WO2018131071A1 - 燃料電池システムの制御方法及び燃料電池システム - Google Patents
燃料電池システムの制御方法及び燃料電池システム Download PDFInfo
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- WO2018131071A1 WO2018131071A1 PCT/JP2017/000483 JP2017000483W WO2018131071A1 WO 2018131071 A1 WO2018131071 A1 WO 2018131071A1 JP 2017000483 W JP2017000483 W JP 2017000483W WO 2018131071 A1 WO2018131071 A1 WO 2018131071A1
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- fuel cell
- anode
- anode electrode
- frequency
- reaction resistance
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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
- H01M8/04228—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids during start-up or shut-down; Depolarisation or activation, e.g. purging; Means for short-circuiting defective fuel cells during shut-down
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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
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/043—Processes for controlling fuel cells or fuel cell systems applied during specific periods
- H01M8/04303—Processes for controlling fuel cells or fuel cell systems applied during specific periods applied during shut-down
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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
- H01M8/04537—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
- H01M8/04858—Electric variables
- H01M8/04865—Voltage
- H01M8/0488—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
- H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
- H01M8/04858—Electric variables
- H01M8/04895—Current
- H01M8/0491—Current 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
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
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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 control method for a fuel cell system and a fuel cell system.
- a predetermined anode electrode protection process is performed from the viewpoint of preventing oxidative degradation of the anode electrode catalyst at the time of starting the fuel cell.
- JP2014-523081A proposes an EAP (Electric Anode Protection) process that applies a reverse current (protection current) to the fuel cell stack when the system is stopped.
- the stack temperature is estimated based on the resistance information of the stack obtained by superimposing the high-frequency AC signal on the DC signal of the fuel cell stack, and the estimated stack temperature information
- the set current of the EAP process is adjusted based on the above.
- EAP treatment is effective as a method for preventing oxidative degradation of the anode catalyst, it consumes a large amount of power.
- an object of the present invention is to provide a control method of a fuel cell system and a fuel cell system capable of suppressing power consumption while suppressing oxidative deterioration of an anode electrode catalyst.
- a control method for a fuel cell system having a solid oxide fuel cell that generates electric power by receiving supply of anode gas and cathode gas includes an anode electrode protection execution determination process for determining whether to perform an anode electrode protection process in which a predetermined protection current is applied to the fuel cell in order to suppress catalytic oxidation of the anode electrode of the fuel cell.
- the anode electrode protection execution determination process the internal impedance of the fuel cell at the anode sensitive frequency at which the anode reaction resistance of the fuel cell can be detected is obtained, and the anode electrode protection process is executed based on the internal impedance of the anode sensitive frequency. Judge whether to do.
- FIG. 1 is a schematic configuration diagram of a fuel cell system according to an embodiment.
- FIG. 2 is a diagram schematically illustrating a DRT spectrum of a fuel cell stack according to an embodiment.
- FIG. 3 is a flowchart illustrating a flow of EAP execution determination processing according to an embodiment.
- FIG. 4 is a flowchart illustrating a method for specifying an anode sensitive frequency according to an embodiment.
- FIG. 5 shows an example of the DRT spectrum of the fuel cell stack.
- FIG. 6 is a flowchart illustrating a flow of EAP execution determination processing according to an embodiment.
- FIG. 7 is a flowchart illustrating a method for specifying an anode sensitive frequency according to an embodiment.
- FIG. 1 is a schematic configuration diagram of a fuel cell system according to an embodiment.
- FIG. 2 is a diagram schematically illustrating a DRT spectrum of a fuel cell stack according to an embodiment.
- FIG. 3 is a flowchart illustrating a flow of EAP execution determination
- FIG. 8 is a flowchart illustrating a flow of EAP execution determination processing according to an embodiment.
- FIG. 9 is a flowchart illustrating a flow of EAP processing according to an embodiment.
- FIG. 10 is a diagram for explaining the temperature dependence of the anode reaction resistance peak position in the DRT spectrum of the fuel cell stack.
- FIG. 11 is a flowchart illustrating a specific flow of anode sensitive frequencies according to one embodiment.
- FIG. 1 is a schematic configuration diagram of a fuel cell system 100 according to the present embodiment.
- a fuel cell system 100 includes a solid oxide fuel cell stack 10 that generates power by receiving supply of fuel gas (hydrogen gas) as an anode gas and air as a cathode gas.
- fuel gas hydrogen gas
- Type fuel cell system which is mounted on a vehicle or the like.
- the fuel cell stack 10 is a stacked battery in which a plurality of solid oxide fuel cells (SOFC: Solid Oxide Fuel Cell) are stacked.
- SOFC Solid Oxide Fuel Cell
- Each solid oxide fuel cell (fuel cell) constituting the stacked battery includes an electrolyte layer formed of a solid oxide such as ceramic, an anode electrode to which a fuel gas containing hydrogen, hydrocarbons, and the like is supplied, It is configured by being sandwiched between cathode electrodes to which air is supplied.
- an anode passage anode electrode passage
- cathode electrode passage cathode electrode passage
- the fuel cell stack 10 is provided with a stack temperature sensor 12 for detecting the temperature (hereinafter also referred to as “stack temperature Ts”).
- stack temperature Ts the temperature
- the stack temperature sensor 12 transmits a signal of the detected stack temperature Ts to the controller 80.
- the fuel cell system 100 includes a fuel supply mechanism 20 that supplies fuel gas to the fuel cell stack 10, an activation combustion mechanism 30 that combusts the fuel gas and air, and an air supply mechanism 40 that supplies air to the fuel cell stack 10.
- the exhaust mechanism 50 that exhausts the anode exhaust gas and the cathode exhaust gas discharged from the fuel cell stack 10, the power mechanism 60 that inputs and outputs power between the fuel cell stack 10, and the overall operation of the fuel cell system 100.
- a controller 80 for overall control is provided.
- the fuel supply mechanism 20 includes a fuel supply passage 21, a fuel tank 22, a filter 23, a pump 24, an injector 25, an evaporator 26, a heat exchanger 27, a reformer 28, and a pressure regulating valve 29. It is equipped with.
- the fuel supply passage 21 is a passage connecting the fuel tank 22 and the anode inlet 10 a of the fuel cell stack 10.
- the fuel tank 22 is a container that stores liquid fuel for reforming in which, for example, ethanol and water are mixed.
- the filter 23 is disposed in the fuel supply passage 21 between the fuel tank 22 and the pump 24.
- the filter 23 removes foreign matters and the like contained in the reforming fuel before being sucked into the pump 24.
- the pump 24 is provided in the fuel supply passage 21 on the downstream side of the fuel tank 22.
- the pump 24 sucks the reforming fuel stored in the fuel tank 22 and supplies the fuel to the injector 25 and the like.
- the output control of the pump 24 can also be executed by the controller 80.
- the injector 25 is disposed in the fuel supply passage 21 between the pump 24 and the evaporator 26.
- the injector 25 injects and supplies the fuel supplied from the pump 24 into the evaporator 26.
- the evaporator 26 is provided in the fuel supply passage 21 on the downstream side of the injector 25.
- the evaporator 26 vaporizes the fuel supplied from the injector 25 and supplies it to the heat exchanger 27.
- the evaporator 26 vaporizes the fuel by using the heat of the exhaust discharged from the exhaust combustor 53 described later.
- the heat exchanger 27 is provided in the fuel supply passage 21 downstream of the evaporator 26 and is disposed adjacent to the exhaust combustor 53. The heat exchanger 27 further heats the fuel vaporized in the evaporator 26 using the heat transmitted from the exhaust combustor 53.
- the pressure regulating valve 29 is provided in the fuel supply passage 21 between the evaporator 26 and the heat exchanger 27.
- the pressure regulating valve 29 adjusts the pressure of the vaporized fuel supplied to the heat exchanger 27.
- the opening degree of the pressure regulating valve 29 is controlled by the controller 80.
- the reformer 28 is provided in the fuel supply passage 21 between the heat exchanger 27 and the fuel cell stack 10.
- the reformer 28 reforms the fuel from the heat exchanger 27 using a catalyst provided in the reformer 28.
- the fuel from the heat exchanger 27 is reformed by a catalytic reaction in the reformer 28 into a fuel gas containing hydrogen, hydrocarbons, carbon monoxide and the like.
- the fuel gas thus reformed is supplied into the anode electrode passage through the anode inlet 10a of the fuel cell stack 10 in a high temperature state.
- the fuel supply passage 21 includes branch paths 71 and 72 that branch from the fuel supply passage 21.
- the branch path 71 branches from the fuel supply passage 21 between the pump 24 and the injector 25 and is connected to an injector 71 ⁇ / b> A that supplies fuel to the diffusion combustor 31.
- the branch path 71 is provided with an on-off valve 71B that opens and closes the branch path 71.
- the injector 71A is provided with an electric heater 71C as a heating device for vaporizing the liquid fuel.
- the branch path 72 branches from the fuel supply passage 21 between the pump 24 and the injector 25 and is connected to an injector 72A that supplies fuel to the catalytic combustor 32.
- the branch path 72 is provided with an on-off valve 72B that opens and closes the branch path 72.
- the on-off valves 71B and 72B described above are controlled to be opened and closed by the controller 80 when the fuel cell system 100 is started or stopped, for example.
- the air supply mechanism 40 includes an air supply passage 41, a filter 42, an air blower 43, a heat exchanger 44, and a throttle 45.
- the startup combustion mechanism 30 includes a diffusion combustor 31 and a catalytic combustor 32.
- the air supply passage 41 is a passage connecting the air blower 43 and the cathode inlet 10 b of the fuel cell stack 10.
- the air blower 43 takes outside air (air) through the filter 42 and supplies the taken air to the fuel cell stack 10 as cathode gas. Note that the output of the air blower 43 can be controlled by the controller 80.
- the filter 42 removes foreign matters contained in the air before being taken into the air blower 43.
- the heat exchanger 44 is provided in the air supply passage 41 on the downstream side of the air blower 43.
- the heat exchanger 44 is a device that heats the air using the heat of the exhaust discharged from the exhaust combustor 53.
- the air heated by the heat exchanger 44 is supplied to the diffusion combustor 31.
- the throttle 45 is provided in the air supply passage 41 between the air blower 43 and the heat exchanger 44.
- the opening degree of the throttle 45 is adjusted by the controller 80 in accordance with, for example, the air flow rate required by the fuel cell stack 10.
- the diffusion combustor 31 is disposed downstream of the heat exchanger 44 in the air supply passage 41.
- the diffusion combustor 31 is supplied with, for example, fuel gas vaporized during the warm-up operation when the fuel cell system 100 is started up and air from the air blower 43.
- the fuel injected through the injector 71 ⁇ / b> A of the branch path 71 is heated and vaporized by the electric heater 71 ⁇ / b> C to become fuel gas, and this fuel gas is supplied to the diffusion combustor 31.
- the air from the air blower 43 is supplied to the diffusion combustor 31 while being heated by the heat exchanger 44.
- the diffusion combustor 31 the supplied mixed gas of combustion gas and air is ignited and burned by an ignition device (not shown). That is, the diffusion combustor 31 functions as a preheating burner that supplies a high-temperature combustion gas (preheating combustion gas) to the catalytic combustor 32.
- the catalytic combustor 32 is provided in the air supply passage 41 between the diffusion combustor 31 and the fuel cell stack 10.
- the catalytic combustor 32 is a device that includes a catalyst therein and generates high-temperature combustion gas using the catalyst.
- the catalyst combustor 32 is supplied with gas (air and preheating combustion gas) from the air supply passage 41 and fuel injected through the injector 72A of the branch path 72.
- gas air and preheating combustion gas
- the catalyst of the catalytic combustor 32 is heated by the preheating combustion gas, and air and fuel are combusted on the heated catalyst to generate combustion gas.
- the combustion gas is a high-temperature inert gas containing almost no oxygen, and is supplied to the fuel cell stack 10 to heat the fuel cell stack 10 and the like. Thereby, the temperature of the fuel cell stack 10 can be raised to a desired operating temperature. Note that the fuel supply to the catalytic combustor 32 is stopped in the normal operation other than the warm-up operation. Therefore, in this case, the air supplied from the air blower 43 passes through the catalytic combustor 32 and is supplied to the fuel cell stack 10.
- the exhaust mechanism 50 includes an anode exhaust gas discharge passage 51, a cathode exhaust gas discharge passage 52, an exhaust combustor 53, a merged exhaust passage 54, and the like.
- the anode exhaust gas discharge passage 51 connects the anode outlet 10 c in the fuel cell stack 10 and the anode side inlet of the exhaust combustor 53.
- the anode exhaust gas discharge passage 51 is a passage through which anode exhaust gas containing fuel gas discharged from the fuel flow path of the fuel cell stack 10 flows.
- the cathode exhaust gas discharge passage 52 connects the cathode outlet 10 d in the fuel cell stack 10 and the cathode side inlet of the exhaust combustor 53.
- the cathode exhaust gas discharge passage 52 is a passage through which the cathode exhaust gas discharged from the cathode flow path in the fuel cell stack 10 flows.
- the anode exhaust gas from the anode exhaust gas discharge passage 51 and the cathode exhaust gas from the cathode exhaust gas discharge passage 52 are merged, and these are catalytically combusted to generate exhaust gas mainly composed of carbon dioxide and water.
- the exhaust combustor 53 Since the exhaust combustor 53 is disposed adjacent to the heat exchanger 27, heat generated by catalytic combustion in the exhaust combustor 53 is transmitted to the heat exchanger 27. The heat transferred to the heat exchanger 27 in this way is used to heat the fuel supplied to the reformer 28.
- a combined exhaust passage 54 is connected to the gas outlet (downstream end) of the exhaust combustor 53. Exhaust gas discharged from the exhaust combustor 53 is discharged outside the fuel cell system 100 through the merged exhaust passage 54.
- the combined exhaust passage 54 is configured to pass through the evaporator 26 and the heat exchanger 44, and the evaporator 26 and the heat exchanger 44 are heated by the exhaust gas that passes through the combined exhaust passage 54.
- the power mechanism 60 includes a DCDC converter 61 that functions as a protection current application device, a battery 62, a drive motor 63, an impedance measurement device 64, a current sensor 65, and a voltage sensor 66.
- the DCDC converter 61 is electrically connected to the fuel cell stack 10, boosts the output voltage of the fuel cell stack 10, and supplies power to the battery 62 and the drive motor 63.
- the battery 62 is configured to charge the power supplied from the DCDC converter 61 and supply power to the drive motor 63.
- the DCDC converter 61 is operated from the battery 62 in a scene where the anode electrode may be in an oxidizing atmosphere such as when the operation (power generation) of the fuel cell stack 10 is stopped based on a command from the controller 80.
- the process of applying the protection current is an anode electrode protection process (hereinafter, also referred to as “EAP process”) executed for the purpose of suppressing oxidative deterioration of the anode electrode. That is, the DCDC converter 61 functions as a protective current application device. In the present embodiment, the DCDC converter 61 is controlled by the controller 80.
- the drive motor 63 is a three-phase AC motor and functions as a power source for the vehicle.
- the drive motor 63 is connected to the battery 62 and the DCDC converter 61 via an inverter (not shown).
- the drive motor 63 generates regenerative power when the vehicle is braked, and this regenerative power is used for charging the battery 62, for example.
- the impedance measuring device 64 is a device that measures the internal impedance Z of the fuel cell stack 10 based on the output voltage and output current of the fuel cell stack 10. Specifically, the impedance measuring device 64 applies an AC signal having a predetermined frequency to the fuel cell stack 10 and calculates the internal impedance Z based on the AC signal (AC voltage and AC current) included in the output of the fuel cell stack 10. To do. Then, the impedance measuring device 64 outputs the measured internal impedance Z to the controller 80.
- the current sensor 65 detects the output current of the fuel cell stack 10.
- the voltage sensor 66 detects the output voltage of the fuel cell stack 10, that is, the inter-terminal voltage between the anode electrode side terminal and the cathode electrode side terminal.
- a controller 80 that comprehensively controls the operation of the entire system includes a central processing unit (CPU), a read-only memory (ROM), a random access memory (RAM), and an input / output interface (I / O interface). Consists of a computer. The controller 80 executes a process for controlling the fuel cell system 100 by executing a specific program.
- CPU central processing unit
- ROM read-only memory
- RAM random access memory
- I / O interface input / output interface
- the controller 80 includes signals from various measuring devices and sensors such as the stack temperature sensor 12, the impedance measuring device 64, the current sensor 65, and the voltage sensor 66, an outside temperature sensor 90 that detects the outside temperature, and operation of the EV key. Signals from an external sensor that detects a vehicle state, such as an EV key switch operation signal detection sensor 91 that detects a signal and an accelerator stroke sensor 92 that detects the amount of depression of an accelerator pedal, are input. Based on these signals, the controller 80 controls the opening of various valves and injectors and controls each actuator such as the DCDC converter 61.
- the controller 80 calculates the generated power target value of the fuel cell stack 10 based on the detection values from the various measuring devices and sensors and the operating state of the fuel cell stack 10 so that the generated power target value can be realized.
- Actuators such as various valves and injectors are controlled to adjust the amount of fuel gas and air supplied to the fuel cell stack 10.
- the controller 80 acquires the internal impedance Z at the anode sensitive frequency at which the anode reaction resistance of the fuel cell stack 10 can be detected from the impedance measuring device 64.
- the controller 80 performs an anode electrode protection execution determination process for determining whether or not to execute an anode electrode protection process for suppressing oxidation of the catalyst of the anode electrode based on the acquired internal impedance Z. This anode electrode protection execution determination process will be described in detail later.
- anode catalytic oxidation reaction occurs in which the nickel that is formed is oxidized to form nickel oxide.
- the anode catalytic oxidation reaction is of particular concern at the time of starting to start power generation of the fuel cell stack 10 or when the operation is stopped to stop power generation.
- the stack temperature Ts is close to the operation temperature suitable for power generation (for example, 700 ° C. to 900 ° C.) and exceeds the oxidation deterioration point.
- the supply of the fuel gas to the anode electrode of the fuel cell stack 10 is stopped or at least the supply flow rate is reduced.
- the pressure in the anode electrode decreases, and the outside air (air) flows backward from the merged exhaust passage 54 to the anode electrode through the anode exhaust gas discharge passage 51, increasing the oxygen concentration in the anode electrode and increasing the anode catalyst oxidation reaction. Is encouraged.
- the supply of air to the cathode electrode may be continued for the purpose of cooling while the flow rate of the fuel gas supplied to the anode electrode decreases.
- the pressure in the anode electrode is decreasing, the pressure in the cathode electrode is not greatly decreased. Therefore, the differential pressure between the anode and the cathode is increased, and so-called reverse diffusion in which air diffuses from the cathode to the anode is likely to occur. This reverse diffusion also increases the oxygen concentration in the anode electrode and promotes the anode catalyst oxidation reaction.
- the EAP treatment is performed when the operation is stopped to suppress the anode catalyst oxidation reaction.
- the EAP process consumes power, it is desired not to execute the EAP process as much as possible or to reduce the EAP current even if it is executed.
- the stack is based on stack resistance information (internal impedance) obtained by superimposing a high-frequency AC signal on the DC signal of the fuel cell stack.
- the temperature Ts was estimated, and the EAP current was adjusted according to the estimated stack temperature Ts.
- the internal impedance Z of the fuel cell stack 10 depends on the frequency of the AC signal used for measurement (hereinafter also referred to as “measurement frequency”), the anode electrode reaction resistance, the anode electrode diffusion resistance, and the cathode electrode reaction.
- Various elements hereinafter also referred to as “internal impedance components” such as resistance and diffusion resistance of the cathode electrode, and solid electrolyte information are included.
- each internal impedance component shows different responsiveness (sensitivity) for each measurement frequency. That is, the frequency that strongly influences the value of the internal impedance differs depending on the internal impedance component. More specifically, there are various types having high sensitivity to high frequencies and high sensitivity to low frequencies depending on the types of internal impedance components.
- the internal impedance in the high frequency band of several tens of kHz or more is strongly influenced by internal impedance components such as the state of the anode and cathode substrates and the contact resistance between the anode and cathode and the electrolyte.
- the stack temperature Ts does not necessarily correspond strictly to an internal impedance component that is highly sensitive to frequencies in this high frequency band.
- the EAP current is adjusted by the stack temperature Ts estimated by the internal impedance of the high frequency, the EAP current may be insufficient and the anode catalyst oxidation reaction may not be appropriately suppressed. Conversely, it is conceivable that the EAP current is set higher than the actual demand appropriate for suppressing the anode catalyst oxidation reaction, resulting in excessive power consumption.
- an anode sensitive frequency that is a frequency at which the anode reaction resistance can be detected is specified, and it is determined whether or not to execute the EAP process based on the internal impedance of the anode sensitive frequency.
- FIG. 2 is a diagram schematically showing a DRT (Distribution of Relaxation Time) spectrum of the fuel cell stack 10 in a peripheral frequency band including the anode sensitive frequency.
- FIG. 2 shows each DRT spectrum curve for each degree of oxidizing atmosphere in the anode electrode (catalyst oxidation progress of the anode electrode).
- the spectral curve C1 when the anodic oxidation degree is the smallest is indicated by a broken line
- the spectral curve C2 when the anodic oxidation degree is the next smallest is indicated by a dotted line
- the spectral curve C3 when the anodic oxidation degree is the highest is indicated by a solid line. It shows with.
- frequency and “angular frequency” are regarded as the same, and strictly speaking, even when “angular frequency” is meant, this is referred to as “frequency”.
- the DRT spectrum of the fuel cell stack 10 is a spectrum of the internal impedance Z corresponding to the relaxation time (reciprocal of frequency) obtained by executing DRT analysis (relaxation time distribution method) on the fuel cell stack 10.
- Non-Patent Document 1 Details of the DRT analysis are disclosed in, for example, “SOFC Moderlling and Parameter Identification” (Andre, Leonide, Yannick, Apel, Ellen, Ivers-Tiffee, The Electrochemical Society, May 1, 2009). Hereinafter, this document is simply referred to as “Non-Patent Document 1”.
- a relaxation time distribution (frequency distribution) is calculated from internal impedance measurement values at a plurality of frequencies in a predetermined frequency range (for example, 10 kHz to 0.1 Hz), and the calculated value is used using an appropriate equivalent circuit. And fitting using the complex nonlinear least squares method (Complex-non-linear least squares method). Thereby, DRTg (f) can be calculated, and the DRT spectrum of the fuel cell stack 10 shown in FIG. 2 is obtained.
- the DRT spectrum obtained by the DRT analysis information on various internal impedance components is displayed according to the difference in each relaxation time, that is, according to the difference in the sensitive frequency.
- the anode reaction resistance and the cathode reaction resistance as main internal impedance components are included in the frequency range of 10 Hz to 10 kHz.
- the DRT spectrum of FIG. 2 includes a peak correlated with the cathode reaction resistance (hereinafter also referred to as “cathode reaction resistance peak P 2c ”), and a first peak correlated with the anode reaction resistance (hereinafter referred to as “cathode reaction resistance peak P 2c ”).
- a peak correlated with the cathode reaction resistance hereinafter also referred to as “cathode reaction resistance peak P 2c ”
- a first peak correlated with the anode reaction resistance hereinafter referred to as “cathode reaction resistance peak P 2c ”.
- Also described as a low frequency side anode electrode reaction resistance peak P 2A and a second peak correlated with the anode electrode reaction resistance (hereinafter, also referred to as “high frequency side anode electrode reaction resistance peak P 3A ”).
- the frequency ⁇ P2c of the cathode electrode reaction resistance peak P 2c is located in the vicinity of 10 Hz
- the ⁇ P2A of the low frequency side anode electrode reaction resistance peak P 2A is located between 100 Hz and 1 kHz
- ⁇ P3A corresponding to the anode electrode reaction resistance peak P 3A is located in the vicinity of 10 kHz.
- the low frequency side anode electrode reaction resistance peak P 2A and the high frequency side anode electrode reaction resistance peak P 3A are changed in accordance with the progress of the catalytic oxidation of the anode electrode.
- the progress of the catalytic oxidation of the anode electrode in FIG. 2 is defined by, for example, the oxygen concentration when a predetermined amount of air corresponding to the specifications of the fuel cell stack 10 is supplied into the anode electrode. That is, by supplying air into the anode electrode, hydrogen in the anode electrode is discharged, and the hydrogen concentration in the anode electrode decreases and the oxygen concentration increases, so that the anode catalyst oxidation reaction further proceeds.
- the low frequency side anode electrode reaction resistance peak P 2A and the high frequency side anode electrode reaction resistance peak P 3A become higher as the progress of the catalytic oxidation of the anode electrode becomes larger and the anode catalytic oxidation reaction proceeds. That is, the low frequency side anode electrode reaction resistance peak P 2A and the high frequency side anode electrode reaction resistance peak P 3A increase as the catalytic oxidation of the anode electrode proceeds.
- the cathode reaction resistance peak P 2c does not substantially correlate with the progress of the catalytic oxidation of the anode electrode. That is, even if the catalytic oxidation of the anode proceeds, the theoretical change in the cathode reaction resistance peak P 2c is zero except for the variation ⁇ P 2c due to other errors.
- the present inventors have found that the low-frequency side anode reaction resistance peak P 2A frequency omega P2A and the high-frequency side anode reaction resistance peak P 3A frequency omega least one of P3A, or frequency omega P2A of We focused on referring to the magnitude of the internal impedance at at least one of the peripheral frequency and the peripheral frequency of the frequency ⁇ P3A . Then, the present inventors have arrived at the idea of diagnosing the progress of the catalytic oxidation of the anode electrode based on the magnitude of the internal impedance and determining whether to perform the EAP process in the fuel cell system 100.
- the peripheral frequency of the frequency ⁇ P2A means any frequency within a frequency range in which the influence of the catalytic oxidation of the anode electrode can be detected from the DRT spectrum. That is, it is a frequency in the vicinity of the frequency ⁇ P2A corresponding to the spread width of the low frequency side anode electrode reaction resistance peak P 2A , and the catalytic oxidation of the anode electrode is more than the internal impedance Z ( ⁇ P2A ) at a single frequency ⁇ P2A .
- the amount of change corresponding to the change is low, it is a frequency at which detection is possible and the internal impedance Z can change to some extent.
- the definition of the peripheral frequency of the frequency ⁇ P3A is the same as the peripheral frequency of the frequency ⁇ P2A .
- the frequency ⁇ P2A and its peripheral frequencies are collectively referred to as “frequency ⁇ P2A ”, and the frequency ⁇ P3A and its peripheral frequencies are collectively referred to as “frequency ⁇ P3A ”. That is, in the following description, “frequency ⁇ P2A ” and “frequency ⁇ P3A ” are not limited to only one point of the frequency, but are concepts that can include the respective peripheral frequencies. That is, the anode-sensitive frequency in this embodiment means one of the frequency ⁇ P2A and its peripheral frequency, or the frequency ⁇ P3A and its peripheral frequency, or both.
- the DRTg (f P2A ) ( ⁇ internal impedance Z ( ⁇ P2A )) of the frequency ⁇ P2A increases by a change amount ⁇ P 2A according to the change in the anode reaction resistance caused by the catalytic oxidation of the anode electrode. Further, the DRTg (f P3A ) ( ⁇ internal impedance Z ( ⁇ P3A )) of the frequency ⁇ P3A increases by a change amount ⁇ P 3A according to the change in the anode reaction resistance caused by the catalytic oxidation of the anode electrode.
- the internal impedance Z ( ⁇ P2A ) and the internal impedance Z ( ⁇ P3A ) have almost no correlation with the fluctuation of the internal impedance components other than the anode electrode reaction resistance such as the cathode electrode reaction resistance described above. That is, ⁇ P 2A of the internal impedance Z ( ⁇ P2A ) and ⁇ P 3A of the internal impedance Z ( ⁇ P3A ) due to changes in the anode electrode reaction resistance are very large compared to the internal impedance components other than the anode electrode reaction resistance.
- the progress of the anode catalytic oxidation reaction can be properly diagnosed, and the EAP process in the fuel cell system 100 can be performed. Implementation decisions can be made appropriately.
- the operating state of the fuel cell stack 10 such as the internal gas pressure and the stack temperature Ts changes variously at the required load.
- differences in electrochemical characteristics due to individual differences in the fuel cell stack 10 also occur. It is assumed that the above-mentioned DRT spectrum changes variously due to such factors.
- the low frequency anode reaction resistance peak P 2A may shift to the low frequency side, or the width of the cathode reaction resistance peak P 2c may increase.
- the low frequency anode reaction resistance peak P 2A is mixed with the cathode reaction resistance peak P 2c .
- the internal impedance Z ( ⁇ P2A ) of the frequency ⁇ P2A includes not only the progress information of the oxidation reaction of the anode electrode but also the information of the cathode electrode reaction resistance having a low correlation with the oxidation reaction of the anode electrode.
- the high-frequency anode reaction resistance peak P 3A farther from the cathode reaction resistance peak P 2c is used. That is, based on the internal impedance Z ( ⁇ P3A ) of the frequency ⁇ P3A , the execution determination of the EAP process is performed.
- the flow of the EAP execution determination process based on the internal impedance Z ( ⁇ P3A ) of the frequency ⁇ P3A will be described.
- FIG. 3 is a flowchart showing the flow of the EAP execution determination process according to the present embodiment.
- the EAP execution determination process of the present embodiment is executed, for example, triggered by reception of an EV key-off signal (an instruction to stop operation of the fuel cell stack 10). That is, before the cooling process executed when the operation of the fuel cell stack 10 is stopped, and the like, there is a possibility that the anode electrode may become an oxidizing atmosphere even though the stack temperature Ts is equal to or higher than the oxidation deterioration point. Is executed.
- the following routine is repeatedly executed by the controller 80 at a predetermined cycle.
- step S110 the frequency ⁇ P3A corresponding to the high-frequency anode reaction resistance peak P 3A is specified as the anode sensitive frequency by DRT analysis.
- FIG. 4 is a flowchart showing a flow of specifying the frequency ⁇ P3A that is the anode sensitive frequency.
- step S111 the controller 80 measures the internal impedance measurement values at a plurality of frequencies belonging to a predetermined frequency band (for example, 0.1 Hz to 100 kHz) among the measurement values of the internal impedance Z measured by the impedance measurement device 64 (see FIG. (Hereinafter also referred to as “internal impedance measurement value group”) is extracted from a memory or the like.
- a predetermined frequency band for example, 0.1 Hz to 100 kHz
- step S112 the controller 80 calculates a relaxation time distribution from the acquired internal impedance measurement value group, and fits the calculated value by a complex nonlinear least square method using an appropriate equivalent circuit. Thereby, DRTg (f) is obtained. That is, the DRT spectrum represented by DRTg (f) corresponds to a regression curve of a group of measured internal impedance values using the equivalent circuit as a model.
- step S113 the controller 80 extracts the frequency ⁇ P3A from the obtained DRT spectrum according to a preset frequency extraction program. Specifically, the controller 80 first calculates a differential value of DRTg (f) in the frequency band of 100 Hz to several tens of kHz where the high frequency side anode electrode reaction resistance peak P 3A is likely to appear. Then, the controller 80 records the frequency ⁇ p at which the differential value of DRTg (f) is zero or less than a predetermined value close to zero.
- the controller 80 extracts this as the frequency ⁇ P3A .
- the controller 80 when recording the frequency omega p there are multiple, among the frequency omega p, extracts a small frequency omega p to the second as a frequency omega P3A.
- the reason why the second smallest frequency ⁇ p is thus set to the frequency ⁇ P3A is that when a plurality of frequencies ⁇ p are recorded, the smallest frequency ⁇ p is applied to the low-frequency anode reaction resistance peak P 2A . This is because the corresponding frequency ⁇ P2A is highly likely, while the third and subsequent frequencies ⁇ p are likely to be internal impedance components of other high frequency responses.
- the frequency ⁇ P3A corresponding to the high-frequency anode reaction resistance peak P 3A can be specified by the process described above.
- step S120 the controller 80 calculates the anode reaction resistance Ra ( ⁇ P3A ). Specifically, the controller 80 acquires the internal impedance Z ( ⁇ P3A ) corresponding to the frequency ⁇ P3A extracted in step S110 from the internal impedance measurement value group. Then, the controller 80 calculates the absolute value of the internal impedance Z ( ⁇ P3A ) to obtain the anode electrode reaction resistance Ra.
- step S130 the controller 80 determines whether or not the acquired anode reaction resistance Ra exceeds a predetermined threshold value Rath recorded in advance in a memory or the like.
- the threshold value Rath is determined from the viewpoint of whether or not the catalytic oxidation of the anode electrode is progressing to the extent that the EAP process needs to be performed.
- the anode reaction resistance Ra increases as the oxygen concentration in the anode electrode increases (the hydrogen concentration decreases).
- the oxygen concentration does not increase so much, it is assumed that the oxidation reaction does not proceed to the extent that the irreversible deterioration of the catalyst occurs even if the EAP treatment is not performed.
- an increase amount of the oxygen concentration that may adversely affect the anode electrode catalyst through experiments and the like and the anode electrode corresponding to the increase amount of the oxygen concentration.
- the relationship of the increase amount of the reaction resistance Ra is determined, and the threshold value Rath is determined based on the increase amount of the anode reaction resistance Ra.
- step S140 the controller 80 sets the predetermined EAP current and executes the EAP process so as to suppress the catalytic oxidation of the anode electrode.
- step S150 the controller 80 does not execute the EAP process or stops the EAP process if it is already executed.
- the anode reaction resistance Ra is equal to or less than the threshold value Rath, it is considered that the catalyst oxidation does not proceed to such an extent that the irreversible deterioration of the catalyst occurs without performing the EAP process. In this case, the EAP process is not performed. Thus, power consumption can be suppressed.
- the control method of the fuel cell system 100 of the present embodiment described above has the following operational effects.
- an anode electrode protection execution determination process for performing an EAP process determination as an anode electrode protection process in which a predetermined protection current is applied to the fuel cell stack 10 in order to suppress catalytic oxidation of the anode electrode of the fuel cell stack 10.
- the EAP execution determination process is included.
- the internal impedance Z ( ⁇ P3A ) of the fuel cell stack 10 at the frequency ⁇ P3A as the anode sensitive frequency that can detect the anode reaction resistance Ra of the fuel cell stack 10 is acquired (step S120 in FIG. 3). ) Based on the acquired internal impedance Z ( ⁇ P3A ), it is determined whether or not to execute the EAP process (step S130 in FIG. 3).
- the internal impedance Z ( ⁇ P3A ) at the frequency ⁇ P3A as the anode sensitive frequency varies depending on the progress of the catalytic oxidation in the anode electrode that can cause irreversible deterioration of the anode electrode catalyst. Therefore, by determining the execution timing of the EAP process based on the internal impedance Z ( ⁇ P3A ), the EAP process can be accurately executed at a necessary timing, and the increase in power consumption due to the execution of the unnecessary EAP process is achieved. Can be suppressed. On the other hand, since the EAP process can be appropriately executed in a necessary scene, the oxidative deterioration of the anode electrode catalyst can be suppressed.
- the control method of the fuel cell system 100 of the present embodiment the anode sensitive frequency variation [delta] P 3A of variation [delta] P 3A of the internal impedance Z due to changes in the anode reaction resistance Ra ( ⁇ P3A) (DRTg ( f) ) Is a frequency ⁇ P3A that is equal to or higher than a predetermined value.
- the internal impedance Z ( ⁇ P3A ) is more strongly correlated with the progress of catalytic oxidation in the anode electrode. Therefore, it is possible to further improve the accuracy of execution determination of EAP processing based on the internal impedance Z ( ⁇ P3A ).
- the “predetermined value” various values are assumed depending on the configuration of the fuel cell stack 10 (the number of stacked fuel cell cells, electrode materials, and individual differences).
- the “predetermined value” is determined so that the amount of change in the internal impedance Z ( ⁇ P3A ) can be detected before the catalyst oxidation in the anode electrode proceeds more than a certain level and irreversible deterioration of the anode electrode catalyst begins. It is preferable.
- the frequency ⁇ P3A is a change amount ⁇ P 3A of the internal impedance Z ( ⁇ P3A ) due to the change of the anode electrode reaction resistance Ra, and the change of internal impedance components (cathode electrode reaction resistance, etc.) other than the anode electrode reaction resistance Ra.
- This is a frequency that is larger than the amount of change in internal impedance Z ( ⁇ P3A ) due to.
- the internal impedance Z ( ⁇ P3A ) reflects the influence of the progress of the catalytic oxidation in the anode electrode more strongly than the influence of changes in other internal impedance components. Therefore, it is possible to further improve the accuracy of execution determination of the EAP process based on the internal impedance Z ( ⁇ P3A ).
- the internal impedance component of this embodiment includes a cathode reaction resistance that is the cathode reaction resistance of the fuel cell stack 10.
- the anode sensitive frequency is a high frequency side anode electrode reaction resistance peak P 3A and a low frequency which are two peaks correlated with the anode electrode reaction resistance Ra in DRTg (f) as spectrum data representing the internal impedance Z ( ⁇ ).
- the frequency ⁇ P3A corresponding to the high frequency side anode electrode reaction resistance peak P 3A which is one of the side anode electrode reaction resistance peaks P 2A is included.
- the term “frequency ⁇ P3A ” includes not only the constant frequency ⁇ P3A strictly matching the high-frequency anode reaction resistance peak P 3A , but also the surrounding frequencies. Is also included.
- EAP Implementation determination processing will be performed. That is, in the EAP execution determination process, it is possible to use the internal impedance Z ( ⁇ P3A ) in which the influence of the cathode reaction resistance peak P 2c is less likely to be included and the progress of catalytic oxidation in the anode electrode becomes more dominant. Therefore, even when the cathode reaction resistance peak P 2c spreads due to factors such as the operating state of the fuel cell stack 10 and individual differences, the catalytic oxidation of the anode electrode can be detected with high accuracy. The accuracy can be further improved.
- the anode sensitive frequency specifying process (see step S110 in FIG. 3) for specifying the frequency ⁇ P3A is executed. More specifically, the controller 80 is programmed to perform processing for specifying the anode sensitive frequency. That is, even in the fuel cell system 100 mounted on the vehicle, it is possible to acquire in real time the frequency ⁇ P3A of the appropriate internal impedance Z ( ⁇ ) for performing the EAP execution determination process.
- the EAP execution determination process is executed when the anode electrode reaction resistance Ra is higher than a predetermined threshold value Rath.
- the EAP execution determination process can be performed more appropriately by appropriately setting the threshold value Rath according to a difference in electrochemical characteristics due to individual differences of the fuel cell stack 10 or the like.
- the EAP execution determination process is executed when the operation of the fuel cell stack 10 is stopped. More specifically, the controller 80 is programmed to perform an EAP execution determination process when an EV key-off signal, which is a fuel cell operation stop command, is received.
- the EAP execution determination process can be performed particularly in a scene when the fuel cell stack 10 is shut down, which is highly likely to cause oxidative deterioration of the anode electrode catalyst. Therefore, irreversible oxidative deterioration of the anode electrode catalyst occurs. Can be prevented more reliably.
- the fuel cell system 100 suppresses the catalytic oxidation of the fuel cell stack 10 as a solid oxide fuel cell that generates power by receiving supply of hydrogen gas and air, and the anode electrode of the fuel cell stack 10.
- DCDC converter 61 as a protective current application device that applies a protective current to the fuel cell stack 10, an impedance measurement device 64 that measures the internal impedance Z ( ⁇ ) of the fuel cell stack 10, and a measurement by the impedance measurement device 64.
- a controller 80 that executes an EAP process for applying the protection current by controlling the DCDC converter 61 based on the internal impedance Z ( ⁇ ).
- the controller 80 acquires the internal impedance Z ( ⁇ P3A ) of the fuel cell stack 10 at the frequency ⁇ P3A as the anode sensitive frequency that can detect the anode electrode reaction resistance Ra (step S120 in FIG. 3), and the frequency ⁇ P3A Is programmed to execute an EAP execution determination process (step S130 in FIG. 3) for determining whether or not to execute the EAP process based on the internal impedance Z ( ⁇ P3A ).
- the EAP process can be accurately executed at the necessary timing, so that an increase in power consumption due to the execution of the unnecessary EAP process can be suppressed, and the EAP process is appropriately executed when necessary. Oxidative deterioration of the anode electrode catalyst can be suppressed.
- FIG. 5 shows an example of the DRT spectrum of the fuel cell stack 10 having a general configuration. Note that the DRT spectrum shown in FIG. 5 is obtained in the following flow.
- the internal impedance Z is measured in a measurement frequency range of 100 kHz to 0.1 Hz while changing the hydrogen concentration in the anode electrode of the fuel cell stack 10 while balancing with an inert gas (nitrogen gas). That is, the contents of air other than hydrogen and nitrogen in the anode are fixed.
- the internal impedance Z is measured when the hydrogen concentration is 65%, 30%, 20%, 15%, and 10%.
- a spectrum S1, a hydrogen concentration of 65%, a spectrum S2, a spectrum 30%, a spectrum 20% S3, a spectrum S4 15%, and a spectrum S5 10% are represented by a solid line, a broken line, a dotted line, a dashed line, And indicated by a two-dot chain line. That is, in each of the spectra S1 to S5, the hydrogen concentration in the anode electrode decreases in this order. Therefore, as the hydrogen concentration in the anode electrode decreases in the order of the spectra S1 to S5, the ratio of oxygen to the hydrogen gas in the anode electrode increases, and the reaction resistance of the anode electrode increases. That is, the spectra S1 to S5 in FIG. 5 can be regarded as the possibility that the catalytic oxidation of the anode electrode is increased in this order.
- the low-frequency anode reaction resistance peak P 2A of spectrum S1 appears in the vicinity of 100 Hz, and the low-frequency anode reaction resistance peak P 2A of spectra S2 to S5 is between 10 Hz and 100 Hz.
- all of the high-frequency anode reaction resistance peaks P 3A in the spectra S1 to S5 appear between 100 Hz and 1 kHz.
- both the low frequency side anode electrode reaction resistance peak P 2A and the high frequency side anode electrode reaction resistance peak P 3A move from the spectrum S1 to the spectrum S5, that is, the catalytic oxidation of the anode electrode occurs. It shows a tendency to increase as it progresses.
- the low-frequency anode reaction resistance peak P 2A of all the spectra S1 to S5 shown in FIG. 5 overlaps with the cathode reaction resistance peak P 2c .
- the low frequency side anode electrode reaction resistance peak P 2A includes not only the information on the progress of catalytic oxidation of the anode electrode but also information on the cathode electrode reaction resistance. Therefore, if the oxidation reaction in the cathode electrode is hindered due to insufficient oxygen partial pressure in the cathode electrode, the low-frequency anode reaction resistance peak may be obtained even if the catalyst oxidation of the anode electrode has not progressed. It is assumed that the value of the internal impedance Z ( ⁇ P2A ) at the corresponding frequency ⁇ P2A of P 2A will increase.
- the high-frequency anode reaction resistance peak P 3A is less affected by the cathode reaction resistance, while the amount of change with respect to the progress of the catalytic oxidation of the anode is low. Less than the frequency side anode electrode reaction resistance peak P 2A .
- the inventors of the present invention are concerned with the catalytic oxidation of the anode electrode such as when the operation of the fuel cell stack 10 is stopped or started up. Focusing on the fact that the possibility of lowering the reaction resistance peak P 2c greatly decreases, the internal impedance Z based on the low frequency anode reaction resistance peak P 2A close to the cathode reaction resistance peak P 2c We came up with making an EAP execution process determination at ( ⁇ P2A ).
- the cathode reaction resistance peak P 2c has an oxygen partial pressure of 0.21 atm in the cathode electrode. In the range from 0.02 to 0.02 atm, the height does not change greatly. In particular, in the range of 0.21 atm to 0.05 atm, the height of the cathode electrode reaction resistance peak P 2c tends to be approximately the same.
- the anode exhaust gas discharge passage 51 The reverse flow of gas into the anode electrode and the back diffusion of the air in the cathode electrode into the anode electrode occur. That is, since the air in the cathode electrode is rather abundant, a situation in which the oxygen partial pressure is less than 0.05 atm is unlikely to occur.
- the internal impedance Z ( ⁇ P2A ) based on the low frequency side anode electrode reaction resistance peak P 2A is substantially unaffected by the cathode electrode reaction resistance, and catalytic oxidation of the anode electrode It will change only according to the progress of.
- the low frequency side anode electrode reaction resistance peak P 2A has a change amount with the progress of oxidation of the anode electrode catalyst compared with the change amount of the high frequency side anode electrode reaction resistance peak P 3A. Big.
- FIG. 6 is a flowchart showing the flow of the EAP execution determination process according to this embodiment.
- FIG. 7 is a flowchart showing a flow of specifying the frequency ⁇ P2A that is the anode sensitive frequency of the present embodiment.
- the EAP execution process determination is basically performed in the same flow as the flow described in the first embodiment with reference to FIGS. 3 and 4, and therefore the same process steps as in the first embodiment are the same. The step number is attached.
- step S110 ′ the frequency ⁇ P2A corresponding to the low frequency anode reaction resistance peak P 2A is specified as the anode sensitive frequency by DRT analysis.
- step S111 the internal impedance measurement value group extraction in step S111 and the DRTg (f) calculation in step S112 are performed as in the first embodiment.
- step S113 ′ the frequency ⁇ P2A is extracted from the obtained DRT spectrum according to a preset frequency extraction program.
- the controller 80 first calculates the differential value of DRTg (f) in the frequency band of 10 Hz to 1 kHz where the low frequency side anode electrode reaction resistance peak P 2A is likely to appear. Then, the controller 80 records the frequency ⁇ p at which the differential value of DRTg (f) is zero or less than a predetermined value close to zero. Furthermore, when the recorded frequency ⁇ p is only one, the controller 80 extracts this as the frequency ⁇ P2A . On the other hand, if the recorded frequency omega p there are multiple, among the frequency omega p, and extracts the smallest frequency omega p as the frequency omega P2A.
- the low frequency side anode electrode reaction resistance peak P 2A is shifted to the low frequency side as the catalytic oxidation of the anode electrode proceeds (indicated by a white dotted line arrow in FIG. 5).
- a frequency corresponding to this also shift phenomenon occurring low frequency side anode reaction resistance peak P 2A ⁇ P2A is approximately 10 Hz or more.
- the smallest one of the frequencies ⁇ p at which the differential value of DRTg (f) in the frequency band of 10 Hz to 1 kHz is zero or less than a predetermined value close to zero is extracted as the frequency ⁇ P2A. Therefore, the frequency ⁇ P2A of the low-frequency side anode electrode reaction resistance peak P 2A can be accurately determined regardless of the progress of the catalytic oxidation of the anode electrode (in any of the states S1 to S5 in FIG. 5). Can be identified.
- the processing after step S120 in FIG. 6 is executed in the same manner as in the first embodiment.
- the value of the internal impedance Z ( ⁇ P2A ) does not substantially change even if the cathode reaction resistance changes.
- the internal impedance Z ( ⁇ P2A) values of the cathode reaction resistance when the steady state where no shortage of oxygen concentration in the cathode electrode is included correspondingly, the internal impedance Z ( ⁇ P2A)
- the anode reaction resistance Ra calculated based on the above becomes larger than the theoretical value. Therefore, in consideration of the fact that the anode reaction resistance Ra includes the cathode reaction resistance in the steady state, the threshold Ra is set higher than the cathode reaction resistance in the steady state. The accuracy can be further improved.
- the control method of the fuel cell system 100 of the present embodiment described above has the following operational effects.
- the internal impedance component of this embodiment includes a cathode electrode reaction resistance that is a cathode electrode reaction resistance of the fuel cell stack 10.
- the anode sensitive frequency is a high frequency side anode electrode reaction resistance peak P 3A and a low frequency which are two peaks correlated with the anode electrode reaction resistance Ra in DRTg (f) as spectrum data representing the internal impedance Z ( ⁇ ). among the side anode reaction resistance peak P 2A, it includes a frequency omega P2A corresponding to the low frequency side anode reaction resistance peak P 2A closer to the cathode reaction resistance peak P 2c is a peak which correlates to the cathode reaction resistance.
- EAP execution determination processing can be performed based on the internal impedance Z ( ⁇ P2A ).
- the low frequency side anode electrode reaction resistance peak P 2A has a higher correlation (sensitivity) to the progress of the catalytic oxidation of the anode electrode than the high frequency side anode electrode reaction resistance peak P 3A .
- the EAP execution determination process can be executed with higher accuracy. .
- the anode sensitivity frequency includes the frequency ⁇ P2A corresponding to the low frequency side anode electrode reaction resistance peak P 2A and the frequency ⁇ P3A corresponding to the high frequency side anode electrode reaction resistance peak P 3A. This is also true for the EAP execution determination based on the impedances Z ( ⁇ P2A ) and Z ( ⁇ P3A ).
- FIG. 8 is a flowchart showing the flow of EAP processing execution determination according to the present embodiment. As shown in the figure, the processes of step S110 ′ and step S120 are executed as in the second embodiment.
- the reference anode electrode reaction resistance Ra0 is, for example, the value of the anode electrode reaction resistance Ra in the steady state of the fuel cell stack 10, and is experimentally determined in advance according to the specifications of the fuel cell stack 10 and the like.
- the anode reaction resistance Ra in the steady state of the fuel cell stack 10 means that the inside of the anode electrode is sufficiently kept in a reducing atmosphere and no catalytic oxidation of the anode electrode occurs, and the stack temperature Ts is the fuel cell. This is the internal impedance of the fuel cell stack 10 in an open circuit state when the stack 10 is at an appropriate operating temperature (for example, 700 ° C. to 900 ° C.).
- step S130 the controller 80 determines whether or not the increase rate ⁇ Ra obtained in step S125 exceeds a predetermined threshold value ⁇ Rath recorded in advance in a memory or the like.
- the threshold value ⁇ Rath is determined from the viewpoint of whether or not the catalytic oxidation of the anode electrode has progressed to an extent that requires execution of the EAP process, as compared with the steady state of the fuel cell stack 10.
- the threshold ⁇ Rath is individually determined according to specifications such as the number of stacked fuel cell stacks 10 and constituent materials, and individual differences, while taking a safety margin so that the catalytic oxidation of the anode electrode does not lead to irreversible deterioration. It is determined so that an increase factor ⁇ Ra as large as possible is allowed.
- step S140 executes the EAP process.
- step S150 stops the EAP process if the EAP process is not executed or is already executed.
- the anode reaction resistance Ra calculated based on the internal impedance Z ( ⁇ P2A ) includes the value of the cathode reaction resistance in the steady state. It is considered to be larger than the typical value. However, the cathode reaction resistance in the steady state is smaller than the anode reaction resistance Ra. Further, since the cathode reaction resistance does not substantially change for the reason described in the second embodiment, the increase rate ⁇ Ra substantially depends only on the change in the anode reaction resistance Ra. Therefore, even when the threshold value ⁇ Rath is set without considering the influence of the cathode electrode reaction resistance in the steady state, the accuracy of the EAP execution determination can be maintained with high accuracy.
- the control method of the fuel cell system 100 of the present embodiment described above has the following operational effects.
- the anode electrode reaction resistance Ra is estimated based on the internal impedance Z ( ⁇ P2A ) of the anode sensitivity frequency, and the estimated anode electrode reaction
- the reference anode electrode reaction resistance Ra0 in the steady state (the state where the catalytic oxidation of the anode electrode is not progressing) is individually determined according to the specifications such as the number of stacked fuel cell stacks 10 and the constituent materials and individual differences.
- the EAP processing can be executed based on the setting. Therefore, it is possible to make an EAP process execution determination while taking into account variations in the reference anode electrode reaction resistance Ra0 in accordance with specifications such as the number of stacked fuel cell stacks 10 and constituent materials, and individual differences.
- the EAP process can be executed at a proper timing.
- the fourth embodiment will be described below.
- the same reference numerals are given to the same elements as those in the first to third embodiments, and the description thereof is omitted.
- the applied voltage (EAP current) in the EAP process when the EAP process is executed in step S140 is the anode reaction. Adjust based on resistance Ra.
- the EAP process after it is determined that the EAP process is executed in the EAP execution determination based on the internal impedance Z ( ⁇ P2A ) of the frequency ⁇ P2A in the second embodiment will be described.
- the present embodiment can also be applied to the EAP process after it is determined that the EAP process is executed in the EAP execution determination based on the internal impedance Z ( ⁇ P3A ) of the frequency ⁇ P3A in the first embodiment.
- FIG. 9 is a flowchart showing the flow of the EAP process of the present embodiment.
- the controller 80 calculates the EAP current in step S141. Specifically, the EAP current is determined based on the difference between the anode reaction resistance Ra calculated in step S120 of FIG. 6 and a predetermined threshold value R′ath.
- the threshold value R′ath can be determined as an appropriate EAP setting current, for example, from the viewpoint of maintaining a reducing atmosphere in the anode electrode so that the catalytic oxidation of the anode electrode does not proceed so as to cause irreversible deterioration of the catalyst. . That is, the threshold value R′ath is appropriately determined as an index sufficient to determine that the anode electrode is suitably maintained in a reducing atmosphere when the anode electrode reaction resistance Ra does not exceed the threshold value R′ath. .
- the threshold value R′ath is recorded in the memory of the controller 80 or the like.
- the threshold value R′ath may be the same value as the threshold value Rath used in step S130 of FIG. 6 in the EAP process execution determination, or may be a different value.
- the values are different, by setting the threshold value R′ath to be lower than the threshold value Rath, the EAP current is set to be relatively high, and the inside of the anode electrode is more reliably maintained in a reducing atmosphere. Can do.
- step S142 the controller 80 discloses EAP processing. Specifically, the controller 80 controls the DCDC converter 61 to adjust the supply current to the fuel cell stack 10 to the EAP current set in step S ⁇ b> 141 so as to be supplied to the fuel cell stack 10. As a result, a reverse voltage corresponding to the set EAP current is applied to the fuel cell stack 10.
- step S143 the controller 80 determines whether or not the anode reaction resistance Ra exceeds the threshold value R'ath. If the controller 80 determines that the anode electrode reaction resistance Ra does not exceed the threshold value R′ath, the controller 80 proceeds to step S144 and stops the EAP process. On the other hand, when the controller 80 determines that the anode electrode reaction resistance Ra exceeds the threshold value R′ath, the controller 80 repeats the processing after step S141.
- the control method of the fuel cell system 100 of the present embodiment described above has the following operational effects.
- the fuel cell system 100 of the present embodiment adjusts the protection current applied to the fuel cell stack 10 when it is determined to execute the EAP process in the EAP execution determination process (Yes in step S130 in FIG. 6).
- EAP current calculation processing step S141 in FIG. 9) as processing is included.
- the magnitude of the protection current is determined based on the difference between the anode electrode reaction resistance Ra estimated based on the internal impedance Z ( ⁇ P2A ) of the anode sensitive frequency and a predetermined threshold value R′ath. Current).
- the EAP current is appropriately set from the viewpoint of suppressing excessive power consumption while performing the function of suppressing the oxidative deterioration of the catalyst according to the progress of the catalytic oxidation in the anode electrode. be able to.
- the EAP current is calculated based on the difference between the anode reaction resistance Ra estimated based on the internal impedance Z ( ⁇ P2A ) of the anode sensitive frequency and the predetermined threshold value R′ath. It is set.
- the EAP current may be set based on the difference between the increase rate ⁇ Ra described in the third embodiment and a predetermined threshold value ⁇ R′ath.
- FIG. 10 is a diagram for explaining the temperature dependence of the positions of the low frequency side anode electrode reaction resistance peak P 2A and the high frequency side anode electrode reaction resistance peak P 3A in the DRT spectrum of the fuel cell stack 10.
- the positions of the low frequency side anode electrode reaction resistance peak P 2A and the high frequency side anode electrode reaction resistance peak P 3A shift to the high frequency side as the stack temperature Ts increases. That is, the frequency ⁇ P2A and the frequency ⁇ P3A respectively corresponding to the low frequency side anode electrode reaction resistance peak P 2A and the high frequency side anode electrode reaction resistance peak P 3A increase as the stack temperature Ts increases.
- the frequency of the internal impedance Z used for EAP execution determination is corrected.
- the frequency ⁇ P2A and the frequency ⁇ P3A are collectively referred to as a frequency ⁇ PA .
- step S110 of FIG. 4 and step S110 ′ of FIG. 7 when specifying the frequency in step S110 of FIG. 4 and step S110 ′ of FIG. 7, the correction frequency ⁇ ′ PA corrected in consideration of the stack temperature Ts is extracted. This will be described in more detail below.
- FIG. 11 is a flowchart showing a flow of processing for specifying a frequency for acquiring the internal impedance Z in the present embodiment.
- DRTg (f) is obtained through steps S111 and S112 in the present embodiment as in the first embodiment.
- step S113 ′′ the controller 80 extracts the frequency ⁇ PA from the obtained DRT spectrum by the same method as in the first embodiment or the second embodiment.
- step S114 the controller 80 calculates a correction frequency ⁇ ′ PA by multiplying the extracted frequency ⁇ PA by a correction coefficient K (Tst) corresponding to the stack temperature Ts.
- the correction coefficient K (Tst) is determined so as to increase as the stack temperature Ts increases.
- the correction coefficient K (Tst) indicates, for example, the relationship between the stack temperature Ts and the shift amount (value of the frequency to be shifted) of the low frequency side anode electrode reaction resistance peak P 2A or the high frequency side anode electrode reaction resistance peak P 3A.
- a map is determined in advance by experiments or the like, and can be calculated from the detected value of the stack temperature Ts based on the map.
- the controller 80 executes the processing after step S120 described in FIG. 3, FIG. 6, or FIG. That is, the controller 80 determines whether to execute the EAP process based on the internal impedance Z ( ⁇ ′ PA ).
- the control method of the fuel cell system 100 of the present embodiment described above has the following operational effects.
- the EAP execution determination process it is determined whether or not to execute the EAP process in consideration of the stack temperature Ts in addition to the internal impedance Z ( ⁇ PA ) of the anode sensitive frequency. In particular, in the present embodiment, it is determined whether or not to execute the EAP process based on the internal impedance Z ( ⁇ ′ PA ) of the correction frequency ⁇ ′ PA corrected according to the change in the stack temperature Tst.
- the threshold value Rath or the threshold value ⁇ Rath to be compared with the anode electrode reaction resistance Ra or the increase rate ⁇ Ra may be changed according to the change in the stack temperature Tst. More specifically, the threshold value Rath or the threshold value ⁇ Rath may be set lower as the stack temperature Tst becomes higher.
- the controller 80 takes into account that the oxidation reaction of the anode electrode catalyst does not occur theoretically when the stack temperature Tst falls below the oxidation deterioration point, and takes into account the value of the internal impedance Z. Instead, the EAP process may be stopped.
- the process of specifying the frequency ⁇ P2A or the frequency ⁇ P3A of the internal impedance Z used for the EAP execution determination is performed in advance, and the specified frequency ⁇ P2A or the frequency ⁇ P3A is stored in the memory of the controller 80. It may be stored in the memory. Accordingly, it is possible to make an EAP process execution determination without performing a DRT analysis in the EAP execution determination process.
- anode reaction resistance Ra in step S120 of FIG. 3 may be obtained from the internal impedance Z by various other methods besides the method of taking the absolute value of the internal impedance Z.
- the EAP execution determination process is executed using the internal impedance Z ( ⁇ ) of the fuel cell stack 10, but the internal impedance of one fuel cell constituting the fuel cell stack 10 or
- the EAP execution determination process may be executed using a representative value or an average value of internal impedances of a plurality of fuel cells.
- the predetermined frequency band for acquiring the internal impedance measurement value group is the target low frequency side anode electrode reaction resistance peak P 2A .
- the corresponding frequency ⁇ P2 and the frequency ⁇ P3A corresponding to the high frequency side anode electrode reaction resistance peak P 3A may be changed as appropriate. For example, if there is a high possibility that these peaks do not exist in an extremely low frequency band such as between 0.1 Hz and 10 Hz or a high frequency band of 10 kHz or higher, a frequency band for acquiring the internal impedance measurement value group is set It may be set to 10 Hz to 1 kHz.
- the controller 80 can shorten the calculation cycle for performing the EAP execution determination process shown in FIG. This will lead to further improvement in accuracy.
- the frequency ⁇ P2A or the frequency ⁇ P3A can be easily specified.
- the EAP execution determination process shown in FIG. 3 and the like has been mainly described as an example when the operation of the fuel cell stack 10 is stopped.
- EAP execution determination processing may be performed.
- the fuel cell system 100 is in an operating state (EV key is on), there is substantially no power supplied from the fuel cell stack 10 to the battery 62 and the drive motor 63, or from the battery 62 and the drive motor 63.
- the required power is low (in the idling stop state)
- the diffusion of the fuel gas to the fuel cell stack 10 is despread even though the stack temperature Ts is higher than the oxidation deterioration point. It is conceivable that backflow tends to occur and the anode electrode becomes an oxidizing atmosphere.
- the start-up combustion mechanism 30 is set so that the stack temperature Ts quickly reaches the operating temperature.
- the fuel cell stack 10 is heated by, for example, the reformer 28 is not sufficiently high in spite of the stack temperature Ts exceeding the oxidation deterioration point, and the amount of fuel gas supplied to the anode electrode is high. It is assumed that the anode electrode is in an oxidizing atmosphere due to a shortage.
- the EAP execution determination process of each of the above embodiments is performed in a scene in which the anode electrode is relatively susceptible to an oxidizing atmosphere at the time of idle stop or start-up, an increase in power consumption due to the execution of unnecessary EAP process is suppressed.
- the EAP process can be appropriately executed.
- the frequency ⁇ P2 corresponding to the low-frequency anode reaction resistance peak P 2A and the internal impedance Z of one of the frequencies ⁇ P3A corresponding to the high-frequency anode reaction resistance peak P 3A are used.
- the example of performing the EAP execution determination process has been described. However, the EAP execution determination process may be performed based on both the internal impedance Z ( ⁇ P2A ) of the frequency ⁇ P2 and the internal impedance Z ( ⁇ P33 ) of the frequency ⁇ P3A .
- the EAP process may be executed when the anode reaction resistance R a ( ⁇ P3A ) exceeds the threshold value Rath ( ⁇ P3A ), and otherwise, the EAP process may not be executed or stopped.
- the threshold value Rath ( ⁇ P2A ) and the threshold value Rath ( ⁇ P3A ) may be set to the same value or may be set to different values.
- the high-frequency side anode electrode reaction resistance peak P 3A is more sensitive to the progress of the catalytic oxidation of the anode electrode than the low-frequency side anode electrode reaction resistance peak P 2A. Therefore, the threshold value Rath ( ⁇ P3A ) may be set smaller than the threshold value Rath ( ⁇ P2A ).
- the threshold value Rath, the threshold value ⁇ Rath, and the reference anode electrode reaction resistance Ra0 in each of the above-described embodiments have been mainly described with reference to examples using predetermined values. However, these values may be appropriately adjusted based on predetermined learning control or the like in the operation process of the fuel cell system 100 or the fuel cell stack 10.
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Abstract
Description
図1は、本実施形態による燃料電池システム100の概略構成図である。
以下、第2実施形態について説明する。なお、第1実施形態と同様の要素には同一の符号を付し、その説明を省略する。本実施形態では、特に、低周波側アノード極反応抵抗ピークP2Aに対応する周波数ωP2Aの内部インピーダンスZ(ωP2A)に基づいて、EAP実施判断処理を行う例について説明する。
以下、第3実施形態について説明する。なお、第1実施形態又は第2実施形態と同様の要素には同一の符号を付し、その説明を省略する。特に、本実施形態では、EAP処理を実行するか否かの判断を、アノード極反応抵抗Raの定常状態における値(所定の基準値)に対する現在のアノード極反応抵抗Raの増加倍率ΔRa(ΔRa={Ra/Ra0})と所定の閾値ΔRathとの大小比較に基づいて行う。なお、以下では、アノード極反応抵抗Raの定常状態における値を、単に「基準アノード極反応抵抗Ra0」とも記載する。
以下、第4実施形態について説明する。なお、第1~第3実施形態と同様の要素には同一の符号を付し、その説明を省略する。特に、本実施形態では、EAP処理を実行すると判断された後(図1及び図6のステップS130)、ステップS140においてEAP処理を実行する際のEAP処理における印加電圧(EAP電流)をアノード極反応抵抗Raに基づいて調節する。
以下、第5実施形態について説明する。なお、第1~第4実施形態と同様の要素には同一の符号を付し、その説明を省略する。特に、本実施形態では、スタック温度Tsに基づいてアノード感応周波数を補正する例について説明する。
Claims (14)
- アノードガス及びカソードガスの供給を受けて発電する固体酸化物型の燃料電池を有する燃料電池システムの制御方法であって、
前記燃料電池のアノード極の触媒酸化を抑制すべく前記燃料電池に所定の保護電流を印加するアノード極保護処理の実施判断を行うアノード極保護実施判断処理を含み、
前記アノード極保護実施判断処理では、
前記燃料電池のアノード極反応抵抗を検知し得るアノード感応周波数における前記燃料電池の内部インピーダンスを取得し、
前記アノード感応周波数における前記内部インピーダンスに基づいて、前記アノード極保護処理を実行するか否かを判断する、
燃料電池システムの制御方法。 - 請求項1に記載の燃料電池システムの制御方法であって、
前記アノード感応周波数は、前記アノード極反応抵抗の変化による前記内部インピーダンスの変化量が、所定値以上となる周波数である、
燃料電池システムの制御方法。 - 請求項1又は2に記載の燃料電池システムの制御方法であって、
前記アノード感応周波数は、
前記アノード極反応抵抗の変化による前記内部インピーダンスの変化量が、該アノード極反応抵抗以外の内部インピーダンス構成要素の変化による前記内部インピーダンスの変化量と比べて大きくなる周波数である、
燃料電池システムの制御方法。 - 請求項3に記載の燃料電池システムの制御方法であって、
前記内部インピーダンス構成要素は、前記燃料電池のカソード極反応抵抗を含み、
前記アノード感応周波数は、
前記内部インピーダンスを表すスペクトルデータにおいて、前記アノード極反応抵抗に相関する2つのピークの内の少なくとも一方に対応する周波数を含む、
燃料電池システムの制御方法。 - 請求項4に記載の燃料電池システムの制御方法であって、
前記アノード感応周波数は、
前記アノード極反応抵抗に相関する2つのピークの内、前記カソード極反応抵抗に相関するピークに近い低周波数側のピークに対応する周波数を含む、
燃料電池システムの制御方法。 - 請求項1~5のいずれか1項に記載の燃料電池システムの制御方法であって、
前記アノード極保護実施判断処理では、
さらに、前記アノード感応周波数を特定するアノード感応周波数特定処理を実行する、
燃料電池システムの制御方法。 - 請求項1~6のいずれか1項に記載の燃料電池システムの制御方法であって、
前記アノード極保護実施判断処理では、
前記アノード感応周波数における前記内部インピーダンスに基づいて、前記アノード極反応抵抗を推定し、
推定した前記アノード極反応抵抗が所定の閾値よりも高い場合に、前記アノード極保護処理を実行すると判断する、
燃料電池システムの制御方法。 - 請求項1~6のいずれか1項に記載の燃料電池システムの制御方法であって、
前記アノード極保護実施判断処理では、
前記アノード感応周波数における前記内部インピーダンスに基づいて、前記アノード極反応抵抗を推定し、
推定した前記アノード極反応抵抗の所定の基準値に対する増加倍率を演算し、
前記増加倍率が所定の閾値よりも高い場合に、前記アノード極保護処理を実行すると判断する、
燃料電池システムの制御方法。 - 請求項7又は8に記載の燃料電池システムの制御方法であって、
前記アノード極保護実施判断処理において前記アノード極保護処理を実行すると判断された場合に、前記保護電流を調節する保護電流調節処理を含み、
前記保護電流調節処理では、
前記アノード感応周波数における前記内部インピーダンスに基づいて推定した前記アノード極反応抵抗又は該推定したアノード極反応抵抗の所定の基準値に対する増加倍率と所定の閾値との差に基づいて前記保護電流の大きさを決定する、
燃料電池システムの制御方法。 - 請求項1~9のいずれか1項に記載の燃料電池システムの制御方法であって、
前記アノード極保護実施判断処理では、
前記アノード感応周波数における前記内部インピーダンスに加えて前記燃料電池の温度を考慮して、前記アノード極保護処理を実行するか否かを判断する、
燃料電池システムの制御方法。 - 請求項1~10のいずれか1項に記載の燃料電池システムの制御方法であって、
前記アノード極保護実施判断処理を、前記燃料電池の運転の停止時及び前記燃料電池の起動時の少なくともいずれかに実行する、
燃料電池システムの制御方法。 - アノードガス及びカソードガスの供給を受けて発電する固体酸化物型の燃料電池と、
前記燃料電池のアノード極の触媒酸化を抑制するための保護電流を前記燃料電池に印加する保護電流印加装置と、
前記燃料電池の内部インピーダンスを計測するインピーダンス計測装置と、
前記インピーダンス計測装置により計測された前記内部インピーダンスに基づいて前記保護電流印加装置を制御して前記保護電流を印加させるアノード極保護処理を実行するコントローラと、を有し、
前記コントローラは、
前記燃料電池のアノード極反応抵抗を検知し得るアノード感応周波数で計測された前記内部インピーダンスを前記インピーダンス計測装置から取得し、
前記アノード感応周波数における前記内部インピーダンスに基づいて、前記アノード極保護処理を実行するか否かを判断するアノード極保護実施判断処理を行うようにプログラムされた、
燃料電池システム。 - 請求項12に記載の燃料電池システムであって、
前記コントローラは、さらに、前記アノード感応周波数を特定する処理を行うようにプログラムされた、
燃料電池システム。 - 請求項12又は13に記載の燃料電池システムであって、
前記コントローラは、さらに、前記燃料電池の運転の停止指令及び前記燃料電池の起動指令の少なくともいずれかを受信したときに、前記アノード極保護実施判断処理を行うようにプログラムされた、
燃料電池システム。
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JPWO2018131071A1 (ja) | 2019-12-12 |
CN110178256A (zh) | 2019-08-27 |
CN110178256B (zh) | 2020-12-15 |
EP3570355A1 (en) | 2019-11-20 |
US10957922B2 (en) | 2021-03-23 |
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