WO2015005229A1 - 燃料電池システム及び燃料電池システムの制御方法 - Google Patents
燃料電池システム及び燃料電池システムの制御方法 Download PDFInfo
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- WO2015005229A1 WO2015005229A1 PCT/JP2014/067846 JP2014067846W WO2015005229A1 WO 2015005229 A1 WO2015005229 A1 WO 2015005229A1 JP 2014067846 W JP2014067846 W JP 2014067846W WO 2015005229 A1 WO2015005229 A1 WO 2015005229A1
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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
- H01M8/04104—Regulation of differential pressures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
- H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
- H01M8/04119—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with simultaneous supply or evacuation of electrolyte; Humidifying or dehumidifying
- H01M8/04156—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with simultaneous supply or evacuation of electrolyte; Humidifying or dehumidifying with product water removal
- H01M8/04179—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with simultaneous supply or evacuation of electrolyte; Humidifying or dehumidifying with product water removal by purging or increasing flow or pressure of reactants
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04223—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids during start-up or shut-down; Depolarisation or activation, e.g. purging; Means for short-circuiting defective fuel cells
- H01M8/04231—Purging of the reactants
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
- H01M8/0438—Pressure; Ambient pressure; Flow
- H01M8/04388—Pressure; Ambient pressure; Flow of anode reactants at the inlet or inside the fuel cell
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
- H01M8/0438—Pressure; Ambient pressure; Flow
- H01M8/04395—Pressure; Ambient pressure; Flow of cathode reactants at the inlet or inside the fuel cell
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
- H01M8/04746—Pressure; Flow
- H01M8/04753—Pressure; Flow of fuel cell reactants
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
- H01M8/04089—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
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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
- H01M8/04335—Temperature; Ambient temperature of cathode reactants at the inlet or inside the fuel cell
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
- H01M8/04537—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
- H01M8/04828—Humidity; Water content
- H01M8/0485—Humidity; Water content of the 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 fuel cell system and a control method for the fuel cell system.
- JP2012-003957A discloses a conventional fuel cell system that controls a compressor and a pressure regulating valve to control the flow rate and pressure of a cathode gas to target values.
- the pressure is controlled to the target pressure by controlling the supply flow rate of the compressor based on the target pressure of the cathode gas.
- the flow rate unnecessary for the fuel cell supplied by the compressor is considered to flow in the bypass passage of the fuel cell.
- transmembrane differential pressure fluctuates as the anode gas pressure pulsates.
- the target pressure of the cathode gas set according to the requirements of the fuel cell is lower than the lower limit pressure for membrane protection obtained by subtracting the allowable transmembrane pressure from the anode gas pressure, It is desirable to control the compressor using the lower limit pressure of the target pressure as the target pressure.
- the lower limit pressure for protecting the membrane is calculated based on the pressure of the anode gas, it pulsates (increases or decreases) in conjunction with the pressure pulsation of the anode gas.
- the compressor When the compressor is controlled using the lower limit pressure for protecting the pulsating membrane as the target pressure of the cathode gas in this way, the supply flow rate of the compressor periodically increases and decreases with the pulsation of the target pressure, and the compressor generates a swell sound and the like. There is a risk of abnormal noise.
- the present invention has been made paying attention to such problems, and suppresses the generation of abnormal noise from the compressor in a fuel cell system that controls the supply flow rate of the compressor based on the target pressure of the cathode gas. For the purpose.
- a fuel cell system that generates power by supplying an anode gas and a cathode gas to a fuel cell.
- the fuel cell system includes a compressor for supplying the cathode gas to the fuel cell, a pulsation operation unit that pulsates the pressure of the anode gas based on the operation state of the fuel cell system, and a first operation of the cathode gas based on the demand of the fuel cell.
- a first target pressure setting unit for setting one target pressure, and a second target pressure for the cathode gas for maintaining the differential pressure in the fuel cell within an allowable differential pressure range in accordance with the pressure of the anode gas in the fuel cell.
- a second target pressure setting unit for setting, and a compressor control unit for controlling the compressor based on the first target pressure and the second target pressure.
- the second target pressure setting unit sets the second target pressure based on the pulsation upper limit target pressure when pulsating the pressure of the anode gas.
- FIG. 1 is a schematic view of a fuel cell system according to a first embodiment of the present invention.
- FIG. 2 is a flowchart illustrating anode gas supply control according to the first embodiment of the present invention.
- FIG. 3 is a table for calculating the pulsation upper limit target pressure and the pulsation lower limit target pressure based on the target output current.
- FIG. 4 is a block diagram illustrating cathode gas supply control according to the first embodiment of the present invention.
- FIG. 5 is a time chart for explaining operations of anode gas supply control and cathode gas supply control according to the first embodiment of the present invention.
- FIG. 6 is a block diagram illustrating cathode gas supply control according to the second embodiment of the present invention.
- FIG. 7 is a time chart for explaining operations of anode gas supply control and cathode gas supply control according to the second embodiment of the present invention.
- FIG. 8 is a block diagram illustrating cathode gas supply control according to another embodiment of the present invention
- an electrolyte membrane is sandwiched between an anode electrode (fuel electrode) and a cathode electrode (oxidant electrode), an anode gas containing hydrogen in the anode electrode (fuel gas), and a cathode gas containing oxygen in the cathode electrode (oxidant) Electricity is generated by supplying gas.
- the electrode reaction that proceeds in both the anode electrode and the cathode electrode is as follows.
- Anode electrode 2H 2 ⁇ 4H + + 4e ⁇ (1)
- Cathode electrode 4H + + 4e ⁇ + O 2 ⁇ 2H 2 O (2)
- the fuel cell generates an electromotive force of about 1 volt by the electrode reactions (1) and (2).
- a fuel cell When a fuel cell is used as a power source for automobiles, it requires a large amount of power, so it is used as a fuel cell stack in which several hundred fuel cells are stacked. Then, a fuel cell system that supplies anode gas and cathode gas to the fuel cell stack is configured, and electric power for driving the vehicle is taken out.
- FIG. 1 is a schematic diagram of a fuel cell system 100 according to a first embodiment of the present invention.
- the fuel cell system 100 includes a fuel cell stack 1, a cathode gas supply / discharge device 2, an anode gas supply / discharge device 3, and a controller 4.
- the fuel cell stack 1 is formed by stacking several hundred fuel cells, and receives the supply of anode gas and cathode gas to generate electric power necessary for driving the vehicle.
- the cathode gas supply / discharge device 2 supplies cathode gas (air) to the fuel cell stack 1 and discharges cathode off-gas discharged from the fuel cell stack 1 to the outside air.
- the cathode gas supply / discharge device 2 is referred to as a cathode gas supply passage 21, a cathode gas discharge passage 22, a filter 23, a cathode compressor 24, an intercooler 25, and a water recovery device (hereinafter referred to as "WRD").
- RDD water recovery device
- the cathode gas supply passage 21 is a passage through which the cathode gas supplied to the fuel cell stack 1 flows.
- the cathode gas supply passage 21 has one end connected to the filter 23 and the other end connected to the cathode gas inlet hole of the fuel cell stack 1.
- the cathode gas discharge passage 22 is a passage through which the cathode off gas discharged from the fuel cell stack 1 flows. One end of the cathode gas discharge passage 22 is connected to the cathode gas outlet hole of the fuel cell stack 1, and the other end is an open end.
- the cathode off gas is a mixed gas such as oxygen not used in the electrode reaction, nitrogen contained in the cathode gas, and water vapor generated by the electrode reaction.
- the filter 23 removes foreign matters in the cathode gas taken into the cathode gas supply passage 21.
- the cathode compressor 24 is provided in the cathode gas supply passage 21.
- the cathode compressor 24 takes air as cathode gas into the cathode gas supply passage 21 through the filter 23 and supplies the air to the fuel cell stack 1.
- the intercooler 25 is provided in the cathode gas supply passage 21 downstream from the cathode compressor 24.
- the intercooler 25 cools the cathode gas discharged from the cathode compressor 24.
- the WRD 26 is connected to each of the cathode gas supply passage 21 and the cathode gas discharge passage 22, collects moisture in the cathode off-gas flowing through the cathode gas discharge passage 22, and cathode that flows through the cathode gas supply passage 21 with the collected moisture. Humidify the gas.
- the orifice 27 is provided in the cathode gas discharge passage 22 downstream of the WRD 26.
- the orifice 27 limits the flow rate of the cathode off gas flowing through the cathode gas discharge passage 22.
- the bypass passage 28 is provided so that a part of the cathode gas discharged from the cathode compressor 24 can be directly discharged to the cathode gas discharge passage 22 without going through the fuel cell stack 1 as necessary. It is.
- One end of the bypass passage 28 is connected to the cathode gas supply passage 21 between the cathode compressor 24 and the intercooler 25, and the other end is connected to the cathode gas discharge passage 22 downstream of the orifice 27.
- bypass valve 29 is provided in the bypass passage 28.
- the bypass valve 29 is controlled to be opened and closed by the controller 4 to adjust the flow rate of the cathode gas flowing through the bypass passage 28 (hereinafter referred to as “bypass flow rate”).
- the first air flow sensor 41 is provided in the cathode gas supply passage 21 upstream of the cathode compressor 24.
- the first air flow sensor 41 detects the flow rate of the cathode gas supplied to the cathode compressor 24 (hereinafter referred to as “compressor supply flow rate”).
- the second air flow sensor 42 is provided in the cathode gas supply passage downstream from the connection portion with the bypass passage 28.
- the second air flow sensor 42 detects the flow rate of the cathode gas supplied to the fuel cell stack 1 out of the cathode gas discharged from the cathode compressor 24 (hereinafter referred to as “stack supply flow rate”).
- the stack supply flow rate is a flow rate obtained by subtracting the bypass flow rate from the compressor supply flow rate.
- the cathode pressure sensor 43 is provided in the cathode gas supply passage 21 in the vicinity of the cathode gas inlet side of the WRD 26.
- the cathode pressure sensor 43 detects the pressure of the cathode gas in the vicinity of the cathode gas inlet side of the WRD 26 (hereinafter referred to as “cathode pressure”).
- the temperature sensor 44 is provided in the cathode gas supply passage 21 between the intercooler 25 and the WRD 26.
- the temperature sensor 44 detects the temperature on the cathode gas inlet side of the WRD 26 (hereinafter referred to as “WRD inlet temperature”).
- the anode gas supply / discharge device 3 supplies anode gas to the fuel cell stack 1 and discharges anode off-gas discharged from the fuel cell stack 1 to the cathode gas discharge passage 22.
- the anode gas supply / discharge device 3 includes a high-pressure tank 31, an anode gas supply passage 32, an anode pressure regulating valve 33, an anode gas discharge passage 34, a purge valve 35, and an anode pressure sensor 45.
- the high-pressure tank 31 stores the anode gas (hydrogen) supplied to the fuel cell stack 1 while maintaining the high-pressure state.
- the anode gas supply passage 32 is a passage for supplying the anode gas discharged from the high-pressure tank 31 to the fuel cell stack 1.
- the anode gas supply passage 32 has one end connected to the high pressure tank 31 and the other end connected to the anode gas inlet hole of the fuel cell stack 1.
- the anode pressure regulating valve 33 is provided in the anode gas supply passage 32.
- the anode pressure regulating valve 33 is controlled to be opened and closed by the controller 4 and adjusts the pressure of the anode gas supplied to the fuel cell stack 1 to a desired pressure.
- the anode gas discharge passage 34 is a passage through which the anode off gas discharged from the fuel cell stack 1 flows.
- the anode gas discharge passage 34 has one end connected to the anode gas outlet hole of the fuel cell stack 1 and the other end connected to the cathode gas discharge passage 22.
- the anode off gas discharged to the cathode gas discharge passage 22 via the anode gas discharge passage 34 is mixed with the cathode off gas in the cathode gas discharge passage 22 and discharged to the outside of the fuel cell system 100. Since the anode off gas contains excess anode gas that was not used for the electrode reaction, the anode off gas is mixed with the cathode off gas and discharged to the outside of the fuel cell system 100, so that the hydrogen concentration in the exhaust gas is preliminarily set. It is set to be equal to or less than a predetermined concentration.
- the purge valve 35 is provided in the anode gas discharge passage 34.
- the purge valve 35 is controlled to be opened and closed by the controller 4 and adjusts the flow rate of the anode off gas discharged from the anode gas discharge passage 34 to the cathode gas discharge passage 22.
- the anode pressure sensor 45 is provided in the anode gas supply passage 32 downstream of the anode pressure regulating valve 33 and detects the pressure of the anode gas supplied to the fuel cell stack 1 (hereinafter referred to as “anode pressure”).
- the controller 4 includes a microcomputer having a central processing unit (CPU), a read only memory (ROM), a random access memory (RAM), and an input / output interface (I / O interface).
- CPU central processing unit
- ROM read only memory
- RAM random access memory
- I / O interface input / output interface
- the controller 4 includes a current sensor 46 that detects a current (output current) extracted from the fuel cell stack 1 and a voltage sensor that detects an output voltage of the fuel cell stack 1. 47. Signals from various sensors such as an accelerator stroke sensor 48 for detecting the amount of depression of the accelerator pedal (hereinafter referred to as “accelerator operation amount”) and an SOC sensor 49 for detecting the battery charge amount are input. The controller 4 detects the operating state of the fuel cell system 100 based on signals from these various sensors.
- the controller 4 controls the supply of the anode gas to the fuel cell stack 1 so that the anode pressure pulsates, and also controls the supply of the cathode gas so that the cathode pressure matches the target.
- the anode gas supply control and the cathode gas supply control performed by the controller 4 will be described.
- FIG. 2 is a flowchart illustrating the anode gas supply control according to the present embodiment.
- step S1 the controller 4 calculates the target output current of the fuel cell stack 1 based on the operating state of the fuel cell system 100. Specifically, the target output power of the fuel cell stack 1 is calculated based on the required power of a drive motor (not shown) that generates the driving force of the vehicle and the auxiliary power such as the cathode compressor 24 and the charge / discharge request of the battery. Based on the target output power, the target output current is calculated from the IV characteristics of the fuel cell stack 1.
- step S2 the controller 4 refers to the table in FIG. 3 and calculates the pulsation upper limit target pressure and the pulsation lower limit target pressure based on the target output current. As shown in the table of FIG. 3, the pulsation upper limit target pressure and the pulsation lower limit target pressure are larger when the target output current is higher than when the target output current is low. Similarly, the pulsation width becomes larger when the target output current is higher than when the target output current is low.
- step S3 the controller 4 determines whether or not the anode pressure is higher than the pulsation upper limit target pressure. If the anode pressure is equal to or higher than the pulsation upper limit target pressure, the controller 4 performs the process of step S4 to reduce the anode pressure. On the other hand, if the anode pressure is less than the pulsation upper limit target pressure, the process of step S5 is performed.
- step S4 the controller 4 sets the target anode pressure to the pulsation lower limit target pressure.
- the opening degree of the anode pressure regulating valve 33 is feedback-controlled so that the anode pressure becomes the lower limit target pressure during pulsation.
- the opening of the anode pressure regulating valve 33 is normally fully closed, and the supply of anode gas from the high-pressure tank 31 to the fuel cell stack 1 is stopped.
- the anode pressure decreases due to the consumption of the anode gas in the fuel cell stack 1 by power generation.
- step S5 the controller 4 determines whether or not the anode pressure is equal to or lower than the pulsation lower limit target pressure. If the anode pressure is equal to or lower than the pulsation lower limit target pressure, the controller 4 performs the process of step S6 to increase the anode pressure. On the other hand, if the anode pressure is higher than the pulsation lower limit target pressure, the process of step S7 is performed.
- step S6 the controller 4 sets the target anode pressure to the pulsation upper limit target pressure.
- the opening degree of the anode pressure regulating valve 33 is feedback-controlled so that the anode pressure becomes the pulsation upper limit target pressure.
- the anode pressure regulating valve 33 is opened to a desired opening, anode gas is supplied from the high-pressure tank 31 to the fuel cell stack 1, and the anode pressure rises.
- step S7 the controller 4 sets the target anode pressure to the same target anode pressure as the previous time.
- the transmembrane pressure difference between the electrolyte membranes on the anode electrode side and the cathode electrode side of each fuel cell varies as the anode pressure pulsates. If this inter-membrane differential pressure is excessive, unexpected stress is applied to the electrolyte membrane, which may reduce the mechanical strength of the electrolyte membrane, which causes deterioration of the fuel cell.
- the target cathode pressure set based on the operating state of the fuel cell system 100 is a lower limit for membrane protection in which a predetermined allowable transmembrane pressure is subtracted from the anode pressure.
- this lower limit pressure is set as the target cathode pressure.
- the lower limit pressure for protecting the membrane is calculated based on the pulsating anode pressure, the lower limit pressure also pulsates.
- the target cathode pressure pulsates.
- the rotational speed of the cathode compressor 24 controlled in accordance with the target cathode pressure periodically increases or decreases with the pulsation of the target cathode pressure, and there is a possibility that abnormal noise such as swell noise is generated from the cathode compressor 24. There is.
- the pressure that limits the pulsation of the target cathode pressure is set as the limited target cathode pressure, and according to the limited target cathode pressure.
- the cathode compressor 24 was controlled.
- the transmembrane differential pressure limit request target pressure obtained by subtracting the allowable transmembrane pressure from the pulsation upper limit target pressure is set as the limited target cathode pressure.
- the pulsation upper limit target pressure is fixed to a predetermined value according to the target output current if there is no fluctuation in the target output current. Therefore, the transmembrane pressure limit request target obtained by subtracting the allowable transmembrane pressure from the pulsation upper limit target pressure.
- the pressure is also fixed at a certain predetermined value. Therefore, when the target cathode pressure pulsates with the pulsation of the anode pressure, the cathode compressor 24 is controlled by controlling the cathode compressor 24 according to the transmembrane differential pressure limit request target pressure held at the predetermined value, thereby rotating the cathode compressor 24. Speed pulsation can be suppressed.
- the cathode gas supply control according to this embodiment will be described.
- FIG. 4 is a block diagram illustrating cathode gas supply control according to the present embodiment.
- the target output current is input to the oxygen partial pressure securing request stack supply flow rate calculation unit 101.
- the oxygen partial pressure securing request stack supply flow rate calculation unit 101 calculates the oxygen partial pressure securing request stack supply flow rate based on the target output current.
- This oxygen partial pressure securing request stack supply flow rate is the stack supply necessary for securing the oxygen partial pressure necessary for the electrode reaction in the cathode electrode of each fuel cell when the target output current is taken out from the fuel cell stack 1. This is the target flow rate.
- the oxygen supply partial pressure securing request stack supply flow rate is larger when the target output current is large than when the target output current is small.
- the wetness control request stack supply flow rate calculation unit 102 receives, for example, the impedance of the fuel cell stack 1 calculated by the AC impedance method and a target impedance that is predetermined according to the target output current of the fuel cell stack 1. Is done.
- the wetness control request stack supply flow rate calculation unit 102 calculates the target value of the stack supply flow rate for setting the impedance to the target impedance as the wetness control request stack supply flow rate based on the deviation between the impedance and the target impedance.
- the stack supply flow rate required for controlling the wetness is the stack supply flow rate necessary for controlling the wetness (moisture content) of the electrolyte membrane to an optimum wetness according to the target output current of the fuel cell stack 1. It is.
- the target stack supply flow rate calculation unit 103 receives the oxygen partial pressure securing request stack supply flow rate and the wetness control request stack supply flow rate. The target stack supply flow rate calculation unit 103 calculates the larger one of these two as the target stack supply flow rate.
- the target bypass valve opening calculation unit 104 receives the stack supply flow rate and the target stack supply flow rate.
- the target bypass valve opening degree calculation unit 104 calculates the opening degree of the bypass valve 29 for changing the stack supply flow rate to the target stack supply flow rate based on the deviation between the stack supply flow rate and the target stack supply flow rate. Calculate as
- the target bypass opening is input to the bypass valve control unit 105.
- the bypass valve control unit 105 controls the opening degree of the bypass valve 29 to the target bypass valve opening degree. Note that the actual opening of the bypass valve 29 may be input to the bypass valve control unit 105, and the opening of the bypass valve 29 may be controlled based on the actual opening and the target bypass valve opening.
- the target output current is input to the oxygen partial pressure ensuring required target pressure calculation unit 106.
- the oxygen partial pressure ensuring required target pressure calculation unit 106 calculates the oxygen partial pressure ensuring required target pressure based on the target output current.
- This target pressure for ensuring oxygen partial pressure is the same as the cathode pressure necessary for securing the oxygen partial pressure necessary for electrode reaction in the cathode electrode of each fuel cell when the target output current is taken out from the fuel cell stack 1. It is a target value.
- the target pressure for ensuring the oxygen partial pressure is higher when the target output current is larger than when the target output current is small.
- the wetness control required target pressure calculation unit 107 receives the impedance of the fuel cell stack 1 and the target impedance. Based on the deviation between the impedance and the target impedance, the wetness control request target pressure calculation unit 107 calculates the target value of the cathode pressure for setting the impedance to the target impedance as the wetness control request target pressure.
- This target pressure for wetness control is a cathode pressure required to control the wetness (moisture content) of the electrolyte membrane to an optimum wetness according to the target output current of the fuel cell stack 1.
- the lower limit pressure calculation unit 108 receives the anode pressure and the allowable transmembrane pressure.
- the lower limit pressure calculation unit 108 calculates a value obtained by subtracting the allowable transmembrane pressure from the anode pressure as the lower limit pressure (membrane protection required target pressure) of the cathode gas.
- the lower limit pressure is a lower limit value of the cathode pressure that needs to be protected for protecting the electrolyte membrane.
- the allowable transmembrane pressure difference is a predetermined value that can be set as appropriate with the maximum value allowable as the transmembrane pressure difference (hereinafter referred to as “allowable maximum transmembrane pressure difference”) as an upper limit.
- the transmembrane differential pressure restriction request target pressure calculation unit 109 receives the pulsation upper limit target pressure and the allowable transmembrane pressure.
- the transmembrane pressure limit request target pressure calculation unit 109 calculates a value obtained by subtracting the allowable transmembrane pressure from the pulsation upper limit target pressure as the transmembrane pressure limit request target pressure.
- the target cathode pressure calculation unit 110 receives an oxygen partial pressure ensuring required target pressure, a wetness control required target pressure, and a lower limit pressure (membrane protection required target pressure). The target cathode pressure calculation unit 110 calculates the largest one of these three input values as the target cathode pressure. As described above, the target cathode pressure calculation unit 110 according to the present embodiment is optimally set based on the requirements of the fuel cell stack 1 such as the oxygen partial pressure securing request, the wetness control request, and the membrane protection request.
- the target cathode pressure and the transmembrane differential pressure limit request target pressure are input to the limit target cathode pressure calculation unit 111.
- the limit target cathode pressure is calculated as the limit target cathode pressure, whichever is larger of these two input values.
- the stack demand compressor supply flow rate calculation unit 112 receives the cathode pressure and the limit target cathode pressure.
- the stack required compressor supply flow rate calculation unit 112 calculates, as the stack required compressor supply flow rate, a target value of the compressor supply flow rate for setting the cathode pressure to the limit target cathode pressure based on the deviation between the cathode pressure and the limit target cathode pressure.
- the stack required compressor supply flow rate is the compressor supply flow rate necessary to satisfy the requirements of the fuel cell stack 1 such as the oxygen partial pressure securing request and the wetness control request.
- the target compressor supply flow rate calculation unit 113 receives the stack request compressor supply flow rate and the dilution request compressor supply flow rate determined according to the target output current of the fuel cell stack 1. For the target compressor supply flow rate, the larger one of these two input values is calculated as the target compressor supply flow rate.
- the dilution demand compressor supply flow rate is a compressor supply flow rate necessary for setting the hydrogen concentration of the exhaust gas discharged outside the fuel cell system 100 to a predetermined concentration or less. In the present embodiment, the dilution request compressor supply flow rate is increased when the target output current is large compared to when the target output current is small, but may be a constant value regardless of the target output current.
- the cathode compressor control unit 114 receives the compressor supply flow rate and the target compressor supply flow rate.
- the cathode compressor control unit 114 calculates a torque command value for the cathode compressor 24 based on the deviation between the compressor supply flow rate and the target compressor supply flow rate, and controls the cathode compressor 24 according to the torque command value.
- the target compressor supply flow rate (stack required compressor supply flow rate) is calculated based on the limited target cathode pressure, and the cathode compressor 24 is controlled so that the compressor supply flow rate becomes the target compressor supply flow rate.
- the cathode pressure is controlled to the limited target cathode pressure. That is, in this embodiment, the cathode compressor 24 is finally controlled based on the target cathode pressure and the transmembrane differential pressure limit request target pressure.
- the cathode compressor 24 controls the cathode compressor 24 so that the compressor supply flow rate becomes the target compressor supply flow rate
- the stack supply flow rate becomes the target stack supply flow rate.
- the bypass valve 29 is controlled. That is, when the cathode compressor 24 supplies more cathode gas than required to the fuel cell stack 1, a flow rate unnecessary for the fuel cell stack 1 is caused to flow to the bypass passage 28 by opening the bypass valve 29. I am doing so.
- FIG. 5 is a time chart for explaining the operation of anode gas supply control and cathode gas supply control according to this embodiment.
- the anode pressure regulating valve 33 is fully closed to control the anode pressure so that the lower pulsation lower limit target pressure is reached, and the supply of the anode gas from the high-pressure tank 31 to the fuel cell stack 1 is stopped. Is done.
- the anode gas in the fuel cell stack 1 is gradually consumed by power generation, and the anode pressure decreases (FIG. 5A).
- the rate of decrease in anode pressure during the transitional transition at which the target output current decreases depends on the consumption rate of anode gas due to power generation, so the anode pressure is temporarily higher than the pulsation upper limit target pressure during the transitional transition. In some cases, it becomes higher (FIG. 5A).
- the wetness control required target pressure is larger than the lower limit pressure (FIG. 5C), so the wetness control required target pressure is set as the target cathode pressure (FIG. 5D).
- the target pressure for wetness control as the target cathode pressure is compared with the target pressure for requesting the restriction of transmembrane pressure, the target pressure for wetness control is larger, so the target pressure for requesting wetness control is limited.
- the target cathode pressure is set (FIG. 5E).
- the stack demand compressor supply flow rate is calculated according to the limit target cathode pressure.
- the stack request compressor supply flow rate is larger than the dilution request compressor supply flow rate. Accordingly, the stack required compressor supply flow rate calculated according to the limited target cathode pressure is set as the target compressor supply flow rate, and the cathode compressor 24 is controlled based on the target compressor supply flow rate.
- the wetness control required target pressure held at a constant value is set as the limited target cathode pressure, so the rotational speed of the cathode compressor 24 is also constant (FIG. 5 ( F)).
- the transmembrane differential pressure limit required target pressure is set as the limited target cathode pressure. It is set (FIG. 5E).
- the lower limit pressure is set as the target cathode pressure, and the target cathode pressure also pulsates with the pulsation of the anode pressure (FIG. 5C). (D)). If the cathode compressor 24 is controlled in accordance with the pulsating target cathode pressure, the rotational speed of the cathode compressor 24 periodically increases and decreases with the pulsation of the target cathode pressure, and the undulation noise is generated from the cathode compressor 24. There is a risk of abnormal noises.
- the larger of the target cathode pressure and the transmembrane differential pressure limit request target pressure is set as the limit target cathode pressure, and the cathode compressor 24 is controlled according to the limit target cathode pressure.
- the cathode compressor 24 operates in accordance with the limited target cathode pressure (transmembrane differential pressure limit request target pressure) held at a constant value. Will be controlled. Accordingly, the rotational speed of the cathode compressor 24 is kept constant after the time t3, and the rotational speed of the cathode compressor 24 does not periodically increase or decrease, so that abnormal noise such as a swell sound is generated from the cathode compressor 24. Can be suppressed (FIG. 5F).
- the transmembrane differential pressure restriction request target pressure becomes the target cathode. It becomes smaller than the lower limit pressure set as the pressure (FIGS. 5C and 5D). As a result, the lower limit pressure is set as the limited target cathode pressure (FIG. 5E).
- the anode pressure may temporarily become higher than the pulsation upper limit target pressure, and the transmembrane differential pressure limit request target pressure may be lower than the lower limit pressure.
- the cathode compressor 24 is controlled with the target pressure that is less than the lower limit pressure as the limit target cathode pressure, the transmembrane pressure may exceed the allowable transmembrane pressure.
- the greater of the transmembrane differential pressure limit request target pressure and the target cathode pressure is set to the limit target cathode. It is supposed to be set as pressure.
- the lower limit pressure becomes higher than the target pressure required for the transmembrane differential pressure limit, the lower limit pressure is set as the limit target cathode pressure, so that the transmembrane differential pressure is prevented from exceeding the allowable transmembrane differential pressure. can do.
- the transmembrane pressure differential restriction request target pressure is set again as the restriction target cathode pressure.
- the cathode compressor 24 is controlled in accordance with the limited target cathode pressure (transmembrane differential pressure limit request target pressure) held at a constant value after time t6. Can be suppressed (FIG. 5F).
- the fuel cell system 100 includes the cathode compressor 24 for supplying the cathode gas to the fuel cell stack 1, the pulsation operation unit, the first target pressure setting unit, and the second target pressure setting unit. And a controller 4 as a compressor control unit.
- the pulsation operation unit pulsates the pressure of the anode gas based on the operation state of the fuel cell system 100.
- the first target pressure setting unit sets the first target pressure (target cathode pressure) of the cathode gas based on the requirements of the fuel cell stack 1 such as the oxygen partial pressure ensuring request, the wetness control request, and the membrane protection request.
- the second target pressure setting unit is configured to maintain the second target pressure of the cathode gas (intermembrane) for maintaining the differential pressure in the fuel cell stack 1 within the allowable differential pressure range according to the pressure of the anode gas in the fuel cell stack 1.
- the differential pressure limit request target pressure is set based on the pulsation upper limit target pressure when the anode gas pressure is pulsated.
- the compressor control unit controls the cathode compressor 24 based on the first target pressure and the second target pressure.
- the pulsation upper limit target pressure is fixed to a predetermined value according to the target output current if there is no fluctuation in the target output current. Therefore, the transmembrane pressure limit request target obtained by subtracting the allowable transmembrane pressure from the pulsation upper limit target pressure. The pressure is also fixed at a certain predetermined value.
- the cathode compressor 24 is controlled in accordance with the target pressure that requires the transmembrane pressure differential restriction. It can suppress that the rotational speed of the cathode compressor 24 increases or decreases periodically. Therefore, it is possible to suppress the generation of abnormal noise such as swell noise from the cathode compressor 24.
- the anode pressure is controlled to be equal to or lower than the upper limit target pressure during pulsation except during a transitional transition in which the target output current decreases. Therefore, by limiting the lower limit of the cathode pressure based on the pulsation upper limit target pressure as in the present embodiment, it is possible to suppress the transmembrane pressure difference from becoming larger than the allowable transmembrane pressure pressure during pulsation operation. Therefore, it is possible to suppress a decrease in mechanical strength of the electrolyte membrane and to suppress deterioration of the fuel cell.
- the target cathode pressure (first target pressure) and the transmembrane pressure difference are considered in consideration of the case where the lower limit pressure is temporarily higher than the transmembrane differential pressure limit request target pressure during the lowering transition.
- the cathode compressor 24 is controlled by setting the larger of the limit request target pressure (second target pressure) as the limit target cathode pressure.
- the lower limit pressure is set as the limited target cathode pressure, so the transmembrane pressure exceeds the allowable transmembrane pressure. Can be suppressed.
- FIG. 6 is a block diagram for explaining the cathode gas supply control according to the present embodiment.
- a selection unit 117 that selects the larger one of the pulsation upper limit target pressure and the anode pressure is provided, and the pressure obtained by subtracting the allowable transmembrane pressure from the pressure output from the selection unit 117 is determined as the transmembrane pressure difference. This is different from the first embodiment in that it is input to the target cathode pressure calculation unit 110 as the limit request target pressure.
- FIG. 7 is a time chart for explaining operations of anode gas supply control and cathode gas supply control according to the present embodiment.
- the largest one of the oxygen partial pressure securing request pressure, the wetness control request target pressure, and the transmembrane differential pressure restriction request target pressure is the target cathode pressure.
- the cathode compressor 24 is controlled in accordance with the calculated target cathode pressure.
- the transmembrane pressure limit request target pressure obtained by subtracting the allowable transmembrane pressure from the pulsation upper limit target pressure is set as the target cathode pressure. (FIGS. 7C and 7D). Therefore, since the cathode compressor 24 is controlled according to the target cathode pressure held at a constant value, it is possible to suppress the generation of abnormal noise such as a swell sound from the cathode compressor 24 (FIG. 7F). .
- the transmembrane differential pressure restriction request target pressure obtained by subtracting the allowable transmembrane pressure from the anode pressure is set as the target cathode pressure (FIGS. 7C and 7D). ). For this reason, it is possible to suppress the transmembrane pressure difference from exceeding the allowable transmembrane pressure pressure during the down transition.
- the transmembrane differential pressure restriction request target pressure obtained by subtracting the allowable transmembrane differential pressure from the pulsation upper limit target pressure is set as the target cathode pressure. Therefore, since the cathode compressor 24 is controlled according to the target cathode pressure held at a constant value again, it is possible to suppress the generation of abnormal noise such as a swell sound from the cathode compressor 24 (FIG. 7F). ).
- the fuel cell system 100 includes the cathode compressor 24 for supplying the cathode gas to the fuel cell stack 1, the pulsation operation unit, the first target pressure setting unit, and the second target pressure setting unit. And a controller 4 as a compressor control unit.
- the pulsation operation unit pulsates the pressure of the anode gas based on the operation state of the fuel cell system 100.
- the first target pressure setting unit sets the first target pressure (target cathode pressure) of the cathode gas based on the request of the fuel cell stack 1 such as the oxygen partial pressure securing request and the wetness control request.
- the second target pressure setting unit is configured to maintain the second target pressure of the cathode gas (intermembrane) for maintaining the differential pressure in the fuel cell stack 1 within the allowable differential pressure range according to the pressure of the anode gas in the fuel cell stack 1.
- the differential pressure limit request target pressure is set based on the pulsation upper limit target pressure when the anode gas pressure is pulsated.
- the compressor control unit controls the cathode compressor 24 based on the first target pressure and the second target pressure.
- the second target pressure setting unit allows the allowable intermembrane pressure from the larger of the pulsation upper limit target pressure and the anode pressure so that the transmembrane differential pressure restriction request target pressure does not pulsate with the pressure pulsation of the anode gas.
- the pressure obtained by subtracting the differential pressure is set as the transmembrane differential pressure limit request target pressure.
- the pressure obtained by subtracting the allowable transmembrane pressure difference from the pulsation upper limit target pressure becomes the transmembrane differential pressure limit request target pressure, except during the down transition, so the transmembrane differential pressure limit request target pressure is set as the target cathode pressure.
- the cathode compressor 24 can be controlled in accordance with the target cathode pressure held at a constant value. Therefore, the same effect as in the first embodiment can be obtained, and the generation of abnormal noise such as swell noise from the cathode compressor 24 can be suppressed.
- a pressure obtained by subtracting the allowable transmembrane pressure from the larger of the pulsation upper limit target pressure and the anode pressure is input to the target cathode pressure calculation unit 110 as the transmembrane pressure limit request target pressure. It was.
- the anode pressure is pulsated as a predetermined fixed value without changing the pulsation upper limit target pressure and the pulsation lower limit target pressure in accordance with the target output current, as shown in FIG. You may comprise the control block of supply control.
- the transmembrane differential pressure limit request target pressure calculation unit 109 calculates the pressure obtained by subtracting the allowable transmembrane pressure from the pulsation upper limit target pressure as the transmembrane differential pressure limit request target pressure, You may input into the target cathode pressure calculation part 110.
- the pulsation upper limit target pressure used for calculation of the transmembrane differential pressure restriction request target pressure includes a value slightly smaller than the pulsation upper limit target pressure. Is included in the technical scope.
- the limited target cathode pressure calculation unit 111 calculates the larger of the target cathode pressure and the transmembrane differential pressure limit request target pressure as the limit target cathode pressure. You may make it correct
- the oxygen partial pressure ensuring required pressure and the wetness control required target pressure may be corrected by the transmembrane differential pressure restriction required target pressure. That is, the case where the first target pressure is corrected by the second target pressure is also included in the technical scope of the present invention.
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Abstract
Description
燃料電池は電解質膜をアノード電極(燃料極)とカソード電極(酸化剤極)とによって挟み、アノード電極に水素を含有するアノードガス(燃料ガス)、カソード電極に酸素を含有するカソードガス(酸化剤ガス)を供給することによって発電する。アノード電極及びカソード電極の両電極において進行する電極反応は以下の通りである。
カソード電極 : 4H+ +4e- +O2 →2H2O …(2)
次に本発明の第2実施形態について説明する。本実施形態は、カソードガス供給制御の内容が第1実施形態と相違する。以下、その相違点を中心に説明する。なお、以下の各実施形態では上述した第1実施形態と同様の機能を果たす部分には、同一の符号を用いて重複する説明を適宜省略する。
Claims (8)
- アノードガス及びカソードガスを燃料電池に供給して発電させる燃料電池システムであって、
前記燃料電池にカソードガスを供給するためのコンプレッサと、
前記燃料電池システムの運転状態に基づいて、アノードガスの圧力を脈動させる脈動運転部と、
前記燃料電池の要求に基づいて、カソードガスの第1目標圧力を設定する第1目標圧力設定部と、
前記燃料電池内のアノードガスの圧力に応じて前記燃料電池内の差圧を許容差圧範囲内に維持するためのカソードガスの第2目標圧力を設定する第2目標圧力設定部と、
第1目標圧力と第2目標圧力とに基づいてコンプレッサを制御するコンプレッサ制御部と、
を備え、
前記第2目標圧力設定部は、
アノードガスの圧力を脈動させるときの脈動時上限目標圧力に基づいて、前記第2目標圧力を設定する、
燃料電池システム。 - 前記第2目標圧力設定部は、
前記脈動時上限目標圧力から前記許容差圧を引いた圧力を、前記第2目標圧力として設定する、
請求項1に記載の燃料電池システム。 - 前記コンプレッサ制御部は、
前記第1目標圧力及び前記第2目標圧力の大きい方の圧力に基づいて前記コンプレッサを制御する
請求項2に記載の燃料電池システム。 - 前記第2目標圧力設定部は、
前記脈動時上限目標圧力及びアノードガスの実圧力の大きい方の圧力から前記許容差圧を引いた圧力を、前記第2目標圧力として設定する、
請求項1に記載の燃料電池システム。 - 前記第1目標圧力設定手段は、
前記燃料電池の負荷に基づいて、前記燃料電池内の酸素分圧を所定以上に保持するために必要な酸素分圧確保要求圧力を算出し、
前記燃料電池の負荷に基づいて、前記電解質膜の目標湿潤度を算出し、
前記目標湿潤度に基づいて、前記電解質膜の湿潤度を前記目標湿潤度に制御するために必要な湿潤度制御要求圧力を算出し、
前記燃料電池の負荷に基づいて制御されるアノードガスの実圧力から、前記許容差圧を引いた膜保護要求圧力を算出し、
前記酸素分圧確保要求圧力、前記湿潤度制御要求圧力及び膜保護要求圧力に基づいて、前記第1目標圧力を設定する、
請求項1から請求項3までのいずれか1つに記載の燃料電池システム。 - 前記第1目標圧力設定手段は、
前記燃料電池の負荷に基づいて、前記燃料電池内の酸素分圧を所定以上に保持するために必要な酸素分圧確保要求圧力を算出し、
前記燃料電池の負荷に基づいて、前記電解質膜の目標湿潤度を算出し、
前記目標湿潤度に基づいて、前記電解質膜の湿潤度を前記目標湿潤度に制御するために必要な湿潤度制御要求圧力を算出し、
前記酸素分圧確保要求圧力と前記湿潤度制御要求圧力とに基づいて、前記第1目標圧力を設定する、
請求項4に記載の燃料電池システム。 - 前記脈動運転制御部は、
前記燃料電池の負荷に基づいて、アノードガスの圧力を脈動させるときの脈動時上限目標圧力及び脈動時下限目標圧力を算出し、前記燃料電池の負荷が低いときに比して、高いときほど当該脈動時上限目標圧力及び当該脈動時下限目標圧力を高くする、
請求項1から請求項6までのいずれか1つに記載の燃料電池システム。 - アノードガス及びカソードガスを燃料電池に供給して発電させる燃料電池システムの制御方法であって、
前記燃料電池システムの運転状態に基づいて、アノードガスの圧力を脈動させる脈動運転工程と、
前記燃料電池の要求に基づいて、カソードガスの第1目標圧力を設定する第1目標圧力設定工程と、
前記燃料電池内のアノードガスの圧力に応じて前記燃料電池内の差圧を許容差圧範囲内に維持するためのカソードガスの第2目標圧力を設定する第2目標圧力設定工程と、
第1目標圧力と第2目標圧力とに基づいて、前記燃料電池にカソードガスを供給するためのコンプレッサを制御するコンプレッサ制御工程と、
を備え、
前記第2目標圧力設定工程は、
アノードガスの圧力を脈動させるときの脈動時上限目標圧力に基づいて、前記第2目標圧力を設定する、
燃料電池システムの制御方法。
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EP3035427B1 (en) * | 2013-08-12 | 2019-04-10 | Nissan Motor Co., Ltd. | Fuel cell system and fuel cell system control method |
CN109216736B (zh) * | 2018-09-25 | 2021-05-11 | 重庆大学 | 燃料电池多模式切换阳极压力脉动水冲刷控制系统 |
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CN106299420A (zh) * | 2015-06-25 | 2017-01-04 | 丰田自动车株式会社 | 燃料电池系统 |
CN106299420B (zh) * | 2015-06-25 | 2018-11-23 | 丰田自动车株式会社 | 燃料电池系统 |
EP3719077A1 (de) | 2019-04-02 | 2020-10-07 | Covestro Deutschland AG | Siloxan-haltige blockcopolycarbonate mit geringer domänengrösse |
WO2020201178A1 (de) | 2019-04-02 | 2020-10-08 | Covestro Intellectual Property Gmbh & Co. Kg | Siloxan-haltige blockcopolycarbonate mit geringer domänengrösse |
US11970615B2 (en) | 2019-04-02 | 2024-04-30 | Covestro Intellectual Property Gmbh & Co. Kg | Siloxane-containing block copolycarbonates having a small domain size |
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CN105531857B (zh) | 2018-01-30 |
EP3021397A4 (en) | 2016-08-10 |
CA2917986C (en) | 2018-07-31 |
CA2917986A1 (en) | 2015-01-15 |
EP3021397A1 (en) | 2016-05-18 |
JP6137315B2 (ja) | 2017-05-31 |
CN105531857A (zh) | 2016-04-27 |
US20160156046A1 (en) | 2016-06-02 |
EP3021397B1 (en) | 2019-04-17 |
US9843057B2 (en) | 2017-12-12 |
JPWO2015005229A1 (ja) | 2017-03-02 |
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