WO2005088753A1 - 燃料電池システムの故障診断方法とこれを用いた故障診断装置、および燃料電池システム - Google Patents
燃料電池システムの故障診断方法とこれを用いた故障診断装置、および燃料電池システム Download PDFInfo
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- WO2005088753A1 WO2005088753A1 PCT/JP2005/004365 JP2005004365W WO2005088753A1 WO 2005088753 A1 WO2005088753 A1 WO 2005088753A1 JP 2005004365 W JP2005004365 W JP 2005004365W WO 2005088753 A1 WO2005088753 A1 WO 2005088753A1
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- fuel cell
- impedance
- cell system
- predetermined
- gas supply
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04298—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
- H01M8/04664—Failure or abnormal function
- H01M8/04679—Failure or abnormal function of fuel cell stacks
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
- G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
- G01R31/392—Determining battery ageing or deterioration, e.g. state of health
-
- 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
- H01M8/04246—Short circuiting means for defective 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
- H01M8/04—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
- H01M8/04007—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids related to heat exchange
- H01M8/04029—Heat exchange using liquids
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
- H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
- H01M8/04119—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with simultaneous supply or evacuation of electrolyte; Humidifying or dehumidifying
- H01M8/04126—Humidifying
- H01M8/04134—Humidifying by coolants
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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
- H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
- H01M8/0618—Reforming processes, e.g. autothermal, partial oxidation or steam reforming
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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 method of diagnosing a fuel cell system for specifying a failure location when a power generation abnormality or a reduction in power generation voltage of a polymer electrolyte fuel cell occurs, a failure diagnosis apparatus using the same, and the like. About.
- a fuel cell In a fuel cell, an oxidizing gas containing oxygen is supplied to a power source, and a fuel gas containing hydrogen is supplied to an anode to generate electric power.
- a fuel cell includes a pair of power sources and an anode.
- the fuel cell is constituted by a fuel cell stack in which a plurality of fuel cells are connected in series.
- a gas containing hydrogen is produced via a fuel gas and a hydrogen generator such as a city gas.
- the oxidizing gas generally supplies air through a blower.
- the fuel gas and the oxidizing gas are supplied after being appropriately humidified via a humidifier or the like.
- peripheral devices for operating a fuel cell are composed of a large number of members and are complicatedly linked.
- the cause of the decrease in the voltage of the fuel cell is that the gas diffusion is inhibited and the diffusion resistance is increased, and the reactivity of the electrode is reduced and the reaction resistance is increased. I can not judge whether it is.
- alternating current at a specific frequency is used.
- the impedance is measured in advance, the AC having a specific frequency is applied during power generation, the impedance is measured, and the two are compared (for example, see JP-A-2002-367650).
- the applied AC voltage is applied at a frequency of at least 5 Hz and 40 Hz, and the imaginary part force diffusion resistance and the reaction resistance of the impedance at each frequency are obtained.
- the present invention specifies a failure location in a fuel cell system when an abnormality in power generation or a decrease in power generation voltage occurs during maintenance of the fuel cell system, It is an object of the present invention to provide a failure diagnosis method and a failure diagnosis device for a fuel cell system capable of performing smooth repair.
- a first aspect of the present invention is to provide a fuel cell system comprising: a fuel cell system that superimposes an alternating current on a direct current generated from a fuel cell system under a certain operating condition; Calculating the impedance of a predetermined portion of the fuel cell of the pond system, and comparing the impedance with the impedance calculated under a predetermined reference operating condition, thereby detecting an abnormality in the predetermined portion of the fuel cell.
- a failure of the fuel cell system is determined using the comparison result to determine whether the cause of the abnormality in the predetermined portion is a deviation of one or more predetermined portions constituting the fuel cell system. This is a diagnostic method.
- the cause of the change in the impedance of the predetermined portion of the fuel cell is as follows. It is possible to judge that the fuel cell system is located at any one of the predetermined locations, and if an abnormality occurs in the fuel cell system, the cause of the abnormality can be quickly identified.
- the cause of the abnormality in the predetermined portion is a force existing in the fuel cell itself of the fuel cell system, or the predetermined portion other than the fuel cell.
- the operating condition at the predetermined location is changed more than that under the reference operating condition, and the diagnostic impedance measured according to the change is compared with the impedance of the characteristic profile.
- the diagnostic impedance can be determined based on the characteristic profile of the impedance force of the characteristic profile, it is determined that the cause is at the predetermined location, and if it cannot be determined, it is determined that the cause is not at the predetermined location.
- a failure diagnosis method for the fuel cell system according to the first or second aspect of the present invention is a failure diagnosis method for the fuel cell system according to the first or second aspect of the present invention.
- a plurality of causes can be separated and quickly specified.
- the fuel cell system includes:
- a power generation unit having the fuel cell having the fuel cell
- An oxidizing gas supply unit that supplies the power generating unit with an oxidizing gas for generating power from the fuel cell;
- a hydrogen gas supply unit that supplies the power generation unit with hydrogen gas for generating power from the fuel cell
- the predetermined location is: It includes at least one of a specific location in the hydrogen gas supply unit, a specific location in the oxidizing gas supply unit, and a specific location in the power generation unit,
- the third aspect of the present invention is a method for diagnosing a failure of a fuel cell system according to the present invention, in which the determination is made by changing the operating conditions of these specific locations.
- the specific portion of the hydrogen gas supply unit may include:
- a fourth aspect of the present invention is a method for diagnosing a failure of a fuel cell system according to the present invention, which includes the reformer.
- the specific portion of the oxidizing gas supply unit is:
- a blower for taking in outside air and guiding it to the fuel cell side, a humidifier for humidifying the outside air taken in by the blower, and a second pump for supplying water to the humidifier,
- a fourth aspect of the present invention is a failure diagnosis method for a fuel cell system according to the present invention, wherein the predetermined portion includes a filter provided in a stage preceding the blower.
- the specific portion of the power generation unit includes:
- the predetermined portion of the fuel cell includes:
- a failure diagnosis method for a fuel cell system wherein the fuel cell is regarded as an equivalent circuit having the predetermined portion as a resistor and is determined by calculating the impedance for each of the alternating currents having different frequencies. .
- the amplitude of the alternating current is substantially 5% of the direct current value.
- a tenth aspect of the present invention provides an AC current source that supplies a variable frequency AC current that is superimposed on a DC current that also generates a fuel cell power of a fuel cell system, Impedance calculating means for calculating an impedance corresponding to a predetermined portion of a fuel cell of the fuel cell system from a signal obtained by superimposing the alternating current on the direct current;
- a diagnostic device for a fuel cell system comprising: diagnostic means for determining whether one or a plurality of predetermined locations constituting the fuel cell system are misaligned.
- the present invention it is possible to determine that the cause of the change in the impedance of the predetermined part of the fuel cell is at any one of the predetermined parts of the fuel cell system.
- the cause of the abnormality can be quickly identified.
- the diagnostic means includes:
- the operating condition at the predetermined location is changed more than that under the reference operating condition, and the diagnostic impedance measured according to the change is compared with the impedance of the characteristic profile.
- the diagnostic impedance can be determined based on the characteristic profile of the impedance force of the characteristic profile, it is determined that the cause is at the predetermined location, and if it cannot be determined, it is determined that the cause is not at the predetermined location.
- a failure diagnostic device for a fuel cell system according to a tenth aspect of the present invention.
- a plurality of causes can be separated and quickly specified.
- a twelfth aspect of the present invention is the fuel cell system having the failure diagnostic device for a fuel cell system according to the tenth or eleventh aspect of the present invention
- a power generation unit having the fuel cell, An oxidizing gas supply unit that supplies the power generating unit with an oxidizing gas for generating power from the fuel cell;
- a hydrogen gas supply unit that supplies the power generation unit with hydrogen gas for generating power from the fuel cell
- the predetermined location is:
- It includes at least one of a specific location in the hydrogen gas supply unit, a specific location in the oxidizing gas supply unit, and a specific location in the power generation unit,
- the diagnostic means makes the determination, which is a fuel cell system.
- the thirteenth aspect of the present invention further includes control means for changing operating conditions of the specific location in the hydrogen gas supply unit, the specific location in the oxidizing gas supply unit, and the specific location in the power generation unit.
- the fuel cell system according to a twelfth aspect of the present invention, wherein the diagnostic unit acquires the parameter of the change in the operating condition from the control unit and makes the determination.
- the specific portion of the hydrogen gas supply unit includes:
- the specific portion of the oxidizing gas supply unit includes:
- a blower for taking in outside air and guiding it to the fuel cell side, a humidifier for humidifying the outside air taken in by the blower, and a second pump for supplying water to the humidifier,
- a twelfth aspect of the fuel cell system according to the present invention wherein the predetermined portion includes a filter provided in a stage preceding the blower.
- the specific portion of the power generation unit may include:
- a signal obtained by superimposing the alternating current on the direct current of the tenth or eleventh aspect of the present invention corresponds to a predetermined part of a fuel cell of the fuel cell system.
- Impedance calculating means for calculating impedance for calculating impedance
- An eighteenth aspect of the present invention is a recording medium recording the program of the seventeenth aspect of the present invention, which is a recording medium processable by a computer.
- a nineteenth aspect of the present invention provides a power generation unit having a fuel cell, an oxidant gas supply unit for supplying an oxidant gas for generating power to the fuel cell to the power generation unit, and
- a hydrogen gas supply unit for supplying hydrogen gas for generating power from the fuel cell.
- the fuel cell system is operated by changing the impedance, and at that time, the operating location is specified as the predetermined location by observing whether or not the impedance of a plurality of predetermined portions of the fuel cell changes. This is a method for identifying a diagnostic location of a fuel cell system.
- the present invention it is possible to specify which part of the fuel cell system to be used for the diagnosis is to be used in the above-described method for diagnosing the failure of the fuel cell system. Becomes possible.
- the present invention has an advantage in that when a fuel cell system is operated, a failure location that causes a power generation abnormality can be quickly identified.
- FIG. 1 An explanatory diagram plotting impedance measured by sweeping a frequency according to an embodiment of the present invention.
- FIG. 2 is an explanatory diagram of an equivalent circuit representing impedance of a cell according to the embodiment of the present invention.
- FIG. 3 is a diagram showing an SZN ratio with respect to an amplitude of an alternating current in the embodiment of the present invention.
- FIG. 4 (a) is an explanatory diagram showing a relationship between impedance and frequency in the embodiment of the present invention.
- FIG. 4 (c) is an explanatory diagram of an equivalent circuit of impedance according to the embodiment of the present invention.
- FIG. 4 (d) is an explanatory diagram of an equivalent circuit of impedance according to the embodiment of the present invention.
- FIG. 5 (a) is a configuration diagram of a fuel cell system according to an embodiment of the present invention.
- FIG. 5 (b) is a configuration diagram of a fuel cell system according to an embodiment of the present invention.
- FIG. 6 (a) is a flowchart illustrating a diagnostic method according to an embodiment of the present invention.
- FIG. 6 (b) is a flowchart illustrating a diagnostic method according to an embodiment of the present invention.
- FIG. 6 (c) is a flowchart illustrating a diagnostic method according to an embodiment of the present invention.
- FIG. 6 (d) is a flowchart illustrating a diagnostic method according to an embodiment of the present invention.
- FIG. 7 (a) A diagram for explaining separation of an abnormal part using a characteristic profile according to the embodiment of the present invention.
- FIG. 7 (b) is a diagram for explaining the separation of an abnormal part using the characteristic profile according to the embodiment of the present invention.
- FIG. 7 (c) is a diagram for explaining the separation of an abnormal part using a characteristic profile according to the embodiment of the present invention.
- FIG. 7 (d) is a diagram for explaining separation of an abnormal part using a characteristic profile according to the embodiment of the present invention.
- FIG. 8 is a diagram showing a chart for explaining a diagnostic location according to the embodiment of the present invention.
- FIG. 9 is a diagram showing a change over time of a cell voltage in Example 1 of the present invention and a comparative example.
- FIG. 10 is a chart showing a diagnostic result after 5000 hours in Example 1 of the present invention.
- FIG. 11 is a chart showing a diagnostic result after 10,000 hours in Example 1 of the present invention.
- FIG. 12 is a configuration diagram showing a cross section of the hydrogen generator according to the embodiment of the present invention.
- a fuel cell constituting a fuel cell is composed of a hydrogen ion conductive electrolyte membrane and electrodes arranged on both sides thereof, and is a so-called polymer electrolyte type.
- a fuel cell is constituted by including a pair of separator plates having gas flow paths for supplying and discharging a fuel gas to one of the electrodes and supplying and discharging an oxygen-containing gas to the other electrode.
- the electrode to which the fuel gas is supplied is the anode, and the electrode to which the oxygen-containing gas is supplied is the power source.
- the impedance of the fuel cell unit also includes the impedance of the anode, the impedance of the force source, the impedance of the electrolyte membrane, and the contact resistance of each component.
- FIG. 1 which is an explanatory diagram plotting impedance measured by sweeping a frequency of an alternating current for superimposition described later in the embodiment of the present invention, shows a typical fuel cell. A plot of the imaginary part versus the real part of the pond cell impedance is shown.
- the inventor has found that, as an equivalent circuit representing the behavior of the impedance, the equivalent circuit representing the impedance of the fuel cell according to the embodiment of the present invention shown in FIG. 2 has the highest accuracy. Was.
- An AC current having a small amplitude of about 10% or less of the current amplitude value of the DC current taken out of the fuel cell and having a frequency f is superimposed on the DC current of the fuel cell, and is taken out later.
- the impedance is calculated from the amplitude and phase of the AC component of the cell voltage and the AC component of the cell current measured at that time.
- the ratio of the signal to noise (SZN ratio) such as the amplitude of the superposed alternating current is large. As shown in Fig. 3, when the amplitude of the AC current exceeds 5% of the DC current, the SZN ratio saturates, and even if the amplitude is further increased, the SZN ratio does not improve!
- the amplitude of the applied AC current is preferably about 5% to 10% of the DC current.
- the fuel cell voltage AC component at the time of measurement is a complex number E
- its real part is Er
- its imaginary part is Ei
- the fuel cell current AC component is a complex number I
- its real part is Ir.
- its imaginary part is Ii
- the complex impedance can be calculated from E and I measured at the time of extracting the alternating current having the frequency f.
- the frequency f of the alternating current to be taken out is swept from about 0.1 Hz to about 100 Hz, and the complex impedance at each frequency is similarly calculated.
- the real part Zr is plotted on a horizontal axis
- the imaginary part Zi is plotted on a complex plane with a minus sign Zi on the vertical axis, and a Cole-Cole plot (Cole- Create a Col e plot).
- the Cole-Cole plot has a semi-circular shape with a constant radius having a center point on the horizontal axis (according to the so-called Cole-Cole arc rule).
- a Cole-Cole plot in the case of an equivalent circuit having resistances (resistance values) Rm, Ra, Rc, capacitors (capacitance values) Ca, Cc, and a pocket impedance Wc is as follows:
- It has a shape in which three arcs are overlapped.
- Rm is the resistance value of the electrolyte membrane
- Ra is the anode reaction resistance
- Rc is the force sword reaction resistance
- Ca is the anode double layer capacity
- Cc is the force sword double layer.
- the capacity, Wc represents the force sword diffusion impedance, respectively.
- Wc is a finite-length whirble impedance described by (Equation 3).
- L is the effective diffusion thickness
- D is the diffusion coefficient
- ⁇ is the angular velocity of the AC signal.
- Rw represents the force-sword diffusion resistance, which is equal to Wc when ⁇ ⁇ 0. Since then, The force sword diffusion resistance Rw is used as a component indicating dance.
- the component calculation accuracy is higher when the frequency is changed as finely as possible, but if only the four components of Rm, Ra, Rc, and Rw are calculated, the complex impedance at the minimum of four frequencies is calculated. By measuring the real components of the above, the four resistance values can be approximately calculated.
- the real component of the complex impedance at a high frequency (for example, lOOOOHz) is almost equal to Rm.
- the real component of is Rm + Ra + Rc
- the real component at 0.1 Hz is Rm + Ra + Rc + Rw.
- a change in each condition for operating the fuel cell is related to a change in each component when the fuel cell is regarded as an equivalent circuit, and a specific condition corresponds to a specific component. Then, help yourself.
- a fuel cell under predetermined operating conditions for example, rated conditions Measure the impedance of the cell and store the rated values of the components of the equivalent circuit.
- the values of the components of the equivalent circuit obtained by measuring the impedance when the operating conditions are changed are stored and compared with the values at the time of the rating, thereby obtaining the components of the equivalent circuit. Determine the change in value. If there is a component that shows an abnormal change, it is known that the change in that component corresponds to the change in the operating conditions at a given location. Can be identified.
- FIG. 5A is a configuration diagram of the fuel cell power generation system and the failure diagnosis device of the fuel cell power generation system according to the embodiment of the present invention.
- the fuel cell system and the failure diagnosis device of the embodiment will be described. The configuration will be described.
- the fuel cell power generation system adds water to city gas, reforms it with hydrogen generator 501 to produce a gas containing hydrogen, and uses it as fuel gas to form an anode
- This is a fuel cell power generation system that supplies water to a hydrogen generator 501 by supplying water to a power source (not shown) by humidifying the air and supplying power to a power sword (not shown).
- Power Fino letter 504 for removing dust and other impurities
- calorimeter 505 for caloring the air passing through the finollet 504
- pump 502b for supplying water to calorimeter 505
- fuel cell DC current (DC) to AC power And an inverter 506, and a control unit 510 for controlling operations of these units
- the failure diagnosis device for the fuel cell system receives the DC current from the fuel cell selectively with the inverter 506, and superimposes the above-described AC current on the DC current source 507; Calculating means 508 for calculating the impedance from the signal on which the signal is superimposed, information from the control means 510, and calculation of the impedance calculating means 508. Diagnostic means 509 for judging an abnormality of the fuel cell of the fuel cell system using the impedance and determining which component of the fuel cell system caused the abnormality.
- the reformer, the burner for heating the reformer, the pump 502a, and the booster 502c constitute a hydrogen gas supply unit of the present invention.
- the blower 503, the pump 502b, the filter 504, and the humidifier 505 constitute an oxidizing gas supply unit of the present invention.
- the pump 502d and the fuel cell 501 constitute a power generation unit of the present invention.
- FIG. 5B shows the configuration of the diagnostic unit 509.
- the diagnostic means 509 receives the impedance calculation result and the parameters of the operating conditions of each part of the fuel cell system which are input from the control means 510, and these forces are used to create characteristic profile creating means 509a for creating a characteristic profile of each part. It has a memory 509b for storing the characteristic profile, a diagnostic main unit 509c for specifying the presence / absence of an abnormality and a fault location by comparing the characteristic profile with the impedance calculation result, and a display unit 509d for displaying the diagnostic result and the like. You. Note that the memory 509 can also store data from the diagnostic body 509, data from the control unit 510, and impedance calculation results.
- the display unit 509d may be realized by a conventionally known means such as a speaker and a display as long as the means can display a diagnosis result or the like by voice, video, or the like.
- the hydrogen generator 501 includes a reformer, a burner for heating the reformer, and a carbon monoxide remover for removing the reformed gas power from the reformer. This is a device that reforms methane and water in city gas in a reformer to produce a reformed gas consisting mainly of hydrogen and carbon dioxide.
- the details of an example of the configuration of the hydrogen generator 501 will be described in each embodiment, but the configuration of the hydrogen generator may be a conventionally known configuration. In short, the present invention is not limited by the specific configuration of the hydrogen generator.
- the load current of the fuel cell 502 is supplied to the inverter 506 to be converted into alternating current and taken out to the outside. Heat generated during power generation is extracted outside through cooling water.
- the load current of the fuel cell was supplied to an AC current source 507 instead of the inverter 506, and an AC signal was superimposed on the DC load current.
- the impedance calculation means 508 was connected to the cell of the fuel cell 502. The voltage detected from the voltage measurement terminal and the current force flowing through the cell also measure the complex impedance, and the measurement result is input to the diagnostic means 509.
- the parameters of the operating conditions of the specific part operated at the time of failure diagnosis are input from the control means 10 to the diagnosis means 501.
- the characteristic profile creation means 509a generates a change in impedance corresponding to a parameter change in the operating condition from the above two inputs as a characteristic profile and stores it in the memory 509a.
- power generation of the fuel cell system is performed under the rated operating conditions as the predetermined reference operating conditions of the present invention, and the impedance at that time is measured to obtain the value of each component of the equivalent circuit. .
- the fuel cell power generation system is operated at a rated operation (S10), and the impedance of the fuel cell 502 at that time is measured by the impedance calculation means 508 (S11).
- the equivalent circuit of FIG. 2 is calculated (S12), and the rated time circuit constants (Ra, R C , R W , and Rm), which are components of this equivalent circuit, are stored in the memory 509b of the diagnostic means 509 ( S13).
- the rated circuit coefficient corresponds to the impedance of the characteristic profile of the present invention.
- the hydrogen gas supply unit, the oxidant gas supply unit, and the power generation unit are each configured.
- the resistance value in the equivalent circuit changes due to the change in the operating conditions of each part the presence of abnormalities in the hydrogen gas supply unit, the oxidizing gas supply unit, and the power generation unit Can be diagnosed and determined.
- the control means 510 controls the booster 502c so as to increase the fuel supply amount to the reformer, that is, the supply amount of the city gas (S20), and the fuel cell 502 after the fuel supply amount increases.
- the impedance calculating means 508 measures the impedance of the circuit (S21), and based on this, a new equivalent circuit of FIG. 2 is calculated (S22). Ra, Rc, Rw, Rm) are calculated (S22) and compared with the rated circuit coefficients already stored in the memory 509b (S23).
- Ra When the amount of fuel supplied to the reformer is increased at rated power, Ra is usually slightly reduced. On the other hand, if there is an anomaly, Ra changes differently. It is determined whether or not the different change is related to an abnormality in a predetermined portion of the hydrogen gas supply unit obtained through experience. The relationship between such a change from the rating of Ra and an abnormality in a predetermined portion of the hydrogen gas supply unit (such as the reforming unit or the booster 502) can be obtained empirically. It is stored in memory 509b of stage 509. Using this, the diagnosis main unit 509c determines whether or not Ra's transformation is related to an abnormality at a predetermined location.
- Ra becomes significantly smaller, it is considered that the fuel utilization factor Uf becomes abnormally large at the time of rating, so it is first determined whether or not Ra has become significantly small (S24). . It is assumed that the reason why Ra is significantly reduced is that the capacity of the booster 502c for pressurizing city gas is reduced and the original capacity is not achieved, and fuel shortage occurs. Based on this, the diagnosis means 509 makes a decision (S25). Adjustment or replacement of the booster 502c based on the diagnostic results will complete the repair.
- Ra when it is determined that Ra does not become significantly small, it is determined whether or not Ra has further increased (S 26).
- the reason for the increase in Ra is as follows. This is because the pass-through rate of methane to hydrogen may decrease in the reformer.
- the diagnosis means 509 determines the catalyst deterioration based on this (S27). Based on the result of the diagnosis, it is possible to take measures such as replacing the reformer.
- the control means 510 controls the pump 502a so as to increase the amount of water added to the reformer, that is, the supply amount of water to be added to the city gas as fuel (S30).
- the impedance calculation means 508 measures the impedance of the fuel cell 502 (S31), and based on this, newly calculates the equivalent circuit in FIG. 2 and its rated circuit constants (Ra, Rc, Rw, Rm) as its components. (S32), and compares it with the rated circuit coefficient already stored in the memory 509b (S33).
- Ra When the amount of water added to the reformer is increased from the rated time, Ra usually becomes slightly larger. On the other hand, if there is an anomaly, Ra will take a different change. Determine whether this different change is related to an empirically-obtained abnormality in the specified location of the hydrogen gas supply unit.
- Ra steam-to-carbon ratio
- SZC steam-to-carbon ratio
- Ra Ra does not decrease
- the reason for the significant increase in Ra is considered to be a decrease in the rate of transfer of methane to hydrogen in the reformer in the hydrogen generator 501 at the time of rating.
- the decrease in the pass-through rate is due to catalyst deterioration.
- Stage 509 determines catalyst degradation (S37). Based on the diagnosis result, it is possible to take measures such as replacing the reformer.
- the control means 510 performs control to control the burner to increase the temperature of the reformer.
- the circuit constants (Ra, Rc, Rw, Rm) as the equivalent circuit and the diagnostic impedance of the present invention are calculated and compared with the rated circuit coefficients already stored in the memory 509b (S40-S42).
- Raising the temperature of the reformer at rated time usually raises Ra slightly. On the other hand, if Ra becomes smaller, it is considered that the pass-through rate is lowered due to the lowering of the temperature of the reformer at the time of rating, so it is determined whether Ra has become smaller (S44). If Ra becomes smaller, it is considered that the pass-through rate of methane to hydrogen is lowered in the reformer. 1S This is caused by a defect in the burner that heats the reformer. Therefore, the diagnostic means 509 determines burner failure based on this (S45). Based on the result of the diagnosis, the burner can be cleaned and replaced.
- the presence or absence of an abnormality in the hydrogen gas supply unit was determined by focusing on the change in Ra.
- changing the operating conditions of the oxidizing gas supply unit changes the air utilization rate, humidity, and the like in the fuel gas supplied to the fuel cell 502, so that Rw, Rc, Rm
- the presence or absence of abnormality in the oxidizing gas supply unit is determined by focusing on the change in The following is a description.
- control means 510 controls blower 503 to increase the amount of air supply to fuel cell 502 (for example, to increase the output and rotation speed of blower 503).
- the equivalent circuit and the circuit constants (Ra, Rc, Rw, Rm) as the diagnostic impedance of the present invention are calculated and compared with the rated circuit coefficients already stored in the memory 509b (S50-S53). .
- Rw When the air supply amount to the fuel cell 502 is increased at the rated time, Rw usually becomes slightly smaller. On the other hand, if there is an abnormality, Rw changes differently. A determination is made as to whether or not the change is related to an abnormality in a predetermined portion of the oxidizing gas supply unit, which is stored in the different change memory 509b and obtained empirically.
- the diagnostic means 509 makes a decision (S54c). If adjustment or replacement of the blower 503c or cleaning or replacement of the filter 504 is performed based on the diagnosis result, it is possible to take measures.
- Rw has changed before and after the control for increasing the air supply amount
- V ⁇ instead, it is considered that the fuel cell of the fuel cell 502 is dry at the time of rating and is in a dry-up state, and the cause is considered to be a decrease in the humidifying capacity of the humidifier 505.
- the diagnostic means 509 makes a decision (S56). Based on the diagnosis result, adjustment or replacement of the humidifier 505 or the pump 502b makes it possible to respond. Further, if it is determined in S55 that Rw has changed before and after the control for increasing the amount of air supplied, it is determined whether Rc has increased (S57).
- the diagnostic means 509 determines that the filter is defective (S58). Based on the result of the diagnosis, it is possible to take measures such as cleaning and replacing the filter 504.
- the ffilj control means 510 controls the pump 502b to control the amount of humidification water, that is, the amount of water supplied to the humidifier 505.
- the increasing control is performed, and based on this, the equivalent circuit and the circuit constants (Ra, Rc, Rw, Rm) as the diagnostic impedance of the present invention are calculated and compared with the rated circuit coefficient already stored in the memory 509b (S60-). S63).
- the diagnostic means 509 makes a decision (S65). Based on the result of the diagnosis, adjustment or replacement of the humidifier 505 or the pump 502b can take measures.
- the abnormality in the power generation unit can be obtained by focusing on the changes in Rw and Rm as circuit constants. Is determined. The following is a description.
- control means 510 controls pump 502d to increase the amount of cooling water of fuel cell 502, that is, the amount of supplied water, and, based on this, the equivalent circuit and the present invention. Calculate the circuit constants (Ra, Rc, Rw, Rm) as the diagnostic impedance of, and compare them with the rated circuit coefficients already stored in the memory 509b (S70-S73).
- the temperature of the fuel cell of the fuel cell 502 is controlled by cooling water.
- the temperature distribution in the fuel cell depends on the amount of cooling water, and the larger the amount of cooling water, the smaller the temperature distribution.
- Rw usually decreases slightly.
- Rw becomes significantly small it is considered that the flooding of the cells constituting the fuel cell 501 in which the temperature distribution of the fuel cell is large at the time of rating is occurring. Then, it is determined whether or not Rw is significantly reduced (S74). If it is determined that Rw has become significantly smaller, flooding has occurred, and this cause was set by controlling the amount of cooling water actually supplied to the fuel cell 502.
- the control means 510 controls the AC current source 507 to reduce the load current output from the fuel cell 502. Do this
- the circuit constants (R a , R c , R w, and R m ) as the equivalent circuit and the diagnostic impedance of the present invention are calculated based on the above, and are compared with the rated circuit coefficients already stored in the memory 509b (S80-S83).
- Rw When the load current taken out of the fuel cell 502 is reduced from the rated time, Rw usually becomes slightly smaller. On the other hand, when Rm is significantly reduced, it is considered that the fuel cell of the fuel cell 502 is in a flooding state at the time of rating. Then, it is determined whether or not Rm has become significantly smaller (S84). If it is determined that Rm has become significantly smaller, it means that flooding has occurred. This is probably due to an increase in wettability due to deterioration of the fuel cell. Based on this, the diagnostic means 509 makes a decision (S85). Adjustment or replacement of the fuel cell 502 based on the result of the diagnosis makes it possible to respond.
- the operating conditions of each specific portion of the hydrogen gas supply unit, the oxidizing gas supply unit, and the power supply unit are changed, and the corresponding impedance change as each circuit coefficient constituting the equivalent circuit of the fuel cell 502 is changed.
- the operation of diagnosing the presence or absence of the hydrogen gas supply unit, the oxidizing gas supply unit, and the power supply unit at a predetermined location has been described above.
- Deterioration force of fuel cell 502 When the impedance contributes to the entire impedance (Ra, Rc, Rw, Rm) of the equivalent circuit, the change in the impedance value obtained by the measurement is caused, for example, by a change in the temperature of the reformer as a specific location. It is necessary to determine whether the operation is performed based on deterioration of the fuel cell 502.
- the characteristic profile creating means 509a uses the impedance value input from the impedance calculating means 508 and the fuel cell power generation obtained from the control means 510. From the parameters that indicate the operating conditions of the system, the change in the impedance corresponding to the change in the parameters of the operating conditions can be used as the characteristic profile. And stored in the memory 509b.
- the failure diagnosis method grasps in advance the effects of operating conditions on parameter change force impedance changes, and observes how impedance changes when operating conditions are changed, thereby observing the failure. It specifies the location.
- the relationship between the operating condition and the impedance typically has a relationship as shown in Fig. 7 (a). That is, for a certain operating condition parameter X, the X changes the impedance component Y.
- the operating condition parameter X is a physical quantity for controlling the fuel cell, for example, an air supply amount, a cooling water supply amount, or the like.
- the impedance component Y is a circuit constant obtained by analyzing the impedance using an equivalent circuit, and Y is a circuit constant that mainly changes according to X. For example, if X is the supply amount of air, Y is equivalent to Rw.
- the operating condition parameter X is set so as to make Y as small as possible.
- energy is required to increase X, and increasing X unnecessarily increases the fuel cell system. This is disadvantageous when considering the overall efficiency. Therefore, taking into account the improvement of power generation by reducing Y and the improvement of energy consumption by reducing X, an appropriate operating range is determined so that the efficiency of the entire system is improved.
- the relationship between the impedance Y and the operating condition parameter X has an inflection point as shown in Fig. 7 (a), and the proper operation range exists near the inflection point.
- the impedance Y force with respect to the operating condition parameter X may have a minimum point as shown in Fig. 7 (b).
- the appropriate operation range is set near the minimum point. For example, the amount of fuel supplied to the fuel cell and the amount of water added to the fuel correspond to this.
- a change in the impedance value when the operating condition of the blower 503, which is a specific part of the oxidizing gas supply unit, in Fig. 6B is changed will be described with reference to Fig. 7C. .
- the characteristic profile 1 shows the impedance change with respect to the air supply amount.
- the failure diagnosis the failure of the peripheral device of the fuel cell such as the blower alone is not enough, and the fuel cell itself deteriorates with time.
- the failure diagnosis method of the present invention abnormality caused by deterioration of the fuel cell itself and abnormality caused by failure of peripheral devices can be distinguished. An example in which the deterioration of the fuel cell is superimposed on the impedance change in FIG. 7 (c) will be described with reference to FIG.
- the initial impedance when controlled by the appropriate flow rate XI is W1.
- Characteristic profile 2 shows the change in impedance when the fuel cell is deteriorated. If the flow rate is controlled at XI, it will be W4. If the blower that supplies air deteriorates and performs control equivalent to XI, but the air flow is equivalent to X2 and the power is not supplied, the impedance should show W5 . At this time, control is performed to increase the air flow rate, and when the actual air flow rate changes from X2 to XI, the impedance greatly decreases from W5 to W4. If the impedance Rw decreases significantly in this way, it indicates that there is an abnormality in the air supply system such as the blower.
- the fuel cell power generation The components that make up the system are divided into a hydrogen gas supply section, an oxidizing gas supply section, and a power generation section.
- the operating conditions of specific sections of each section are changed, and the impedance of the fuel cell corresponding to these sections is changed during rated operation.
- the impedance By comparing the impedance with the impedance, it is possible to diagnose the presence or absence of an abnormality at each predetermined position of the hydrogen gas supply unit, the oxidizing agent gas supply unit, and the power generation unit.
- a fuel cell 502 having a single fuel cell power is representatively shown, but a fuel cell in which a plurality of fuel cells are stacked is shown.
- the battery stack can be connected instead of the fuel cell, and the impedance of the entire fuel cell stack can be measured.
- each of the above-mentioned diagnoses is automatically performed by using the diagnostic means 509 in Fig. 5, and the diagnosis is performed by the diagnostician using the impedance that is the calculation result of the force impedance calculating means 508. You may.
- the value of the comparison result of each component of the impedance may be used by comparing the magnitude of the computed value or the magnitude of the ratio of the force computed value performed by comparing the magnitude of the difference.
- the diagnosis of the present invention is not limited by the processing method after the quantitative comparison, as long as it is based on the magnitude of the value obtained by quantitatively comparing the impedance comparison result.
- the failure part of the present invention may be each means shown in FIG. 5 as described in the above description, or a plurality of parts such as a reformer, a catalyst, a If the component powers are satisfied, you can specify the! Of those components, or the force that is one or more of them, needless to say! / ⁇
- Each diagnosis described above is shown as a series of flowcharts as shown in Figs. 6 (a) to 6 (d), but can be shown as tables in any order in Fig. 8. As long as the diagnosis can be made for every item, each operation may be performed in any order without following the above-mentioned flowchart. Diagnosis of any of the hydrogen gas supply unit, oxidant gas supply unit, and power generation unit In the case of the line, the operation of the corresponding part may be performed.
- a gas diffusion layer was produced by the following method.
- a carbon paper (TGPH-060, manufactured by Toray Industries, Inc.) is impregnated with a dispersion of polytetrafluoroethylene (Rublon LDW-40, manufactured by Daikin Industries, Ltd.) at a dry weight of 10% by weight.
- Water repellency treatment was performed by heating at 350 ° C using a dryer.
- a polymer-containing conductive layer composed of carbon powder and fluorine resin was formed. That is, it was prepared by mixing Denka Black as a carbon powder with a dispersion of polytetrafluoroethylene as a fluorine resin (manufactured by Daikin: Lubron LDW-40) in a dry weight of 30% by weight. The dispersion was applied to the water-repellent carbon paper, and heated at 350 ° C. using a hot air drier to produce a gas diffusion layer including a polymer-containing conductive layer.
- an electrolyte membrane / electrode assembly (MEA) was produced by the following method.
- Conductive carbon powder loaded with 50% by weight of platinum particles having an average particle size of about 30A (Tanaka Kikinzoku Kogyo Co., Ltd .: TEC10E50E) 10 g of water and 10 g of water are added to form a hydrogen ion conductive polymer electrolyte.
- a catalyst paste was prepared by mixing 55 g of a weight% ethanol solution (Flemion, manufactured by Asahi Glass Co., Ltd.). This paste was applied on a polypropylene film by bar coating using a wire bar, and dried to form an oxidant electrode-side catalyst layer. The coating amount of the catalyst layer was adjusted such that the platinum content was 0.3 mg per 1 cm 2 .
- This polypropylene film with a catalyst layer was cut into 6 cm A polymer electrolyte membrane (Japan Gore-Tex Co., Ltd .: Gore Select, film thickness 30 m) is sandwiched between the above-mentioned two pairs of polypropylene films with a catalyst layer so that the catalyst layer is on the inside, and the temperature is 130 ° C. After hot pressing for 10 minutes, the polypropylene film was removed to obtain a polymer electrolyte membrane with a catalyst layer.
- Gore Select film thickness 30 m
- the MEA was sandwiched between a pair of separator plates to form a fuel cell.
- a fuel cell power generation system having the configuration shown in FIG. 5 was manufactured using the fuel cell prepared as described above for the fuel cell 502.
- the hydrogen generator 501 was manufactured according to the method described in JP-A-2003-252604.
- Figure 12 shows a cross-sectional view of the hydrogen generator.
- a hydrogen generator 501 according to the present embodiment includes a parner 16 for generating a combustion gas, and a cylindrical combustion chamber 17 provided above the parner 16.
- a cylindrical reformer 10 is provided coaxially with the combustion chamber 17 on the outer peripheral side of the combustion chamber 17.
- the reformer 10 houses a catalyst layer filled with a steam reforming catalyst, and performs a steam reforming reaction of a raw material gas in the catalyst layer to generate a reformed gas.
- a fuel cell 502 is provided outside the hydrogen generator 501, and the hydrogen generator 501 and the fuel cell 502 constitute the fuel cell system of the present invention.
- the reformed gas generated in the reformer 10 is discharged from the reformed gas outlet 27 and supplied to the fuel cell 502.
- a cylindrical reformed gas channel 11 for guiding the reformed gas generated in the reformer 10 to the reformed gas outlet 27 is provided on the outer peripheral side of the reformer 10.
- a cylindrical combustion gas flow path 12 through which the combustion gas generated in the parner 16 flows is provided coaxially with the combustion chamber 17.
- the combustion gas flow path 12 also serves as a flow path divided by a cylindrical heat insulating material 13 and a cylindrical body 14, and is configured to guide the combustion gas toward a combustion gas discharge port 15.
- a cylindrical evaporation chamber 28 is provided coaxially with the combustion chamber 17 on the outer circumference side of the combustion gas flow path 12 and on the outermost circumference of the hydrogen generator 501.
- the evaporating chamber 28 includes a cylindrical first evaporating chamber 18 and a second evaporating chamber 22 provided between the first evaporating chamber 18 and the cylindrical partition 21. Forces are also configured.
- the second evaporation chamber 22 is located on the combustion gas flow path 12 side, and the first evaporation chamber 18 is located on the outer circumference side of the second evaporation chamber 22 via the partition 21, that is, on the outermost circumference of the hydrogen generator 501. ing.
- a raw material inlet 19 for supplying a raw material X containing at least a compound which also comprises carbon and hydrogen power to the apparatus and a water inlet 20 for supplying the same water Y are formed.
- Compounds composed of at least carbon and hydrogen include, for example, hydrocarbons such as methane, ethane, and propane, city gas, natural gas, alcohols such as methanol, kerosene, and LPG (liquid oil petroleum gas). No. In Fig. 5, city gas is used.
- a steam outlet 24 which is an outlet of the steam generated in the evaporating chamber 28.
- the steam outlet 24 is connected to the reformer 10 via a steam supply pipe 25. Therefore, the steam discharged from the steam outlet 24 is supplied to the reformer 10 via the steam supply pipe 25.
- the filter 504 is composed of an MC hub and a HEPA filter manufactured by Nagase & Co., and removes dust and NOx and SOx from the air.
- a reformed gas (80% hydrogen, 20% carbon dioxide, 20ppm carbon monoxide, dew point 65 ° C) obtained by adding water to city gas and reforming with a hydrogen generator 501 is supplied. Then, humidified air was supplied to the oxygen electrode side with a dew point of 70 ° C, and power was generated at a fuel utilization of 80%, an oxygen utilization of 40%, and a current density of 200 mAZcm 2 .
- the cooling water was adjusted to 70 ° C on the inlet side of the fuel cell and to 72 ° C-75 ° C on the outlet side.
- the voltage of the fuel cell was 0.75V.
- FIG. 9 shows the change over time in the cell voltage.
- the cell voltage gradually decreased with time, and after 5000 hours from the start of operation, the cell voltage dropped to 0.70 V or less.
- the load current was connected to the impedance measuring instrument by the inverter, and 1000Hz, 200Hz
- the complex impedance at Hz, 10 Hz, and 0.1 Hz was measured.
- the impedance calculation means 508 is a frequency response analyzer (SOLARTRON S
- the load current was a current obtained by superimposing a sine wave of ⁇ 10 mAZcm 2 on a DC of 200 mAZcm 2 .
- the real component of the complex impedance at lOOOOHz is Rm
- the real component at 200Hz is Rm + Ra
- the real component at 10Hz is Rm + Ra + Rc
- the real component at 0.1Hz is Rm + Ra + Rc + Rw.
- Rm, Ra, Rc and Rw at the rated time were calculated respectively.
- FIG. 10 shows the resistance values and the judgment before and after the change of the operating conditions. As a result, it was found that flooding of the power sword was occurring, and inspection of the filter 504 showed that the filter was clogged, so the filter 504 was replaced.
- a fuel cell was constructed in the same manner as in Example 1, and a fuel cell power generation system having the structure shown in FIG. 5 was produced using this fuel cell in the same manner as in Example 1.
- a fuel cell power generation system having the same configuration as in Example 1 was produced.
- Embodiments 1 and 2 by comparing the above-described Embodiments 1 and 2 with the comparative example, it is possible to identify a failure portion of the fuel cell system, thereby performing quick repair. Since the fuel cell system can be maintained in an optimal state, it is clear that the fuel cell system can maintain power generation stably for a long time.
- the program working on the present invention is a program for causing a computer to execute the functions of all or a part of the above-described failure diagnosis apparatus for a fuel cell system of the present invention, and It may be a program that operates in cooperation.
- the present invention also relates to a medium carrying a program for causing a computer to execute all or some of the functions of all or some of the above-described failure diagnostic devices for a fuel cell system of the present invention.
- the program may be a medium that is readable by a computer and that executes the function in cooperation with the computer.
- the "partial means" of the present invention means some of the plurality of means, or a part of the function or part of one means. It means the operation of.
- some of the devices of the present invention mean some of the plurality of devices, or some of the means of one of the devices, Or, it means a part of the function of 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 a form in which the program is recorded on a computer-readable recording medium and operates in cooperation with the computer.
- One use form of the program of the present invention may be a form in which the program is transmitted through a transmission medium, read by a computer, and operates in cooperation with the computer.
- the recording medium includes a ROM and the like, and the transmission medium includes a transmission mechanism 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 a CPU, but may include firmware, an OS, and peripheral devices.
- the configuration of the present invention may be realized by software or hardware.
- the failure diagnosis method and the failure diagnosis device for a fuel cell system according to the present invention can quickly identify the cause of the power generation abnormality of the fuel cell and can efficiently perform the repair, which is useful.
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Abstract
Description
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JP2006511015A JPWO2005088753A1 (ja) | 2004-03-12 | 2005-03-11 | 燃料電池システムの故障診断方法とこれを用いた故障診断装置、および燃料電池システム |
US10/592,500 US20070172708A1 (en) | 2004-03-12 | 2005-03-11 | Fuel cell system failure diagnosis method, failure diagnosis device using same, and fuel cell system |
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JPWO2005088753A1 (ja) | 2007-08-09 |
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