the anode exhaust pipe 147 is removed.
- a sixth switching valve 154 is arranged immediately after the outlet of the gas purifying section 122p, whereby the cleaning source gas is supplied to the humidifier 124 (source gas branch pipe 155).
- a switching operation is performed between the case of sending and the case of sending to the fuel generator 123.
- a raw material gas branch pipe 1515 is provided that passes through the inside of the humidifying section 124 and communicates the third switching valve 144 and the sixth switching valve 154. Furthermore, downstream of the first switching valve 12 9.
- a fifth switching valve 15 2 is added in the middle of the fuel gas supply pipe 16 1 that connects the anode side inlet 12 1 a of the fuel cell 12 1
- a second connection pipe 15 3 connecting the five switching valves 15 2 and the anode exhaust pipe 1 47 is provided. The position of the connection between the second connection pipe 153 and the anode exhaust pipe 147 is located between the second check valve 148 and the water removal unit 133.
- the mass flow meter 170c of the force sword 114c for measuring the gas flow rate (hereinafter referred to as the mass flow meter 170c) Is disposed between the humidifier 12 4 and the third switching valve 14 3 and in the middle of the raw material gas branch pipe 15 1.
- the operation of supplying fuel gas and oxidizing gas is divided into the stop storage operation, the start-up operation, the operation to confirm whether or not to start power generation, and the power generation operation. This will be described in detail with reference to the flowchart of FIG.
- the inside of the fuel cell 121 is filled and sealed with raw material gas for long-term storage.
- the switching valve and the shutoff valve are operated as follows for stopping and storing the fuel cell power generation device 110 (step S810).
- the first shut-off valve 13 0 connected to the second switching valve 14 2 and the second shut-off valve 13 1 connected to the third switching valve 14 3 and the fourth shut-off valve 14 4 Close the third shutoff valves 1 3 2 to be connected.
- the first switching valve 12 9 is operated to connect the fuel gas supply pipe 16 1 with the fifth switching valve 15 2, while the fuel gas supply pipe 16 1 is connected to the anode exhaust pipe 1 4 Cut off from 7 ⁇ .
- the second switching valve 14 2 is operated to connect the anode side outlet 1 2 1 b with the first shutoff valve 13 0, while the anode side outlet 1 2 1 b is connected to the second circulation pipe. Cut off from 1 4 6
- the switching valve 143 By operating the switching valve 143 to connect the power source side inlet 121 c with the second shutoff valve 131, the power source side inlet 121 c is cut off from the raw material gas branch pipe 151.
- the fourth switching valve 144 is operated to connect the power source side outlet.
- the fifth switching valve 152 is operated to make the anode side inlet 121 a communicate with the first switching valve 129, while the anode side inlet 121 a is cut off from the anode exhaust pipe 127. In this way, the fuel gas and the oxidizing gas can be reliably sealed in the fuel cell 121.
- the temperature inside the fuel cell 121 is usually near room temperature (about 20 ° C to 30 ° C), which is kept lower than the fuel cell operating temperature (70 ° C).
- a material gas is selected and a treatment for purifying the material gas is performed so as not to adversely affect the catalyst of the fuel cell 121 (step S802).
- Source gas purification method The source gas selection is the same as in the sixth embodiment.
- step S 803 the temperature inside the fuel cell 121 is raised to the operating temperature (70 ° C.) (step S 803).
- the method of raising the temperature inside fuel cell 121 is the same as that described in the sixth embodiment.
- step S 804 it is determined whether the internal temperature of the fuel cell 12 1 has reached the operating temperature (70 ° C.) or higher (step S 804). If the temperature rise is insufficient (No in S 804) ), The temperature raising operation of S803 is continued, and if the temperature reaches 70 ° C. or more (Yes in S804), the process proceeds to the next step.
- the raw material gas is supplied to the humidifier 124 using the heat supplied to the humidifier 124.
- Step S805 hot water is required to humidify the raw material gas, but since the humidifier 124 does not have a combustor as a heat source, it is necessary to appropriately receive heat from outside the humidifier 124 .
- the fuel is generated in the combustor of the fuel generator 123 as shown in FIG. By giving heat to the humidifier 124, the temperature of the humidifier 124 is increased.
- shutoff valves and switching valves are operated as follows (step S806).
- the first shut-off valve 130 connected to the second switch valve 142 and the third shut-off valve 13 1 connected to the third switch valve 144 and the third shut-off valve connected to the fourth switch valve 144 Close valves 1 3 2 respectively.
- the second switching valve 142 is operated to shut off the anode side outlet 121b from the first shutoff valve 130, while communicating the anode side outlet 121b with the second circulation pipe 146.
- the third switching valve 143 is operated to connect the power source side inlet 121c with the raw material gas branch pipe 151, while the power source side inlet 21c is disconnected from the shutoff valve 1331.
- the fourth switching valve 144 is operated to shut off the cathode side outlet 121 d from the second shut-off valve 13 1, while the cathode side outlet 121 d communicates with the second circulation pipe 146. Let it.
- the fifth switching valve 15 2 is operated to shut off the anode-side inlet 1 2 1a from the first switching valve 1 29, while the anode-side inlet 1 2 1a communicates with the anode exhaust pipe 147.
- the sixth switching valve 154 is operated to communicate the gas purifying section 122p with the raw material gas branch pipe 151, while the gas purifying section 122p is shut off from the fuel generator 123. .
- the cleaning source gas is supplied into the fuel cell 121 through the following route (step S807), and the purging process of replacing the inside of the fuel cell 121 with the atmosphere of the humidifying source gas is performed.
- the source gas supplied from the source gas supply means 122 and purified by the gas purifier 122p passes through the source gas supply pipe 163 and is branched into the source gas by the sixth switching valve 154. It is directed in the direction of the pipe 151, flows into the humidifier 124 via the raw material gas branch pipe 151, and is humidified inside the humidifier 124 (more precisely, a hot water humidifier).
- the humidified raw material gas is switched into the direction of the cathode side inlet 121 c of the fuel cell 121 by the third switching valve 144 and flows into the fuel cell 122.
- the power source 114c is exposed to the atmosphere of the humidified raw material gas, and the humidified raw material gas flows out from the power source side outlet 121d.
- the humidified raw material gas is then switched by the fourth switching valve 144 in the direction of the second circulation pipe 144 so that the raw gas flows along one side of the fuel cell 1 2 1 second circulation pipe 1 4
- the fuel cell 1 2 1 is switched by the second switching valve 1 4 2 in the direction of the anode side outlet 1 2 1 b of the fuel cell 1 2 1 and flows into the fuel cell 1 2 1 again.
- the anode 114a is exposed to the atmosphere of the humidified raw material gas, and this humidified raw material gas flows out again from the anode-side inlet 122a.
- the humidified raw material gas after reflow is switched in the direction of the second connection pipe 15 3 by the fifth switching valve 15 2, passes through the second connection pipe 15 3, and passes through the anode exhaust pipe 1 Reach 4 7
- the raw material gas that has reached the anode exhaust pipe 147 is prevented from backflow by the first and second check valves 141, 148, and is guided toward the water removal unit 133.
- the water is sent to the combustion unit of the fuel generator 123 and burned inside the combustor.
- the humidified raw material gas is supplied to the power source side inlet 1 21 c and the cathode side outlet 12 1 d and the anode side outlet 12 1 b of the fuel cell 12 1 as shown by the thick dotted line in FIG.
- Fuel cell 1 2 1 Flows in a cono-shape around the anode exhaust pipe 4 7 1.
- the total supply amount of the humidified raw material gas must be at least three times or more the gas fillable volume of the internal space of the fuel cell 121.
- the humidified raw material It is sufficient to supply the gas to the inside of the fuel cell 121 at a gas flow rate of 1.5 L / min for about 5 minutes, and the total supply amount is determined by the control unit 12 based on the output signal of the mass flow meter 70 c. Monitored by 7.
- the inside of the fuel cell unit 121 can be exposed to the humidified raw material gas, and the fuel cell 211 dried during the suspension storage is stored. Humidifies the electrolyte membrane 111, and if oxygen gas enters the interior of the fuel cell 121 during shutdown storage, it can prevent local combustion with the fuel gas that is also released by the oxygen gas. .
- the humidified raw material gas is introduced into the fuel cell 121 during the transition period from the stop period of the fuel cell 121 to the power generation period, the inside of the fuel cell 122 is extended for a long time. There is no exposure in the atmosphere of the humidified source gas, and the water repellency of the electrodes of the fuel cell 121 is not impaired. '
- both the anode 14a and the power source 114c can be humidified by a single path, and the gas supply pipe can be simplified.
- the switching valve and the shutoff valve are operated as follows to heat the fuel generator 123 (step S80). 8).
- the first shut-off valve 13 0 connected to the second switching valve 14 2 and the second shut-off valve 13 1 connected to the third switching valve 14 3 and the fourth shut-off valve 14 4 Close the third shutoff valves 1 3 2 to be connected.
- the first switching valve 12 9 is operated to connect the fuel gas supply pipe 16 1 with the anode exhaust pipe 1 4 7 while the fuel gas supply pipe 16 1 is connected.
- the fifth switching valve 1 5 2 is shut off.
- the second switching valve 142 is operated to connect the anode side outlet 121b to the first shutoff valve 1 '30, while shutting off the anode side outlet 121b to the second circulation pipe 146. Let it.
- the third switching valve 143 is operated to connect the cathode side inlet 1 2 1 c with the second shutoff valve 13 1, while the power source side inlet 1 21 c is connected to the raw material gas branch pipe 15 1. Cut off.
- the fourth switching valve 144 is operated to connect the power source side outlet 121d with the third shutoff valve 1332, while the cathode side outlet 121d is connected to the second circulation pipe 146. And shut off.
- the fifth switching valve 15 2 is operated to connect the anode side inlet 1 2 1a with the first switching valve 1 29.
- the anode side inlet 1 2 1.a is cut off from the anode exhaust pipe 147. Let it.
- the sixth switching valve 154 is operated to make the gas purifying section 122 p communicate with the fuel generator 123, while disconnecting the gas purifying section 122 p from the raw material gas branch pipe 15 1.
- the gas sent from the fuel generator 123 is switched by the first switching valve 129, and the first connecting pipe 164 and the anode exhaust pipe 147 are connected.
- the water is removed in the water removal section 133 and then returned to the fuel generator 123 to burn the fuel generator 123 Since the fuel can be combusted in the section, the fuel generator 123 can be heated quickly (step S80-9), and the internal temperature of the fuel generator 123 (reforming section 123e) is reduced by the equation (4).
- the temperature can be raised to a temperature at which quality reaction is possible (about 640 ° C or more).
- step S811 it is determined whether or not the temperature of the fuel generator 123 has risen to 640 ° C. or more. If the temperature rise is insufficient (No in S810), S The heating operation of 809 is continued, and when the temperature reaches 640 ° C. or more (Yes in S810), the process proceeds to the next step.
- the method for measuring the conductivity of the electrolyte membrane and the relationship between the conductivity of the electrolyte membrane and the relative humidity are the same as those described in the sixth embodiment.
- the power generation start time of the fuel cell having the stop period and the power generation period is determined based on the conductivity of the electrolyte membrane of the fuel cell. It is possible to predict and improve the reliability of the determination of the power generation start time of the fuel cell power generator.
- the fuel cell 1 2 1 temperature is less than 70 ° C
- the conductivity sigma 1 ⁇ 93 X 1 of the electrolyte membrane 0_ 2 S cm- 1 or more
- the fuel cell 121 is generated by operating the switching valve and the shutoff valve as follows (steps S815 and S816).
- the first shut-off valve 1 30 and the third cut-off which are connected to the second switching valve 142 The second shut-off valve 13 1 connected to the switching valve 14 3 and the third shut-off valve 13 2 connected to the fourth switching valve 1 44 are all opened.
- the first switching valve 12 9 is operated to disconnect the fuel gas supply pipe 16 1- from the anode exhaust pipe 14 7 while the fuel gas supply pipe 16 1 is connected to the fifth switching valve 15 Communicate with 2.
- the second switching valve 14 2 is operated to connect the anode side outlet 1 2 1 b with the first shutoff valve 13 0, while the anode side outlet 1 2 1 b is connected to the second circulation pipe 1. 4 Cut off from 6.
- the third switching valve 14 3 is operated to connect the cathode side inlet 1 2 1 c with the second shutoff valve 13 1, while the cathode side inlet 1 2 1 c is connected to the raw material gas branch pipe 15 1 Cut off.
- the fourth switching valve 144 is operated to connect the power source side outlet 1 2 1 d with the third shutoff valve 13 2, while the cathode side outlet 1 2 1 d is connected to the second circulation pipe 1 4 Cut off from 6.
- the fifth switching valve 15 2 is operated to connect the anode side inlet 12 1 a with the first switching valve 12 9, while the anode side inlet 1 2 1 a is connected to the anode exhaust pipe 1. 4 Cut off from 7.
- the sixth switching valve 154 is operated to connect the gas purifying section 122 p with the fuel generator 123, while the gas purifying section 122 p is blocked from the raw material gas branch pipe 155. Cut off. '
- the hydrogen gas-rich fuel gas is introduced from the fuel generator 12 3 through the fuel gas supply pipe 16 1 into the anode side inlet 1 21 a of the fuel cell 12 1,
- the remaining fuel gas sent from the anode side outlet 1 2 1 b and not consumed by the anode 1 14 a is transferred to the fuel generator 1 2 3 of the fuel cell 1 2 1 via the anode exhaust pipe 1 4 7. Bring to reflux.
- the humidified air (oxidizing gas) sent from the humidifier 12 3 through the oxidizing gas supply pipe 16 2 is introduced into the cathode inlet 12 1 c of the fuel cell 12 1,
- the remaining oxidant gas sent from the power source side outlet 121d and not consumed by the power source 114c is supplied to the fuel electrode via the power source exhaust pipe 160.
- the humidifier 124 of the pond 1 2 1.
- the fuel gas is supplied to the anode 114a, the oxidant gas is supplied to the power source 114c, and hydrogen ions and electrons are generated inside the fuel cell 121, A current can be taken out to the zero-path section 125 through the output terminals 1722a and 72c, and the generated voltage is monitored in the measurement section 126.
- FIG. 20 is a block diagram showing a configuration of a fuel cell power generator according to Embodiment 3.
- Fuel cell 1 2 1, First water supply 1 7 4, Second water supply 1 7 5, Raw material gas supply 1 2 2, Fuel generator 1 2 3, Humidifier 1 2 4, Impedance
- the configurations of the measuring device 173, the circuit portion 125, the measuring portion 126, and the control portion 127 are the same as those described in the sixth embodiment.
- Embodiment 8 differs from Embodiment 6 in that the arrangement of the piping for introducing the humidified raw material gas to the fuel cell 121, the switching valve, the shutoff valve, and the mass flow meter is changed.
- the following describes mainly the changes of the introduction piping, the switching valve, the shutoff valve, and the mass flow meter for the sixth embodiment.
- the second and fourth switching valves 144, 144 and the first and second circulation pipes 144, 146 used in the sixth embodiment (FIG. 12) are removed.
- a diverter valve 155 is disposed immediately after the outlet of the gas purifying section 122 p. The ratio of the flow rate of the raw material gas flowing in the direction can be determined.
- a source gas branch pipe 15 1 that passes through the inside of the humidifying section 124 and connects the third switching valve 144 and the flow dividing valve 15 55 is provided.
- the mass flow meter 170c is connected to the humidifier 124 and the third It is provided between the switching valves 144 and in the middle of the raw material gas branch pipes 151.
- the fuel gas and oxidizing gas supply operations are divided into the stop storage operation, the start-up operation, the operation for confirming the start of power generation, and the power generation operation. 1. The details will be explained with reference to the flowchart in FIG.
- the inside of the fuel cell 121 is kept in a sealed state with the raw material gas for long-term storage.
- the switching valve and the shut-off valve are operated as follows for stopping and storing the fuel cell power generation device 110 (step S1001).
- the first switching valve 12 9 is operated to connect the fuel gas supply pipe 16 1 with the anode exhaust pipe 1 4 7, while the fuel gas supply pipe 16 1 is connected to the anode side inlet 1 2 1 a And shut off.
- the third switching valve 144 is operated to connect the cathode side inlet 121c with the second shutoff valve 131, while the power source side inlet 121c is connected to the source gas branch pipe 1 5 Cut off from 1.
- the inside of the fuel cell 12 1 is maintained at a temperature lower than the operating temperature of the fuel cell (70 ° C.), and is kept at a room temperature (about 20 ° 0 to 30 ° 0).
- the source gas is selected so as not to have an adverse effect on the catalyst of the fuel cell 121, and the source gas is cleaned (step S1002).
- the method of purifying the source gas is the same as that of the sixth embodiment.
- the temperature inside the fuel cell 121 is raised to the operating temperature (7 (J ° C)) (step S1003). Same as what you did.
- step S 1004 it is determined whether the internal temperature of the fuel cell 121 has reached the operating temperature (70 ° C.) or higher (step S 1004). If the temperature rise is insufficient (No in S 1 Q 04) Then, the temperature raising operation of S 1003 is continued, and when the temperature reaches 70 ° C. or more (Yes in S 1004), the process proceeds to the next step.
- step S1005 In order to preheat the inside of the fuel generator 123, the switching valve and the shutoff valve are operated as follows (step S1005).
- First shutoff valve 130 connected to anode side outlet 121b and second shutoff valve 131 connected to third switching valve 143 and third shutoff valve connected to power source outlet 121d Close 132 respectively.
- the first switching valve 129 is operated to connect the fuel gas supply pipe 161 with the anode exhaust pipe 147, while disconnecting the fuel gas supply pipe 161 from the anode inlet 121a. Further, the third switching valve 143 is operated to make the cathode side inlet 121 c communicate with the second shutoff valve 131, while the cathode side inlet 121 c is cut off from the raw material gas branch pipe 151. Further, the fuel gas supply pipe 16 with respect to the flow rate of the source gas flowing through the source gas supply pipe 1 63 is operated so that the flow dividing valve 1 55 is operated to guide the entire amount of the source gas flowing through the source gas supply pipe 163 to the fuel generator 123. Set the split ratio of the flow rate of the source gas flowing through 1 to 1.
- Step S1006 The heating temperature range of the preheating of the fuel generator 123 is the same as that described in the sixth embodiment. (The temperature of the fuel generator 123 (reforming unit 123 e) is set to 250 ° C to 300 ° C (The temperature rises to the range of).
- step S1007 it is determined whether or not the temperature of the fuel generator 123 (reforming section 123 e) has risen to a range of 250 ° C to 300 ° C (step S1007). If there is any (No in S1007), the preheating operation of the fuel generator 123 in S1006 is continued, and the temperature is raised to the range of 250 ° C to 300 ° C (Yes in S1007). Proceed to step.
- the dew point of the raw material gas supplied from the raw material gas supply means 122 in the fuel generator 123 and the humidifier 124 is equal to or higher than the operating temperature of the fuel cell 121 (70 ° C).
- the raw material gas is shifted to a state where it can be humidified so as to maintain the temperature (step S1008).
- the temperature of the fuel generator 123 is raised to around 300 ° C, and the water required for humidification is supplied from the second water supply means 175 to the fuel generator 123, whereby the raw material gas is converted into fuel. It can be humidified inside the generator 123.
- the raw material gas is supplied to the inside of the humidifier 124 by the heat supplied to the humidifier 124 from the water supply fuel generator 123 supplied from the first water supply means 174 to the inside of the humidifier 124. Can be humidified.
- the switching valve and the shut-off valve are operated as follows to supply the humidified raw material gas.
- the first shutoff valve 130 connected to the second switching valve 142 and the third shutoff valve 132 connected to the fourth switching valve 144 are opened.
- the first switching valve 129 is operated to make the anode-side inlet 121 a communicate with the fuel gas supply pipe 161, while disconnecting the anode-side inlet 121 a from the anode exhaust pipe 147. Further, the third switching valve 143 is operated to connect the cathode side inlet 121 c with the source gas branch pipe 151. On the other hand, shut off the power source side inlet 1 2 1 c with the shutoff valve 1 3 1. In addition, diversion valve 1
- the humidified raw material gas sent out from the gas purifying section 122 p is humidified inside the fuel cell 121 and guided to the outside as follows, and the inside of the fuel cell 122 is humidified raw material gas.
- a purging process is performed to replace the atmosphere (step S101).
- the raw material gas which is purified by the gas purifying unit 1 2 2 p and sent out via the raw gas supply pipe 16 3, is supplied with the first raw gas flowing through the raw gas branch pipe 15 1 and the fuel gas supply pipe 16 The gas is diverted to the second source gas flowing through 1 almost equally (diversion ratio: 0.5).
- the source gas supply piping 1 For the first source gas, the source gas supply piping 1
- Purified raw material gas sent out through 6 3 is divided by the diversion valve 15 5, passed through the raw material gas branch pipe 15 1, guided to the humidifier 1 24, and humidified in the humidifier 1 2 4 You.
- the humidified raw material gas is switched to the cathode side inlet 121 c of the fuel cell 121 by the third switching valve 144 and the cathode 111 is passed through the raw gas branch pipe 151. supplied to c.
- the humidified raw material gas flows out from the power source side outlet 121 d.
- the humidified raw material gas after flowing out returns to the humidifying section 124 through the power source exhaust pipe 160, is treated in the humidifying section 124, is appropriately diluted, and is discharged to the atmosphere.
- the cleaning source gas sent from the gas purifying section 122 p through the source gas supply pipe 163 is split by the diverter valve 155, and the fuel is generated by the fuel generator 123. And humidified inside the fuel generator 123. Thereafter, the humidified raw material gas sent out from the fuel generator 123 is supplied to the first switching valve 129. Therefore, the fuel cell is supplied to the anode 114 a of the fuel cell 121 via the fuel gas supply pipe 161 by switching the direction to the anode side inlet 121 a of the fuel cell. After exposing the anode 114'a to the atmosphere of the humidified raw material gas, the humidified raw material gas flows out of the fuel cell 121 from the anode outlet 121b.
- the humidified raw material gas that has flowed out passes through the anode exhaust pipe 147, is removed in the water removal section 133, is returned to the combustion section of the fuel generator 123, and is combusted in the combustion section. It is used to heat the fuel generators 123.
- the total supply amount of the humidifying raw material gas must be at least three times or more the gas fillable volume of the internal space of the fuel cell 12 1.
- the gas fillable volume is about 1.OL
- the humidification It is sufficient to supply the source gas to the inside of the fuel cell 121 for about 5 minutes with a flow rate of 1.5 LZ
- the total supply amount is the output of the mass flow meter 170 a and the mass flow meter 170 c. Monitored by the control unit 127 based on the signal.
- the interior of the fuel cell 121 can be exposed to the humidified raw material gas during the transition period from the suspension period of the fuel cell 121 to the power generation period.
- the electrolyte membrane 111 can be humidified, and if oxygen gas enters the inside of the fuel cell during the stopped storage, local combustion with the fuel gas caused by the oxygen gas can be prevented.
- the humidified raw material gas is introduced into the fuel cell 121, so that the inside of the fuel cell 121 is humidified for a long time. There is no exposure in the atmosphere of the raw material gas, and the water repellency of the fuel cell electrode is not impaired.
- the first source gas and the second source gas are independent of each other without being mixed with each other, and the first source gas is passed through the power source 114 c of the fuel cell 121, Since the second source gas is configured to pass through the anode 114 of the 121, both the anode 114a and the cathode 114c can be reliably humidified.
- the switching valve and the shutoff valve are operated as follows to heat the fuel generator 123 (step S101 1).
- the first shutoff valve 130 connected to the anode side outlet 121b and the second shutoff valve 131 connected to the third switching valve 143, and the third shutoff valve 132 connected to the power source side outlet 121d Close each.
- the first switching valve 129 is operated to connect the fuel gas supply pipe 161 to the anode exhaust pipe 147, while the fuel gas supply pipe 161 is disconnected from the anode-side inlet 121a.
- the third switching valve 143 is operated to make the power source side inlet 121c communicate with the second shutoff valve 131, while the power source side inlet 121c is cut off from the raw material gas branch pipe 151. Let it.
- the fuel gas supply pipe 16 1 corresponding to the flow rate of the source gas flowing through the raw gas supply pipe 163 is connected so that the entire amount of the raw gas flowing through the raw gas supply pipe 163 is guided to the fuel generator 123 by operating the branch valve 1 55. Set the split ratio of the flowing source gas flow to 1.
- the gas delivered from the fuel generator 123 is passed through the first connection pipe 164 by the switching operation of the first switching valve 129 (the first check valve 141 is in a direction allowing the flow),
- the second check valve 148 prevents a backflow in the direction of the anode side outlet 121b, and is returned to the combustion part of the fuel generator 123 to be burned in the combustion part.
- the generator 123 is heated (step S101 2).
- step S1013 it is determined whether or not the temperature of the fuel generator 123 has risen to 640 ° C. or higher. If the temperature rise is insufficient (No in S1013), S101 The heating operation of 2 is continued, and when the temperature reaches 640 ° C. or more (Yes in S1013), the process proceeds to the next step.
- step S 10 14 it is determined whether or not the internal temperature of the fuel cell 12 1 is equal to or higher than the operating temperature (70 ° C.) (step S 10 14). (No in S1004), re-execute the temperature raising operation in step S1003 (step S1005), and when the temperature rises to 70 ° C or more (S1004) At Y es), then go to step. .
- the method for measuring the conductivity of the electrolyte membrane and the relationship between the conductivity of the electrolyte membrane and the relative humidity are the same as those described in the sixth embodiment.
- the power generation start time of the fuel cell having the stop period and the power generation period is determined based on the conductivity of the electrolyte membrane of the fuel cell. It is possible to predict and improve the reliability of the determination of the power generation start time of the fuel cell power generator.
- the switching valve and the shutoff valve are operated as described below to cause the fuel cell 21 to generate power (step S1018 and step S1019).
- a predetermined value the internal temperature of the concrete fuel cell 1 2 1 7 0 ° C or more
- the conductivity of the electrolyte membrane ⁇ 1. 9 3 X 1 0_ 2 S cm- 1
- the switching valve and the shutoff valve are operated as described below to cause the fuel cell 21 to generate power (step S1018 and step S1019).
- All 3rd shut-off valves 1 3 2 are opened.
- the first switching valve 12 9 is operated to shut off the fuel gas supply pipe 16 1 from the anode exhaust pipe 1 4 7 while the fuel gas supply pipe 16 1 is connected to the anode side inlet 1 2 1 Communicate with a.
- the third switching valve 14 4 3 is operated to connect the cathode inlet 12 1 c with the second shutoff valve 13 1, while the cathode inlet 12 1 c is connected to the source gas branch pipe 15 Cut off from 1.
- the flow rate of the source gas flowing through the source gas supply pipe 163 is adjusted so that the diverter valve 155 is operated to guide the entire amount of the source gas flowing through the source gas supply pipe 163 to the fuel generator 123.
- the flow ratio of the raw material gas flowing through the fuel gas supply pipe 1 through 1 is set to 1.
- the hydrogen-rich fuel gas delivered from the fuel generator 123 through the fuel gas supply pipe 161 is introduced into the anode inlet 122a of the fuel cell 122.
- the remaining fuel gas sent from the anode side outlet 1 2 1 b and not consumed by the anode 1 14 a is discharged to the fuel generator 1 2 of the fuel cell 1 2 1 through the anode exhaust pipe 1 4 7.
- Reflux to 3 humidified air (oxidizing gas) is introduced from the humidifier 12 3 through the oxidizing gas supply pipe 16 2 into the cathode inlet 12 1 c of the fuel cell 12 1 and the cathode outlet.
- the remaining oxidant gas sent from the 1 2 1 d power and not consumed by the power source 1 14 c is returned to the humidifier 124 of the fuel cell 1 2 1 via the power source exhaust pipe 160. Let it.
- the fuel gas is supplied to the anode 114a, the oxidant gas is supplied to the cathode 114c, and hydrogen ions and electrons are generated inside the fuel cell 121, and the output is generated.
- a current can be taken out to the circuit section 125 through the terminals 17a and 72c, and the generated voltage is monitored in the measuring section 126.
- the effect of stabilizing the performance of the fuel cell brought about by the purging process of the humidified raw material gas described in the sixth to eighth embodiments was evaluated by the following characteristic evaluation of the fuel cell 121 (voltage evaluation of the MEA 17). Verified.
- the characteristic evaluation of the fuel cell 121 the following is used as a catalyst material of the fuel cell power generator 1100.
- Catalyst body obtained by supporting Pt catalyst on carbon powder Ketjen Black (Ketjen B lack EC, Ketjen Black International Co., Ltd., particle size 30 nm) (50% by weight? 1) 66 parts by weight of hydrogen ion conductive material and binder perfluorocarbon sulfonate ionomer (5% by weight Nafion dispersion liquid manufactured by A1drich, USA) 33 parts by weight (polymer (Dry weight) to form a catalyst reaction layer 12a, 12c (10 to 20 ⁇ ).
- the carbon powder acetylene black (denka black manufactured by Denki Kagaku Kogyo Co., Ltd., particle size 35 nm) 'was replaced with a polytetrafluoroethylene (PTFE) permanent disparge (D1 manufactured by Daikin Industries, Ltd.)
- PTFE polytetrafluoroethylene
- D1 manufactured by Daikin Industries, Ltd. a polytetrafluoroethylene (PTFE) permanent disparge
- gas diffusion layers 13a, 13c and the catalytic reaction layers 12a, 12'c thus produced were combined with a polymer electrolyte membrane 111 (an electrolyte membrane of Nafion 112 of DuPont, USA). Bonded on both sides to complete MEA117.
- a polymer electrolyte membrane 111 an electrolyte membrane of Nafion 112 of DuPont, USA. Bonded on both sides to complete MEA117.
- the fuel cell 1 2 1 is started up (generated) and stopped up to 4000 times, and the humidified raw material gas is not purged.
- the following table summarizes the change in MEA voltage in the humidification source gas purging process described in 8.
- the horizontal axis indicates the number of times the fuel cell is started and stopped, and the vertical axis indicates the voltage of MEA117, and the MEA1 in the humidified material purge process (Embodiment 8) and the comparative example.
- the state of the voltage change of Fig. 7 is shown.
- the purging process using the humidified raw material gas in the sixth to eighth embodiments local combustion or the like based on the repetitive operation of stopping the power generation can be prevented.
- the voltage of the fuel cell 121 is stably maintained for a long time without any problem. .
- the fuel cell power generator 1 The fuel cell system corresponds to the fuel cell system of the invention, the fuel cell 1 2 1 corresponds to the fuel cell of the invention, the fuel gas supply pipe 16 1 corresponds to the fuel gas pipe of the invention, and the first switching valve 12 9 Corresponds to the fuel gas on-off valve of the present invention, and these constitute the fuel gas supply means of the present invention.
- the oxidizing gas supply pipe 16 2 corresponds to the oxidizing gas pipe of the present invention
- the second shutoff valve 13 1 corresponds to the oxidizing gas on-off valve of the present invention.
- the supply means is constituted.
- the source gas supply pipe 15 1 and the pipe connecting between the third switching valve 14 3 and the cathode side inlet of the fuel cell 12 21 correspond to the source gas pipe of the present invention.
- the third switching valve 144 corresponds to the source gas on-off valve of the present invention, and these constitute the source gas supply means of the present invention.
- the second switching valve 152 corresponds to the anode-side off-gas on-off valve of the present invention
- the second connection pipe 153 corresponds to the anode-side discharge pipe of the present invention
- the fourth switching valve 144 corresponds to the power source side off-gas on-off valve of the present invention
- the second circulation pipe 146 corresponds to the cathode side discharge pipe of the present invention.
- the second circulation pipe 146 corresponds to the additional source gas pipe of the present invention
- the fourth switching valve 144 and the second switching valve 144 correspond to the additional source gas opening / closing valve of the present invention.
- the control section 127 corresponds to the control means of the present invention.
- Embodiments 6 to 8 above may be applicable to the following embodiments of the invention. That is, as a first invention, there is provided a fuel cell having a fuel gas flow path, and a raw material gas supply means for supplying a raw material gas. During the power generation period of the fuel cell, the raw material gas is supplied to the fuel gas flow path.
- the fuel cell is generated by supplying the fuel gas generated from the fuel cell, and during the transition period of the fuel cell between the stop period and the power generation period in the fuel cell in which stop and power generation are alternately repeated,
- a fuel cell generator that humidifies the source gas delivered from the source gas supply means and exposes the inside of the fuel cell to the atmosphere of the humidified source gas. It may be an electric device.
- an electrolyte membrane inside the fuel cell is exposed to the atmosphere of the raw material gas by flowing the raw material gas through the fuel gas flow path. It may be.
- the fuel cell power generator according to the second invention may be configured to humidify the source gas so that the dew point of the source gas can be maintained at or above the operating temperature of the fuel cell.
- the raw material gas supply unit includes a gas purifying unit, and after removing an iodine component in the raw material gas by the gas purifying unit, the inside of the fuel cell is brought into an atmosphere of the raw material gas.
- the fuel cell power generator according to any of the first to third inventions to be exposed may be used.
- the fuel cell power generator according to the fourth invention wherein the source gas is any one of methane gas, propane gas, butane gas and ethane gas, may be used.
- a fuel generator for generating a fuel gas to be supplied to the fuel cell from the raw material gas and the water vapor supplied from the raw material gas supplying means, wherein the raw material gas supplying means is provided during the transition period.
- the first temperature is lower than a lower limit temperature at which the raw material gas is carbonized in the fuel generator, and the temperature of the fuel generator is maintained.
- the fuel cell power generator of the invention may be used.
- the fuel cell power generator according to the sixth invention in which the temperature of the fuel generator is maintained at 300 ° C. or less, may be provided.
- an anode and a cathode sandwiching an electrolyte membrane are arranged inside the fuel cell, and after exposing the anode to the atmosphere of the source gas, exposing the power source to the atmosphere of the source gas.
- the fuel cell power generator of the first invention may also be used.
- a fuel generator for generating a fuel gas to be supplied to the fuel cell from the raw material gas supplied from the raw material gas supply means and water vapor, wherein the fuel gas is supplied to the fuel generator.
- the fuel-cell power generating device according to the eighth aspect of the present invention which humidifies inside, may be used.
- an anode and a cathode sandwiching an electrolyte membrane are disposed inside the fuel cell, and after the cathode is exposed to the atmosphere of the source gas, the anode is exposed to the atmosphere of the source gas.
- the fuel cell power generation device of the first invention may be used.
- a fuel cell system according to the tenth aspect, further comprising a humidifier for humidifying an oxidizing gas for power generation reaction with the fuel gas, the humidifier being supplied to the power source,
- the fuel cell power generator of the invention may be used.
- an anode and a cathode that sandwich an electrolyte membrane are arranged inside the fuel cell, and the cathode is exposed to an atmosphere of the first raw material gas that is divided from the raw material gas, and the anode is May be exposed to an atmosphere of the second raw material gas which is separated from the raw material gas.
- a fuel generator for generating a fuel gas to be supplied to the fuel cell from the raw material gas and water vapor supplied from the raw material gas supply means, and an oxidizing agent supplied to the cathode.
- a fuel cell according to a 12th aspect of the present invention further comprising a humidifier for humidifying a gas, humidifying the first raw material gas inside the humidifier, and humidifying the second raw material gas inside the fuel generator. It may be a power generator.
- the fuel cell power generation device according to the first invention may include an electrolyte membrane inside the fuel cell, and start the power generation period based on the conductivity of the electrolyte membrane.
- the power generation period is started based on a conductivity of the electrolyte membrane corresponding to a predetermined relative humidity inside the fuel cell.
- the fuel cell power generation device of the invention of 4 may be used.
- Embodiment 9 A fuel cell system according to Embodiment 9 of the present invention will be described with reference to FIG.
- FIG. 24 is a configuration diagram of the fuel cell system of the present embodiment.
- the fuel cell stack 201 is configured by stacking a plurality (n) of cells (C1 to Cn).
- the cell includes a hydrogen ion conductive polymer electrolyte membrane, a pair of electrodes sandwiching the electrolyte membrane, and a pair of separator plates having a gas flow path for supplying a fuel gas and an oxidizing gas to the pair of electrodes, respectively.
- the oxidizing gas control device 202 controls the supply amount of the oxidizing gas based on the voltage and the internal resistance of the fuel cell stack on the air electrode side of the fuel cell stack.
- the oxidizing gas supply pipe 210 in which the humidifier 200 and the hot water humidifier 210 are installed is connected.
- the fuel electrode side is connected to a fuel gas supply pipe 200 having a fuel generator 203 for generating a fuel gas from a raw material gas and a gas purifying section 208 for purifying the raw material gas. I have.
- the fuel gas supply pipe 201 and the oxidizing gas supply pipe 201 are provided with solenoid valves 207 to 279 for switching a gas flow path.
- a power circuit section 6 is connected to a current collector (not shown) of the fuel cell stack 1, and the voltage of each cell (Cl to Cn) is detected by a voltage detector 204, and the voltage of each cell is detected.
- the internal resistance is measured by a measuring unit such as a high-frequency resistance meter 201.
- the control unit 205 controls the fuel cell stack, the fuel generator, the gas cleaning unit, the humidification unit, the power circuit unit, and the measurement unit. In particular, based on the detected voltage and internal resistance, the power circuit unit 205 6 controls the amount of power output in 6, the amount of fuel gas generated in the fuel generator 203, and the opening and closing of the solenoid valves 2071 to 279.
- Table 2 shows the fuel cell system of this embodiment.
- the process (sequence) of the operation method of the stem is shown in Fig. 25 to Fig. 29.
- the average value of the internal resistance of the cell, the temperature of the fuel cell stack, the generated power, and the voltage of the cell in each step of Table 2 are shown in Figs.
- the transition of the average value of is shown.
- step 1 humidified air is supplied to the air electrode, and humidified reformed gas (S RG) is supplied to the fuel electrode to generate power.
- S RG humidified reformed gas
- a dry inert gas is supplied to the fuel cell stack before the operation is stopped, and the internal resistance of the cell is set to 1.0 ⁇ ⁇ cm 2 or more (1). ).
- the internal resistance of the cell in the step (1) is preferably 1.0 to 3.0 ⁇ ⁇ cm 2 . If it exceeds 3.0 ⁇ ⁇ cm 2 , drying during shutdown and humidification during When the process is repeated, the change in the water content increases, the volume change due to the repeated swelling and shrinking of the polymer electrolyte membrane increases, and the electrode is easily damaged.
- step 2 the gas supplied to the air electrode is switched to dry inert gas, and the external output is stopped.
- the battery voltage gradually decreases, and the average voltage of the unit cell is about 0.10 to 0.15V.
- the inside of the cathode is replaced with inert gas, and hydrogen at the anode spontaneously diffuses into the cathode, bringing the potentials of the cathodes closer.
- the flow volume of the air electrode and the flow volume of the fuel electrode are almost the same. When hydrogen and oxygen diffuse and react, hydrogen is present in excess, so the potential of both electrodes is Approaching 0 V for standard hydrogen electrode ⁇ .
- step 3 dry inert gas is supplied to both electrodes until the partial resistance of the unit cell in the fuel cell stack becomes 1.0 ⁇ ⁇ cm 2 or more.
- step 3 the temperature of the fuel cell stack was maintained at 70 ° C.
- step (1) corresponds to step 3.
- the internal resistance of the unit cell is 1.0 ⁇ ⁇ cm 2 or more.
- step 4 the gas flow path of the fuel electrode and air electrode is sealed, gas flow is stopped, and the battery temperature is reduced. And stop operation.
- the humidified inert gas to the fuel cell Sutatsu clicks before starting power generation and supply, process and 0. 3 ⁇ ⁇ cm 2 or less internal resistance of the single cell (2) Perform operations including: This operation can suppress an increase in internal resistance due to the generation of heat during startup.
- the internal resistance of the unit cell in the step (2) is preferably 0.1 to 0.3 ⁇ ⁇ cm 2 .
- the internal resistance of the cell during operation is about 0.1 ⁇ ⁇ cm 2 .
- step 5 the fuel cell stack until heated while you Keru internal resistance of the single cell in the fuel cell stack is 3 ⁇ ⁇ cm 2 or less 0.1, supplying an inert gas which is humidified to the air electrode and the fuel electrode I do. This step 5 allows drying during shutdown The polymer electrolyte membrane in the state is humidified, and the fuel cell stack is ready for power generation.
- step 6 the gas supplied to the fuel electrode is switched to humidified reformed gas (SRG), and the cell is operated for a while at an average voltage of about 0.10 to 0.15V. At this time, the hydrogen moves from the fuel electrode to the air electrode by natural diffusion, whereby the electrode catalyst is reduced and purified.
- SRG humidified reformed gas
- step 7 the gas supplied to the air electrode is switched to humidified air, and 1 kW of power is generated.
- a source gas purified by the gas cleaning unit 208 can be used.
- the odorant (S component) contained in the city gas' is removed as an impurity, and the purified odorant is used as the inert gas. .
- the removal of the impurities is performed to prevent the poisoning of Pt contained in the medium layer.
- Examples of the dry inert gas used in Steps 2 and 3 include, for example, a raw material gas that has passed through a gas purifying section 208 and a bypass 203 b provided between the fuel generators 203. Used.
- the humidified inert gas used in Steps 5 and 6 for example, a raw material gas that has passed through a gas purifier 208 and passed through a fuel generator 203 at a temperature of 300 ° C. or less is used.
- the temperature of the fuel generator 203 is equal to or lower than 300 ° C.
- the raw material gas is not reformed into a hydrogen-containing gas, and only the humidification of the raw material gas is performed.
- the humidified inert gas passes through, for example, the gas purifying section 208 and then passes through the connecting pipe 201 a connecting the fuel gas supply pipe and the air supply pipe.
- a feed gas humidified by a hot water humidifier 2010 using heat and water generated by the fuel generator 203 can be used.
- the above-mentioned raw material gas supplied to the fuel cell stack 201 as an inert gas can be reused as a fuel for combustion of the fuel generator 203. Since the raw material gas can be used as the inert gas as described above, it is not necessary to separately provide a device for supplying the inert gas such as a nitrogen gas pump. Therefore, it is possible to easily suppress the deterioration of the fuel cell stack without increasing the cost without complicating the fuel cell system.
- FIG. 29 is a schematic vertical sectional view showing a part of the fuel cell stack.
- Acetylene black (Denka black manufactured by Denki Kagaku Kogyo Co., Ltd., particle size 35 nm) is used as the carbon powder, and water-based displaced porion of polytetrafluoroethylene (PTFE) (D1 manufactured by Daikin Industries, Ltd.) To obtain a water-repellent ink containing 20% by weight of PTFE as a dry weight. This ink is applied and impregnated on carbon paper (TGPH060H manufactured by Toray Industries, Inc.) as a base material for the gas diffusion layer, and then heat-treated at 300 ° C with a hot-air drier to obtain a thickness of about 200 ⁇ m. m gas diffusion layers 2023a and 2023b were obtained.
- PTFE polytetrafluoroethylene
- Ketjen Black (Ketjen B lack £. Manufactured by Ketzin Plak International Co., Ltd., particle size 3011111) as a carbon powder, and 50% by weight of Pt is deposited.
- a catalyst powder was obtained.
- the catalyst powder and a hydrogen ion conductive polymer electrolyte and a binder, a perfluorocarbon sulfonic acid ionomer (A 1drich, USA, 5 wt% Na fion dispersion) was mixed at a weight ratio of 2: 1 by dry weight, and the mixture was molded to form catalyst layers 2022a and 2022b having a thickness of 10 to 20 im.
- the catalyst layers 202 2 a and 20 22 b and the gas diffusion layers 202 3 a and 20 23 b obtained above were used as hydrogen ion conductive polymer electrolyte membranes 21 (DuPont, USA, Nafion 1). 1 and 2 membranes).
- a membrane-electrode assembly (hereinafter referred to as MEA) composed of 2024 b was obtained.
- a rubber gasket 2025 was joined to the outer periphery of the polymer electrolyte membrane 2021 in the MEA 2027.
- a gasket 2025 was formed with a manifold hole through which fuel gas, oxidizing gas, and cooling water flowed.
- the surface of the anode-side separator plate 2026a having the gas flow path 2028a is overlapped with the surface of the anode-side separator plate 20'26b of the MEA 2027, and the surface of the cathode-side separator plate 20'26b having the gas flow path 2028b is further overlapped.
- the cell was overlaid on the surface of the power sword 20 24 b of ME A 2027 to obtain a cell. 70 unit cells were stacked to obtain a cell stack.
- the surface of the separator 2026 a having the cooling water flow path 20 29 and the cooling water flow path 2029 of the separator 2026 b are connected.
- the cooling section was formed for each single cell by superimposing the surfaces.
- a rubber seal portion 2030 was provided on the surface of the separator plate having the cooling portion so as to surround the cooling water flow path to prevent the cooling water from flowing out.
- a current collector plate made of stainless steel, an insulating plate and an end plate made of an electrically insulating material were arranged at both ends of the battery stack, and the whole was fixed with fastening rods, thereby producing a fuel cell stack.
- the fastening pressure was 1 S kgf Zcm 2 per area of the separator plate.
- the fuel cell stack 201 obtained above was connected to the fuel cell system having the same configuration as that of FIG. 24 described above, and an operation test as shown below was performed in the same process as in Table 2 described above.
- Step 1 the fuel gas supply pipe and the oxidizing gas supply pipe in the fuel cell system obtained above were supplied with 13% gas as the source gas and air as the oxidizing gas, respectively.
- the battery temperature in the fuel cell stack was 70 ° C
- the fuel gas utilization rate (U f) was 70%
- the air utilization rate (Uo) was 40%.
- the fuel gas and air were humidified to have dew points of 65 ° C and 70 ° C, respectively.
- 13A gas passed through the gas cleaning section 8 was used as the gas for purging.
- Step 1 80 minutes
- Step 2 20 minutes
- Step 3 30 minutes
- Step 4 48 hours
- Step 5 30 minutes
- Step 6 Steps 1 to 6 were performed 100 cycles as 20 minutes.
- the operation test was performed at room temperature (27 ° C) (Experiment number 1).
- the dried inert gas used was the source gas purified in the gas cleaning section. Also, the humidified inert gas passes through a fuel generator at 300 ° C or lower. Used raw material gas.
- step 1 the internal resistance of the cell was 0.1 ⁇ ⁇ cm 2 in any of the execution numbers 1 to 12.
- Table 3 shows the results of the operation tests for the execution numbers 1, 2, 6 to 8 with the time of step 3 changed.
- the internal resistance in Table 4 indicates the average value of the internal resistance of each cell at the end of steps 3 and 5.
- the deterioration rate indicates the average value of the voltage drop of each cell per cycle (steps 1 to 6) when starting and stopping are alternately repeated. (Table 4)
- Table 5 shows the results of the operation tests for Run Nos. 1, 3, 9, and 10.
- Table 6 shows the results of the operation tests for Run Nos. 1, 2, 4 to 8, 11, and 12.
- Nafion 112 was used as the polymer electrolyte membrane, but similar effects were obtained with other materials used as the polymer electrolyte membrane.
- the test temperature was set to a room temperature of 27 ° C., but other temperatures may be used, for example, in Reference 1 (Handbook of Fuel Cell, vol. 3, p5b7, Fundame
- the effective internal resistance range according to the present invention can be calculated from an Arrhenius plot of the conductive individual of Nafion 112 described in “nta 1 s, Technology and Applications”.
- Embodiment 9 described above may also correspond to the following embodiments of the invention. That is, as a first invention, a hydrogen ion conductive polymer electrolyte membrane, a pair of electrodes sandwiching the electrolyte membrane, and a flow path for supplying a fuel gas and an oxidizing gas to the pair of electrodes, respectively.
- a fuel cell stack in which a plurality of unit cells each composed of a pair of separator plates are stacked;
- a power circuit for extracting power from the fuel cell stack A measurement unit for measuring voltage and resistance of the unit cell; and a control unit for controlling the fuel cell stack, a fuel generator, a gas cleaning unit, a humidification unit, a power circuit unit, and a measurement unit.
- the internal resistance of the cell is 1.
- the fuel cell system may have a characteristic of 0 ⁇ ⁇ cm 2 or more. Further, as a second invention, the fuel cell system according to the first aspect, wherein the measurement unit includes a high-frequency resistance meter. .
- the control unit supplies a dry inert gas to the fuel cell stack while maintaining the operation temperature before stopping the operation of the fuel cell system.
- the fuel cell system according to the first aspect of the present invention in which the internal resistance of the unit cell is controlled to be equal to or more than 1.0 ⁇ ⁇ cm 2 .
- the fuel cell system according to the third invention may be such that the control unit supplies a dried inert gas to the fuel cell stack while maintaining the operation temperature.
- control unit supplies the humidified inert gas to the fuel cell stack before starting operation of the fuel cell system, thereby reducing the internal resistance of the unit cell to 0.1.
- the fuel cell system according to the first invention wherein the fuel cell system is controlled to 3 ⁇ ⁇ cm 2 or less, may be used.
- the fuel cell system according to any one of the third to fifth inventions, wherein the inert gas is a source gas purified by the gas purifying unit may be used.
- the inert gas is a humidified source gas generated at a temperature of 300 ° C. or less in the fuel generator at the time of startup. It may be. ,
- the inert gas is a source gas humidified in the humidifying section using heat and water generated in the fuel generator at the time of startup.
- the invention may be applied to the fuel cell system of the invention.
- the thick gas is supplied to the fuel cell stack and then used as a fuel for combustion of the fuel generator. Is also good.
- a method for operating a fuel cell system comprising:
- the operation method of the fuel cell system according to the tenth invention may be such that the fuel cell stack is maintained at an operating temperature.
- a humidified inert gas is supplied to the fuel cell stack, and the internal resistance of the unit cell is 0.3 ⁇ -cm 2 or less.
- a thirteenth aspect of the present invention includes a step (3) of purifying a raw material gas, wherein in the steps (1) and (2), the purified gas is used as the inert gas.
- the operation method of the fuel cell system according to the twenty-second invention may be adopted.
- a fifteenth aspect of the present invention includes a step (4) of generating the fuel gas from a source gas and a step (5) of humidifying the source gas.
- Fuel of the 12th invention used as an active gas The operation method of the battery system may be used.
- the operation method of the fuel cell system according to the fifteenth invention wherein the raw material gas is humidified in the step (5) using heat and water generated in the step (4). .
- FIG. 30 shows a basic configuration of a polymer electrolyte fuel cell (hereinafter referred to as PEFC) among fuel cells according to Embodiment 10 of the present invention.
- PEFC polymer electrolyte fuel cell
- Fuel cells electrochemically react a fuel gas such as hydrogen with an oxidant gas such as air by a gas diffusion electrode, and generate electricity and heat simultaneously. .
- the side that participates in fuel gas such as hydrogen is called an anode
- the symbol of the related means is denoted by a
- the side that is involved in the oxidant gas such as air is called the force sword
- the symbol of the related means is c. I attached.
- Reference numeral 301 denotes an electrolyte, which is used by a polymer electrolyte membrane or the like that selectively transports hydrogen ions.
- electrolyte 1 On both surfaces of the electrolyte 1 (hereinafter sometimes referred to as a membrane), catalytic reaction layers 302 a and 302 c mainly composed of carbon powder carrying a platinum-based metal catalyst are closely arranged. It is. In the catalytic reaction layer, the above-mentioned reactions (Chem. 1) and (Chem. 2) occur.
- the fuel gas containing at least hydrogen (hereinafter referred to as anode gas) undergoes the reaction shown in Chemical Formula 1 (hereinafter referred to as anode reaction).
- the hydrogen ions transferred through the electrolyte 1 react with the oxidizing gas (hereinafter referred to as force gas) and the reaction shown in (Fig. 2) (hereinafter referred to as force force reaction) in the catalytic reaction layer 302c. It produces water, which generates electricity and heat.
- force gas oxidizing gas
- Fig. 2 reaction shown in the catalytic reaction layer 302c. It produces water, which generates electricity and heat.
- the outer surfaces of the catalytic reaction layers 302a and 302c have gas permeability and conductivity.
- the diffusion layers 303a and 303c which are also provided, are disposed in close contact with the diffusion layers.
- the diffusion layers 303a and 303c and the catalytic reaction layers 302a and 302c constitute electrodes 304a and 304c.
- Reference numeral 304 denotes a membrane electrode assembly (hereinafter, referred to as MEA), which is formed by electrodes 304 a and 304 c and an electrolyte 301.
- MEA membrane electrode assembly
- MEA 305 is mechanically fixed, adjacent ME A 305 is electrically connected to each other in series, and reactant gas is supplied to the electrode.
- a pair of conductive separators 307a and 307c formed with gas flow paths 306a and 306c for carrying away the gas in contact with MEA 5 are arranged.
- Membrane 301 a pair of catalytic reaction layers 302a, 302c, a pair of diffusion layers 303a, 303c, and a pair of electrodes 304a, 304c
- a basic fuel cell (hereinafter, referred to as a cell) is formed by the pair of separators 307a and 307c.
- the separators 307a and 307c are in contact with the separator 307c or 307a of the adjacent cell on the surface opposite to the MEA305.
- Reference numerals 308a and 308c denote cooling water passages provided on the side where the separators 307a and 307c are in contact with each other, through which cooling water flows.
- the cooling water transfers heat to adjust the temperature of MEA 305 through separators 3a and 307c.
- Reference numeral 309 denotes a MEA gasket that seals the MEA 305 and the separators 307a and 307c.
- the membrane 301 has a fixed charge, and a hydrogen ion exists as a counter ion of the fixed charge.
- the membrane 301 is required to have a function of selectively permeating hydrogen ions.
- the membrane 301 needs to hold moisture.
- the fixed charges fixed in the film 301 are ionized, and hydrogen, which is a counter ion of the fixed charges, is ionized and can move. This is because that.
- FIG. 31 is a perspective view of a stack in which cells are stacked.
- the voltage of a fuel cell is usually as low as 0.75 V, a plurality of cells are stacked in series to achieve a high voltage.
- Reference numeral 3002 is a current collecting plate for extracting current from the stack to the outside
- reference numeral 3022 is an insulating plate for electrically insulating the cell from the outside
- Reference numeral 3023 denotes an end plate for fastening and mechanically holding a stack of stacked cells.
- FIG. 32 is a diagram illustrating a fuel cell power generator according to Embodiment 1 of the present invention.
- Reference numeral 303 denotes an outer casing of the fuel cell system.
- Reference numeral 3302 denotes a cleaning section for removing substances that adversely affect the fuel cell from the fuel gas, and guides the fuel gas from a raw material gas pipe.
- Reference numeral 303 denotes a gate valve for controlling the flow of the raw material gas.
- Reference numeral 304 denotes a fuel generator, which generates a fuel gas containing at least hydrogen from the raw material gas.
- the raw material gas is led to the fuel generator 30 34 via the raw gas pipe and the gate valve 30 35.
- Reference numeral 3036 denotes a stack, the details of which are shown in FIGS. 30 and 31. Fuel gas is led from the fuel generator 304 to the fuel cell stack 330 through the fuel gas pipe.
- a gate valve 303 controls the flow of fuel gas to the fuel cell stack 303. Further, the gate valve 3037 functions to purge and seal the inert gas in the stack during the stop storage. Further, the gate valve 3037 functions to purge and seal the inert gas in the stack during the stop storage.
- the inert gas is not necessarily a so-called noble gas such as helium or neon or nitrogen, but may be a gas that is inert to the fuel cell, such as a source gas purified in a gas purifying section.
- the specified purge gas (The same applies hereinafter).
- Reference numeral 310 denotes a blower, and the oxidizing gas is introduced into the fuel cell stack 330 through an intake pipe.
- a gate valve 304 controls the flow of the fuel gas to the fuel cell stack 303.
- the oxidant gas not used in the fuel cell stack 303 is exhausted through the gate valve 304. Further, at the time of stop storage, the gate valve 3042 functions to purge and seal the inert gas in the stack.
- the fuel gas not used in the fuel cell stack 303 is regenerated by the off-gas pipe and flows into the fuel generator 304.
- the gas from the off-gas pipe is used for combustion, etc., and is used for an endothermic reaction to generate fuel gas from raw material gas.
- the gate valve 3042 functions to purge and seal the inert gas in the stack.
- a gate valve 304 controls off-gas flowing from the fuel cell stack 303 to the fuel generator 304.
- Reference numeral 3044 denotes a power circuit unit for extracting electric power from the fuel cell stack 30336, and 3044 denotes a control unit for controlling a gas, a power circuit unit, a gate valve, and the like.
- Reference numeral 304 denotes a pump for flowing water from the cooling water inlet pipe to the water path of the fuel cell stack 303.
- the water flowing through the fuel cell stack 303 is transported to the outside from the cooling water outlet pipe.
- the flow of water through the fuel cell stack 303 allows the generated heat to be used outside the fuel cell system while keeping the fuel cell stack 303 at a constant temperature.
- Oxygen concentration detectors 305 and 305 fill the fuel cell stack 306 When the detected oxygen concentration change of the inert gas is detected and the oxygen concentration of the predetermined concentration or more is detected, a signal is transmitted to the control unit 3045 to operate the gate valve.
- the fuel cell power generator according to Embodiment 10 includes a fuel cell stack 3036 composed of a fuel cell, a gas purifying section 3302, a fuel generator 3004, and a power circuit section 30. 4, a control section 304, and an oxygen concentration detector.
- the means including the oxygen concentration detectors 300, 310 corresponds to the oxygen concentration detecting means of the present invention, and the control section 304 corresponds to the purging gas injection means of the present invention.
- the fuel cell power generator of the embodiment corresponds to the fuel cell operation device of the present invention.
- the gas purifying section 303 corresponds to the fuel gas purifying means of the present invention.
- the gate valve 3041 corresponds to the oxidant gas flow path upstream valve of the present invention
- the gate valve 3042 corresponds to the oxidant gas flow path downstream valve of the present invention
- the gate valve 300 7 corresponds to the fuel gas passage upstream valve of the present invention
- the gate valve 3043 corresponds to the fuel gas passage downstream valve of the present invention.
- valve 303 is opened, and the raw material gas flows into the gas cleaning section 3302 from the raw material gas pipe.
- a hydrocarbon gas such as natural gas or propane gas can be used.
- 13 A which is a mixed gas of methane, ethane, propane, and butane gas is used.
- the gas purifying section 32 includes, in particular, TBM (tertiary heptyl mercaptan), DMS (dimethyl sulfide), THT (tetrahydrothiothioin), etc.
- a member for removing the gas odorant is used. Sulfur compounds such as odorants are adsorbed on the catalyst of the fuel cell and become a catalyst poison, inhibiting the reaction.
- hydrogen is generated by the reaction shown in (Chem. 9) and the like. '(Chem. 9)
- a fuel gas containing hydrogen and moisture is created and flows into the fuel cell stack 330 of the fuel cell via the fuel gas pipe.
- the oxidizing gas passes through the humidifier 304 by the blower 310 and then flows into the fuel cell stack 330.
- the exhaust gas of the oxidizing gas is exhausted from the exhaust pipe.
- the humidifier 304 a device in which an oxidizing gas flows into warm water or a device in which water is blown into the oxidizing gas can be used.
- a total heat exchange type is used. This is to transfer the water and heat in the exhaust gas into the oxidizing gas as the raw material carried from the intake pipe when passing through the humidifier 304.
- a cooling water inlet pipe and a cooling water outlet pipe are usually provided with a water heater or the like. The heat generated by the fuel cell stack 303 of the fuel cell can be extracted and used for hot water supply.
- An oxidizing gas such as air is caused to flow through the gas flow path 306c, and a fuel gas containing hydrogen is caused to flow through the gas flow path 306a.
- Hydrogen in the fuel gas diffuses through the diffusion layer 303a and reaches the catalytic reaction layer 3.02a.
- hydrogen is divided into hydrogen ions and electrons. The electrons are transferred to the force sword through an external circuit. Hydrogen ions permeate through membrane 301 It moves to the sword side and reaches the catalytic reaction layer 302c.
- oxygen reacts with electrons to form oxygen ions
- oxygen ions react with hydrogen ions to generate water.
- the oxidizing gas and the fuel gas react around MEA 305 to generate water, and electrons flow.
- Exhaust gas that does not use the oxidizing gas passes through the humidifier 340 to pass heat and moisture to the oxidizing gas sent from the blower 309, and is then discharged to the outside.
- the off-gas whose fuel gas has not been used flows into the fuel generator 304 again through the off-gas pipe.
- the gas from the off-gas pipe is used for combustion in the fuel generator 304.
- the reaction for generating the fuel gas from the raw material gas is an endothermic reaction as shown in (4) and is used as heat required for the reaction.
- the power circuit section 4 plays a role of extracting DC power from the fuel cell stack 36 after the fuel cell starts generating power.
- the control section 304 controls the other parts of the fuel cell system so as to keep the other parts in optimal control.
- the source gas used was 13 A of city gas, and air was used as the oxidant gas.
- the fuel cell temperature was 70 ° C
- the fuel gas utilization rate (U f) was 70%
- the oxygen utilization rate (U o) was 40%.
- the fuel gas and air were humidified so that each had a dew point of 70 ° C.
- a current was taken out from the power circuit section 304. The current was adjusted so as to be 0.2 AZ cm 2 per apparent area of the electrode.
- Hot water storage tanks (not shown) are attached to the cooling water inlet pipe and the cooling water outlet pipe.
- the temperature of the water in the cooling water inlet piping is 70 ° C, and the temperature of the water in the cooling water outlet piping is
- Fig. 34 shows the change in stack voltage and the change in oxygen concentration.
- the current from the stack is taken out by the power circuit section 304, but when the voltage of a typical single cell of the fuel cell stack 330 falls below 0.5 V, the current taking out stops. .
- the blower 30 is stopped, the supply of air to the fuel cell stack 303 is stopped, the gate valve 304 is opened, and odor is generated in the gas cleaning section 330.
- the gate valve 300 and the gate valve 304 on the anode side are closed, the gate valve 304 and the gate valve 304 on the cathode side are closed, and the fuel cell stack is closed.
- the inside of the device was filled with the material gas and sealed, and the pump was stopped. Also, the pump 304 was stopped, and the movement of cooling water to the outside was stopped.
- the storage process 1 is performed.
- the temperature of the fuel generation unit 304 and the fuel cell stack 303 which are high in temperature, gradually decreases, and eventually becomes the same as the external temperature.
- the oxygen concentration detectors 3500 and 3501 detected the oxygen concentration of lO ppm (approximately the lower limit of the oxygen concentration that can be detected by the normal measurement method), so the control was performed.
- the gate valve 3 0 3 7 and the gate valve 3 0 4 3 on the anode side are opened by the signal from the section 3 0 4 5, and the gate valve 3 0 4 1 and the gate valve 3 0 4 2 on the force source side. Open the pump, operate the pump 304, re-inject the raw material gas into the fuel cell stack 31036 again, and close the gate valve 3007 on the anode side.
- the gate valve 304, the gate valve 3041, and the gate valve 3042 on the cathode side were closed and sealed.
- gate valves are installed upstream and downstream of the oxidizer electrode and fuel electrode in the oxidizer gas and fuel gas supply paths, and an oxygen concentration detector is placed between both electrodes and the downstream gate valve. By detecting the predetermined concentration, the gate valves arranged above, below and above the two poles are opened and closed, and the inert gas is injected again.
- the gate valve 3035 is opened, the raw material gas is flowed to the fuel generator 304, and the concentration of non-fuel substances, including hydrogen, such as carbon monoxide, is reduced to a certain level or less. Then, shut off the gate valve 304, stop the pump 304, open the gate valve 300 and gate valve 304 on the anode side, and open the fuel cell stack 303 was supplied with a source gas.
- the fuel cell stack 303.36 may operate the pump 304, circulate water having a higher temperature than the fuel cell stack 303, and increase the temperature. Next, start-up process 2 is started.
- the blower 3039 was operated to open the gate valve 3041 and the gate valve 3042 on the force sword side, and air was sent to the fuel cell stack 303.
- the present invention is not limited to this, and the same effect is obtained even if the same operation is performed several times when the oxygen concentration detector detects the predetermined concentration. Obtained.
- the fuel electrode and oxidizer electrode of the fuel cell power generator are purged and sealed with an inert gas to prevent the catalyst from deteriorating due to oxygen, measure the oxygen concentration of both electrodes during storage, and measure
- the concentration is detected, the deterioration of the catalyst is suppressed by re-injecting the inert gas again, and it is possible to realize a fuel cell power generation device with excellent durability that does not cause catalyst deterioration even during long-term storage.
- the raw material gas purified in the gas purifying section as an inert gas for the fuel cell, the deterioration due to the start-stop and storage can be reduced easily.
- the detection of the oxygen concentration of the oxidizing gas flow path in the portion between the gate valve 3041 and the gate valve 3042 ⁇ and (b) the gate valve 303 Both the detection of the oxygen concentration of the fuel gas passage in the portion between 7 and the gate valve 3043 was performed.
- the present invention is not limited to this. Detection of the oxygen concentration in the oxidizing gas flow path in the portion between the gate valve 3041 and the gate valve 3042, or (b) the gate valve 303 and the gate valve 3
- One of the detections of the oxygen concentration of the fuel gas passage in the portion between 0 and 4 may be performed.
- the injection of the predetermined purging gas is performed in such a manner that both the detected oxygen concentration of the oxidizing gas flow path and the detected oxygen concentration of the fuel gas flow path have a predetermined value. This was done when it was over.
- the injection of the predetermined purge gas is not limited to this, and the injection of the predetermined oxidizing gas flow path acid may be performed. This may be performed when one of the elemental concentration and the detected oxygen concentration of the fuel gas channel is equal to or higher than a predetermined value.
- FIG. 33 is a diagram illustrating a fuel cell power generator according to Embodiment 11 of the present invention.
- the fuel cell power generation device of the present embodiment is basically the same as the fuel cell power generation device of Embodiment 10 shown in FIG. 32, except that the oxygen concentration detector is replaced with the anode of the fuel cell stack 3036.
- This is a fuel cell power generator in which a voltage detector 3052 for observing a change in cathode potential is arranged.
- the principle of the present embodiment lies in observing a potential rise caused by an adsorption potential caused by adsorption of oxygen to the electrode.
- MEA305 (see FIG. 30) was created as follows.
- Acetylene black (Denka black, manufactured by Denki Kagaku Kogyo Co., Ltd., particle size: 35 nm), which is a carbon powder, is replaced with aqueous tetrafluoroethylene (PTFE.) 1) to prepare a water-repellent ink containing 20% by weight of PTFE as a dry weight.
- PTFE aqueous tetrafluoroethylene
- This ink is applied and impregnated on carbon paper (TGPH060H manufactured by Toray Industries, Inc.) as a base material of the gas diffusion layer, and is heat-treated at 300 ° C. using a hot-air drier to obtain a gas diffusion layer ( About 200 / im).
- carbon paper TGPH060H manufactured by Toray Industries, Inc.
- a catalyst body (50 wt.%) Obtained by supporting a Pt catalyst on carbon powder Ketjen Black (Ketjen B lack £. Ketjen Black International Co., Ltd., particle size 3011111). 1;) 66 parts by weight of hydrogen ion conductive material and binder
- the gas diffusion layer and catalyst layer obtained as described above were joined to both sides of a polymer electrolyte membrane (Nafion 112 membrane of DuPont, USA) to produce MEA305. .
- a rubber gasket plate was joined to the outer periphery of the MEA 305 membrane 301 prepared as described above to form a manifold hole for circulation of cooling water, fuel gas and oxidizing gas.
- a conductive plate made of a graphite plate impregnated with phenol resin, having an outer dimension of 20 cmX32 cmXl.3 mm, and having a gas channel and a cooling water channel having a depth of 0.5 mm. Separators 307a and 307c were used.
- the control section 30445 corresponds to a means including the first purging gas injection means and the second purging gas injection means of the present invention, and the voltage detector 52 detects the potential difference of the present invention.
- the fuel cell power generator of the present embodiment corresponds to the fuel cell operation device of the present invention.
- gas purifying section 30 32 corresponds to the fuel gas purifying means of the present invention. Next, the operation of the fuel cell power generator according to the present embodiment will be described.
- the gate valve 3041 and the gate valve 3042 on the power sword side are temporarily opened, and the raw material gas is injected only into the power sword.
- the voltage detector 3052 determines that the potential difference between the anode and cathode is 1 OmV compared to the value before the raw material gas is temporarily injected (the lower limit of the oxygen concentration that can be detected by ordinary measurement
- the partition on the anode side is detected by the signal from the control unit 3045. Open valve 3 0 3 7 and gate valve 3 0 4 3.
- the gate valve 304 and the gate valve 304 on the force source side are opened, the pump 304 is activated, and the raw material gas is re-injected into the fuel cell stack 303, and the anode
- the gate valve 3007, the gate valve 304, and the gate valve 3041, and the gate valve 3042 on the cathode side were closed and sealed.
- Figure 35 shows the change in the voltage of the stack and the change in the potential of the anode different from that of the cathode into which the source gas was injected.
- the temporary source gas injection was performed on the cathode side, but the present invention is not limited to this, and the same result was obtained by performing the temporary injection operation on the anode side.
- the reason that the material gas is first injected into only one of the cathode and the anode as described above is because oxygen invades the entire fuel cell stack 303 through the sealing portion of the fuel cell stack 330. This is because the potentials of the two electrodes often change almost equally.
- the inert gas is temporarily purged to one of the fuel electrode and the oxidizer electrode, a change in the potential difference between the two electrodes is detected, and the catalyst is degraded by re-injecting the inert gas again.
- a fuel cell power generation device with excellent durability that suppresses catalyst deterioration even during long-term storage.
- gate valves are installed upstream and downstream of the oxidizer electrode and fuel electrode in the oxidizer gas and fuel gas supply paths, and a voltage detector that detects the potential difference between the oxidizer electrode and the fuel electrode is installed.
- a voltage detector that detects the potential difference between the oxidizer electrode and the fuel electrode is installed.
- the voltage detector activates the gate valve to re-inject the inert gas.
- the change in the potential difference between the two electrodes is set to 1 OmV or more. Fuel cell power generation with excellent durability without deterioration The device can be realized.
- the comparative example is similar to the tenth and tenth embodiments, except that the oxygen concentration detector and the voltage detector are not provided, and the re-injection of the raw material gas in the storage step 2 is performed. This is a method of starting and stopping and storing only when a predetermined potential difference is detected. '
- FIG. 36 shows the voltage change of the stack and the potential change of the anode of the comparative example.
- the change in the stack voltage shown in Fig. 34 no change is seen in the voltage of the fuel cell stack 303 even if oxygen enters the fuel cell stack 36 during the storage process (as described above).
- the potentials of the two electrodes change almost equally, and the voltage of the fuel cell stack 36, which is the difference between these potentials, does not change.
- the oxygen concentration detectors 3500 and 3501 in the outer housing 303 the effect of oxygen in the fuel cell stack 36 can be observed.
- the potential difference between the two electrodes is zero, the potential itself often rises (for the above-described reason, the potential difference between the two electrodes is zero even if oxygen has entered the fuel cell stack 330).
- Ru elution occurs.
- the change in the potential rise can be observed by a voltage detector using the change in the potential of each cell when the source gas is temporarily supplied to one of the electrodes. That is, by performing the operation of Embodiment 11, not only the catalyst deterioration due to oxygen but also the catalyst deterioration due to the potential rise can be prevented, and a fuel cell power generator with excellent durability even when the start / stop operation is performed. Can be provided.
- -Fig. 37 shows the results of the durability of the stack using the start / stop method of the tenth embodiment, the eleventh embodiment, and the comparative example.
- the present embodiment it is possible to provide a fuel cell power generator that can exhibit high durability without causing deterioration of the catalyst even when the fuel cell power generator is stopped and stored for a long time.
- Embodiments 10 and 11 described above may also be equivalent to the following embodiments of the invention. That is, as a first invention, during the storage period of the fuel cell, (1) the oxidant gas flow path for supplying and discharging a predetermined oxidant gas to and from the oxidant electrode of the fuel cell; An oxidizing gas flow path upstream valve provided upstream of the electrode; and an oxidizing gas flow path downstream valve provided downstream of the oxidizing gas electrode in the oxidizing gas flow path. Detecting the oxygen concentration of the oxidizing gas flow path in the fuel cell, or (2) upstream of the fuel electrode in the fuel gas flow path for supplying and discharging a predetermined fuel gas to and from the fuel electrode of the fuel cell.
- a fuel cell operation device may be provided with a purge gas injection means for injecting a purge gas.
- the apparatus further comprises a fuel gas purifying means for purifying the predetermined fuel gas
- the predetermined purge gas may be the fuel cell operating device according to the first aspect of the present invention, wherein the fuel gas is the purified fuel gas.
- the fuel cell operation device according to the first invention, wherein the predetermined value is 10 ppm.
- the oxidant gas flow path for supplying and discharging a predetermined oxidant gas to and from the oxidant electrode of the fuel cell; Between an oxidizing gas flow path upstream valve provided upstream of the electrode and an oxidizing gas flow path downstream valve provided downstream of the oxidizing gas electrode at V in the oxidizing gas flow path.
- the detected oxygen concentration in the oxidizing gas passage and / or the detected oxygen concentration in the fuel gas passage is equal to or more than a predetermined value.
- the program may be a program for causing a computer to execute a purge gas injection step of injecting a predetermined purge gas into a portion between a road upstream valve and the fuel gas flow path downstream valve.
- the oxidant gas flow path for supplying and discharging a predetermined oxidant gas to and from the oxidant electrode of the fuel cell;
- An oxidizing gas flow path upstream valve provided upstream of a pole; and a predetermined portion of an oxidizing gas flow path downstream valve provided downstream of the oxidizing gas flow path in the oxidizing gas flow path.
- an electric potential difference detecting means for detecting a potential difference between the electric potential of the oxidant electrode and the electric potential of the fuel electrode
- the fuel cell operation device may be provided with an injection means.
- the apparatus further comprises a fuel gas purifying means for purifying the predetermined fuel gas
- the predetermined purge gas may be the fuel cell operating device according to a sixth aspect of the present invention, which is the purified fuel gas.
- the fuel cell operation device according to the sixth invention, wherein the predetermined value is 1 OmV.
- the oxidant gas flow path for supplying and discharging a predetermined oxidant gas to and from the oxidant electrode of the fuel cell;
- An oxidizing gas flow path upstream valve provided upstream of a pole; and a predetermined portion of an oxidizing gas flow path downstream valve provided downstream of the oxidizing gas flow path in the oxidizing gas flow path.
- a predetermined oxidant gas is supplied to and discharged from the oxidant electrode of the fuel cell.
- An oxidizing gas flow path upstream valve provided upstream of the oxidizing electrode in the oxidizing gas flow path, and an oxidizing gas provided downstream of the oxidizing electrode in the oxidizing gas flow path Injection of a predetermined purge gas into a portion between the fuel cell and the downstream valve of the flow path, or (2) the fuel gas flow path for supplying and discharging a predetermined fuel gas to and from a fuel electrode of the fuel cell.
- Purge gas for injecting purge gas An injection step, injection of a predetermined purging gas into a portion between the oxidizing gas flow path upstream valve and the oxidizing gas flow path downstream valve, or the fuel gas flow path upstream valve and the fuel gas flow path
- a change in the detected potential difference before and after the injection of the predetermined purge gas into the portion between the downstream valve and the predetermined purge gas is equal to or more than a predetermined value, (a) the oxidizing gas flow path upstream valve and Injection of a predetermined purge gas into a portion between the oxidizing gas passage downstream valve and (b) injection into a portion between the fuel gas passage upstream valve and the fuel gas downstream valve.
- the program may be a program for causing a computer to execute a second purge gas injection step of re-injecting
- a recording medium carrying the program of the fifth or tenth invention may be a recording medium which can be processed by a computer. Les ,.
- the program according to the present invention is a program for causing a computer to execute the functions of all or a part of the above-described fuel cell system of the present invention (or devices, elements, circuits, units, and the like). Therefore, it may be a program that operates in cooperation with a computer.
- the present invention is a medium that carries a program for causing a computer to execute all or a part of the functions of all or part of the above-described fuel cell power generation system of the present invention, and is readable by a computer.
- the read program may be a medium that executes the function in cooperation with the computer.
- partial means or device, element, circuit, part, etc.
- partial steps or process, operation, operation, etc.
- some of the devices (or elements, circuits, parts, etc.) of the present invention mean some of the plurality of devices, or one of the devices. It means some means (or elements, circuits, parts, etc.), or means some functions in one means.
- the present invention also includes a computer-readable recording medium that records the program of the present invention.
- One use form of the program of the present invention may be such that the program is recorded on a computer-readable recording medium and operates in cooperation with the computer.
- One embodiment of the program of the present invention is a mode in which the program is transmitted through a transmission medium, read by a computer, and operates in cooperation with the computer. There may be.
- the data structure of the present invention includes a database, a data format, a data table, a data list, a data type, and the like.
- the recording medium includes ROM and the like
- the transmission medium includes transmission mechanisms such as the Internet, light, radio waves, and sound waves.
- the computer of the present invention described above is not limited to pure hardware such as CPU, but may include firmware, OS, and peripheral devices.
- the configuration of the present invention may be realized by software or hardware. Industrial applicability
- the fuel cell system according to the present invention can appropriately cope with problems such as promotion of drying of an electrolyte membrane and local reactions, and can stabilize the performance of a fuel cell even when fuel cell shutdown and power generation are repeated.
- it is useful as a portable power supply, a power supply for portable equipment, a power supply for electric vehicles, and a fuel cell system for home use.
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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)
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA2518419A CA2518419C (en) | 2003-08-25 | 2004-08-24 | Fuel cell system, method of starting fuel cell system |
EP04772414.1A EP1659653B1 (en) | 2003-08-25 | 2004-08-24 | Fuel cell system and method for starting operation of fuel cell system |
KR1020057020241A KR101121273B1 (ko) | 2003-08-25 | 2004-08-24 | 연료전지 시스템, 연료전지 시스템의 기동방법 |
Applications Claiming Priority (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2003-299581 | 2003-08-25 | ||
JP2003299581A JP4617647B2 (ja) | 2003-08-25 | 2003-08-25 | 燃料電池システムとその運転方法 |
JP2003-306621 | 2003-08-29 | ||
JP2003306621A JP4442163B2 (ja) | 2003-08-29 | 2003-08-29 | 燃料電池システム |
JP2003-350058 | 2003-10-08 | ||
JP2003350058A JP2005116375A (ja) | 2003-10-08 | 2003-10-08 | 燃料電池運転装置、燃料電池運転方法、プログラム、および記録媒体 |
JP2003415579A JP2005174829A (ja) | 2003-12-12 | 2003-12-12 | 燃料電池システムおよびその運転方法 |
JP2003-415579 | 2003-12-12 | ||
JP2004-011550 | 2004-01-20 | ||
JP2004011550A JP4593119B2 (ja) | 2004-01-20 | 2004-01-20 | 燃料電池発電装置 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2005020360A1 true WO2005020360A1 (ja) | 2005-03-03 |
Family
ID=34222624
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2004/012444 WO2005020359A1 (ja) | 2003-08-25 | 2004-08-24 | 燃料電池システム、燃料電池システムの停止方法 |
PCT/JP2004/012458 WO2005020360A1 (ja) | 2003-08-25 | 2004-08-24 | 燃料電池システム、燃料電池システムの起動方法 |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2004/012444 WO2005020359A1 (ja) | 2003-08-25 | 2004-08-24 | 燃料電池システム、燃料電池システムの停止方法 |
Country Status (4)
Country | Link |
---|---|
EP (2) | EP1659653B1 (ja) |
KR (2) | KR101121273B1 (ja) |
CA (2) | CA2518419C (ja) |
WO (2) | WO2005020359A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20110229782A1 (en) * | 2006-07-11 | 2011-09-22 | Canon Kabushiki Kaisha | Activation method for fuel cell system |
US8765313B2 (en) * | 2006-09-28 | 2014-07-01 | Toyota Jidosha Kabushiki Kaisha | Fuel cell system and method of controlling same |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
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US8003239B2 (en) * | 2004-06-14 | 2011-08-23 | Panasonic Corporation | Method of preserving polymer electrolyte fuel cell stack and preservation assembly of polymer electrolyte fuel cell stack |
WO2006088077A1 (ja) * | 2005-02-18 | 2006-08-24 | Matsushita Electric Industrial Co., Ltd. | 燃料電池システムおよびその運転方法 |
KR100971745B1 (ko) | 2007-10-30 | 2010-07-21 | 삼성에스디아이 주식회사 | 연료 전지 시스템 및 그 운전방법 |
KR100957369B1 (ko) * | 2008-04-25 | 2010-05-12 | 현대자동차주식회사 | 연료전지의 공기극 개폐장치 |
USD786322S1 (en) | 2015-10-01 | 2017-05-09 | Samsung Electronics Co., Ltd. | Door guard for refrigerator |
KR102095573B1 (ko) * | 2019-06-27 | 2020-05-18 | 주식회사 엔알티 | 촉매형 수소 제거장치를 이용한 폭발방지 시스템 |
US11621429B2 (en) | 2020-09-21 | 2023-04-04 | Hyaxiom, Inc. | Fuel cell component including scale-accommodating flow channels |
CN115198562B (zh) * | 2022-09-16 | 2022-12-02 | 融科氢能源有限公司 | 一种燃料电池用碳纸处理装置及处理方法 |
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- 2004-08-24 CA CA2518419A patent/CA2518419C/en not_active Expired - Fee Related
- 2004-08-24 EP EP04772414.1A patent/EP1659653B1/en not_active Expired - Fee Related
- 2004-08-24 CA CA2518416A patent/CA2518416C/en not_active Expired - Fee Related
- 2004-08-24 WO PCT/JP2004/012444 patent/WO2005020359A1/ja active Application Filing
- 2004-08-24 KR KR1020057020241A patent/KR101121273B1/ko active IP Right Grant
- 2004-08-24 KR KR1020057020245A patent/KR101114649B1/ko not_active IP Right Cessation
- 2004-08-24 WO PCT/JP2004/012458 patent/WO2005020360A1/ja active Application Filing
- 2004-08-24 EP EP04772400A patent/EP1659652B1/en not_active Expired - Fee Related
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US20110229782A1 (en) * | 2006-07-11 | 2011-09-22 | Canon Kabushiki Kaisha | Activation method for fuel cell system |
US8765313B2 (en) * | 2006-09-28 | 2014-07-01 | Toyota Jidosha Kabushiki Kaisha | Fuel cell system and method of controlling same |
Also Published As
Publication number | Publication date |
---|---|
EP1659652A4 (en) | 2008-09-17 |
CA2518419C (en) | 2015-11-24 |
WO2005020359A1 (ja) | 2005-03-03 |
CA2518416A1 (en) | 2005-03-03 |
EP1659653A4 (en) | 2008-09-17 |
CA2518419A1 (en) | 2005-03-03 |
EP1659652B1 (en) | 2012-05-09 |
EP1659653B1 (en) | 2014-10-01 |
EP1659652A1 (en) | 2006-05-24 |
EP1659653A1 (en) | 2006-05-24 |
KR101121273B1 (ko) | 2012-05-17 |
CA2518416C (en) | 2013-01-15 |
KR20060035594A (ko) | 2006-04-26 |
KR101114649B1 (ko) | 2012-03-29 |
KR20060035593A (ko) | 2006-04-26 |
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