WO2010058747A1 - Système de pile à combustible et procédé de commande associé - Google Patents

Système de pile à combustible et procédé de commande associé Download PDF

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Publication number
WO2010058747A1
WO2010058747A1 PCT/JP2009/069425 JP2009069425W WO2010058747A1 WO 2010058747 A1 WO2010058747 A1 WO 2010058747A1 JP 2009069425 W JP2009069425 W JP 2009069425W WO 2010058747 A1 WO2010058747 A1 WO 2010058747A1
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WIPO (PCT)
Prior art keywords
pressure
fuel
fuel cell
cell system
electrode
Prior art date
Application number
PCT/JP2009/069425
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English (en)
Japanese (ja)
Inventor
靖 市川
圭吾 池添
健一 後藤
謙 中山
光徳 熊田
要介 冨田
Original Assignee
日産自動車株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2008298191A external-priority patent/JP5228835B2/ja
Priority claimed from JP2008302465A external-priority patent/JP5428307B2/ja
Application filed by 日産自動車株式会社 filed Critical 日産自動車株式会社
Priority to RU2011125325/07A priority Critical patent/RU2472256C1/ru
Priority to BRPI0921969 priority patent/BRPI0921969B1/pt
Priority to EP09827528.2A priority patent/EP2357699B1/fr
Priority to US13/129,986 priority patent/US9786931B2/en
Priority to CA2744304A priority patent/CA2744304C/fr
Priority to CN200980146527.2A priority patent/CN102224627B/zh
Publication of WO2010058747A1 publication Critical patent/WO2010058747A1/fr
Priority to US14/742,113 priority patent/US20150288008A1/en

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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
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M2008/1095—Fuel cells with polymeric electrolytes
    • 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
    • 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
    • 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
    • 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.
  • a fuel gas for example, hydrogen
  • an oxidant gas for example, air
  • these gases are reacted electrochemically to generate power.
  • a fuel cell system including a fuel cell for performing the above.
  • Patent Document 1 discloses a method of purging water and accumulated unreacted gas of the fuel cell by changing the gas pressures of the fuel electrode and the oxidant electrode.
  • Patent Document 1 since a relatively large pressure fluctuation is required to purge liquid water and unreacted gas, a large stress is applied to the electrolyte membrane or the like constituting the fuel cell. May affect the durability of the fuel cell.
  • An object of the present invention is to suppress reaction gas heterogeneity while suppressing a decrease in durability of the fuel cell.
  • an object of the present invention is to suppress the stress generated in the fuel cell and fuel gas supply system parts and to suppress the deterioration of the fuel cell system.
  • a fuel cell system includes a fuel cell that generates electric power by electrochemically reacting an oxidant gas supplied to an oxidant electrode and a fuel gas supplied to the fuel electrode; A fuel gas supply device that supplies the fuel gas to the fuel electrode; and when the fuel gas is supplied to the fuel electrode by controlling the fuel gas supply device and the outlet on the fuel electrode side is closed A control device for performing pressure fluctuations, wherein the control device periodically varies the pressure of the fuel gas at the fuel electrode based on a first pressure fluctuation pattern for performing the pressure fluctuations in a first pressure range.
  • a control method for a fuel cell system includes generating an electric power by electrochemically reacting an oxidant gas supplied to an oxidant electrode and a fuel gas supplied to the fuel electrode.
  • the fuel gas is supplied to the fuel electrode, and the fuel gas is supplied to the fuel electrode by controlling the supply of the fuel gas, and the outlet on the fuel electrode side is closed.
  • Pressure fluctuation is sometimes performed, and the pressure of the fuel gas at the fuel electrode is periodically changed based on a first pressure fluctuation pattern in which the pressure fluctuation is performed with a first pressure width.
  • the fuel cell system is a fuel cell that generates electric power by electrochemically reacting an oxidant gas supplied to the oxidant electrode and a fuel gas supplied to the fuel electrode.
  • the fuel gas supply means for supplying the fuel gas to the fuel electrode, and the fuel gas is supplied to the fuel electrode by controlling the fuel gas supply means, and the outlet on the fuel electrode side is closed
  • Control means for sometimes changing the pressure, wherein the control means periodically changes the pressure of the fuel gas at the fuel electrode based on a first pressure fluctuation pattern in which the pressure fluctuation is performed with a first pressure width.
  • the fuel electrode side gas can be agitated by periodically changing the pressure of the fuel gas in the fuel electrode based on the first pressure fluctuation pattern in which the pressure fluctuates in the first pressure range.
  • the fuel electrode side gas can be made uniform.
  • the present invention since the amount of fuel gas supply during the execution period of one control pattern is increased, the increase in the number of executions of pressure increase / decrease per unit time can be suppressed. Thereby, the stress applied to the fuel cell / fuel gas supply system parts can be alleviated, and deterioration of the fuel cell system can be suppressed.
  • FIG. 1A is a block diagram schematically showing the configuration of the fuel cell system according to the first embodiment.
  • FIG. 1B is a block diagram schematically showing another configuration of the fuel cell system according to the first embodiment.
  • FIG. 2A is an explanatory diagram showing the state of the fuel electrode side hydrogen in the fuel cell, and shows the hydrogen streamlines in the fuel electrode side gas flow path.
  • FIG. 2B shows the hydrogen concentration distribution in the fuel electrode side gas flow path.
  • FIG. 2C shows the hydrogen concentration distribution on the fuel electrode side reaction surface.
  • FIG. 3A is an explanatory diagram schematically showing a fuel cell, and assumes eight current measurement points.
  • FIG. 3B shows a time-series transition of the current distribution at each measurement point.
  • FIG. 4 is a cross-sectional view schematically showing the structure of the fuel battery cell.
  • FIG. 5 is an explanatory diagram showing the relationship between the nitrogen partial pressure difference between the oxidant electrode and the fuel electrode and the amount of leaked nitrogen.
  • FIG. 6 is an explanatory diagram showing the relationship between the ambient humidity and the amount of leaked nitrogen according to the ambient temperature.
  • Fig.7 (a) is explanatory drawing which shows typically the stirring state of hydrogen and an unreacted gas.
  • FIG. 7B shows the timing of stopping the hydrogen supply (valve closing operation).
  • Fig.8 (a) is explanatory drawing which shows a liquid water discharge state.
  • FIG. 8B shows the timing of stopping the hydrogen supply (valve closing operation).
  • FIG.8 (c) shows another example of the timing which stops hydrogen supply (valve closing operation).
  • FIG. 8D shows still another example of timing for stopping the hydrogen supply (valve closing operation).
  • FIG. 9 is an explanatory diagram showing a current distribution in the power generation plane.
  • FIG. 10 is a flowchart showing a processing procedure of a control method of the fuel cell system according to the second embodiment.
  • FIG. 11 is an explanatory diagram illustrating a control pattern according to the first control method.
  • FIG. 12 is an explanatory diagram illustrating a control pattern according to the second control method.
  • FIG. 13 is an explanatory diagram illustrating a control pattern according to the third control method.
  • FIG. 14 is an explanatory diagram showing changes in pressure increase and decrease in the fuel electrode.
  • FIG. 15 is an explanatory diagram of the first holding time Tp1.
  • FIG. 16 is an explanatory diagram of the second holding time Tp2.
  • FIG. 17 is an explanatory diagram of the first holding time Tp1, the second holding time Tp2, and the load.
  • FIG. 18 is an explanatory diagram of the first holding time Tp1, the second holding time Tp2, and the load.
  • FIG. 19 is an explanatory diagram of the load current and the upper limit pressure P1 and lower limit pressure P2.
  • FIG. 20A is an explanatory diagram schematically showing the fuel electrode side volume Rs and the volume Rt of the volume portion in the fuel cell stack.
  • FIG. 20 (b) shows that about 1/4 of the volume of the fuel system has flowed in new hydrogen.
  • FIG. 21 is an explanatory diagram of the upper limit pressure P1 and the lower limit pressure P2.
  • FIG. 22 is an explanatory diagram of the pressure drop speed.
  • FIG. 1A is a block diagram schematically showing the configuration of the fuel cell system 100 according to the first embodiment of the present invention.
  • the fuel cell system 100 is mounted on, for example, a vehicle that is a moving body, and the vehicle is driven by electric power supplied from the fuel cell system 100.
  • the fuel cell system 100 mainly includes a fuel cell stack 1 configured by stacking a plurality of fuel cells.
  • Each fuel cell constituting the fuel cell stack 1 is a fuel in which a fuel electrode 67 (see FIG. 4 described later) and an oxidizer electrode 34 (refer to FIG. 4 described later) are opposed to each other with a solid polymer electrolyte membrane interposed therebetween.
  • the battery structure is sandwiched between a pair of separators.
  • a pair of internal flow paths extending in the stacking direction of the fuel cells is configured corresponding to each of the fuel gas and the oxidant gas.
  • the supply internal flow path which is the first internal flow path
  • the gas flow path cell flow path
  • the fuel gas is respectively supplied to the reaction surface on the fuel electrode 67 side, and the gas discharged from the fuel electrode 67 side gas flow path of each fuel cell is supplied to the discharge internal flow path which is the second internal flow path.
  • fuel electrode off-gas flows in.
  • the supply internal flow path that is the first internal flow path includes the oxidant electrode 34 side gas flow paths (cell flow paths) of the individual fuel cells. ) Is supplied to the reaction surface on the oxidant electrode 34 side, and the discharge internal flow path, which is the second internal flow path, is supplied from the gas flow path on the oxidant electrode 34 side of each fuel cell.
  • Each discharged gas hereinafter referred to as “oxidant electrode off-gas”) flows in.
  • the fuel cell stack 1 according to the first embodiment employs a so-called counter flow system in which the fuel gas and the oxidant gas flow in directions opposite to each other.
  • the fuel cell stack 1 generates generated power by electrochemically reacting the fuel gas and the oxidant gas supplied to the fuel electrode 67 and the oxidant electrode 34 for each individual fuel cell.
  • the fuel cell system 100 further includes a hydrogen system for supplying hydrogen to the fuel cell stack 1 and an air system for supplying air to the fuel cell stack 1.
  • hydrogen which is a fuel gas
  • a fuel tank 10 for example, a high-pressure hydrogen cylinder
  • the fuel cell stack from the fuel tank 10 via a hydrogen supply channel (fuel electrode inlet channel) L1. 1 is supplied.
  • the hydrogen supply flow path L1 has a first end connected to the fuel tank 10 and a second end connected to the inlet side of the fuel gas supply internal flow path of the fuel cell stack 1. Yes.
  • a tank original valve (not shown in FIG. 1) is provided downstream of the fuel tank 10, and when this tank original valve is opened, the high-pressure hydrogen gas from the fuel tank 10 is opened. Is mechanically reduced to a predetermined pressure by a pressure reducing valve (not shown in FIG.
  • the depressurized hydrogen gas is further depressurized by a hydrogen pressure adjusting valve 11 provided downstream of the depressurizing valve, and then supplied to the fuel cell stack 1.
  • the hydrogen pressure supplied to the fuel cell stack 1, that is, the hydrogen pressure at the fuel electrode 67 can be adjusted by controlling the opening of the hydrogen pressure regulating valve 11.
  • a hydrogen supply device that supplies hydrogen to the fuel electrode 67 of the fuel cell stack 1 by the fuel tank 10, the hydrogen supply flow path L1, and the hydrogen pressure regulating valve 11 provided in the hydrogen supply flow path L1.
  • HS fuel gas supply device HS
  • the fuel cell stack 1 is basically closed at the outlet side of the fuel gas discharge internal flow path in the fuel cell stack 1, and discharge of the fuel electrode off-gas from the fuel cell stack 1 is restricted.
  • the so-called closed system fuel cell system 100 is configured. However, this does not indicate a strict blockage, but in order to discharge an inert gas such as nitrogen or impurities such as liquid water from the fuel electrode 67, an exception is made in the internal flow path for discharging the fuel gas.
  • a discharge system is provided that can open the outlet side. Specifically, a fuel electrode off-gas flow path (discharge flow path) L2 is connected to the outlet side of the internal flow path for fuel gas discharge. The second end of the fuel electrode off-gas channel L2 is connected to an oxidant electrode off-gas channel L6 described later.
  • the fuel electrode off-gas flow path L2 has a predetermined volume Rs (FIG. 20 described later), for example, a volume Rs that is the same as or about 80% of the volume on the fuel electrode 67 side for all fuel cells constituting the fuel cell stack 1.
  • the volume part (volume apparatus) 12 provided as is provided.
  • the volume portion 12 functions as a buffer for temporarily storing impurities contained in the fuel electrode off-gas flowing from the fuel electrode 7 side.
  • a drainage flow path L3 having a first end opened is connected to the lower portion of the volume portion 12 in the vertical direction, and a drainage valve 13 is provided in the drainage flow path L3. Impurities (mainly liquid water) contained in the fuel electrode off gas that has flowed into the volume portion 12 accumulate in the lower portion of the volume portion 12.
  • the accumulated impurities can be discharged by controlling the open / close state of the drain valve 13.
  • a purge valve (shutoff device) 14 is provided in the fuel electrode off-gas flow path L ⁇ b> 2 on the downstream side of the volume portion 12.
  • the fuel electrode off-gas flowing into the volume 12, specifically, a gas containing impurities (mainly inert gas such as nitrogen) and unreacted hydrogen can be discharged by controlling the open / close state of the purge valve 14.
  • the fuel electrode off-gas channel (discharge channel) L2 the volume part (volume device) 12, and the purge valve (blocking device) 14 form a limiting device 70.
  • air that is an air-based oxidant gas will be described.
  • the atmosphere is taken in by the compressor 20, the atmosphere is pressurized and air is supplied to the fuel cell stack 1 via the air supply flow path L5.
  • the air supply flow path L5 has a first end connected to the compressor 20 and a second end connected to the inlet side of the internal flow path for supplying oxidant gas in the fuel cell stack 1. Further, a humidifier 21 for humidifying the air supplied to the fuel cell stack 1 is provided in the air supply flow path L5.
  • An oxidant electrode off-gas channel L6 is connected to the outlet side of the oxidant gas discharge internal channel in the fuel cell stack 1. Thereby, the oxidant electrode off-gas from the oxidant electrode 34 in the fuel cell stack 1 is discharged to the outside through the oxidant electrode off-gas channel L6.
  • the humidifier 21 is provided in the oxidant electrode off-gas flow path L6, and moisture generated by power generation is dehumidified (this dehumidified moisture is used for humidifying the supply air).
  • an air pressure regulating valve 22 is provided on the downstream side of the humidifier 21.
  • the air pressure supplied to the fuel cell stack 1, that is, the air pressure at the oxidant electrode 34 can be adjusted by controlling the opening of the air pressure regulating valve 22.
  • a gas supply device OS is configured.
  • an output extraction device 30 that controls an output (for example, current) extracted from the fuel cell stack 1 is connected to the fuel cell stack 1.
  • the electric power generated by the fuel cell stack 1 is necessary for the electric power generation operation of the vehicle driving electric motor (not shown in FIG. 1), the secondary battery, and the fuel cell stack 1 via the output extraction device 30. Supplied to various accessories.
  • the electric power generated in the output extraction device 30 is also supplied to a secondary battery (not shown in FIG. 1). This secondary battery is provided to compensate for the shortage of power supplied from the fuel cell stack 1 when the fuel cell system 100 is started up or during a transient response.
  • the control unit (control device) 40 has a function of controlling the entire fuel cell system 100 in an integrated manner, and controls the operating state of the fuel cell system 100 by operating according to the control program.
  • a microcomputer mainly composed of a CPU, a ROM, a RAM, and an I / O interface can be used.
  • the control unit 40 performs various calculations according to a control program stored in the ROM, and outputs the calculation results to various actuators (not shown in FIG. 1) as control signals.
  • the control unit 40 controls various elements such as the hydrogen pressure regulating valve 11, the drain valve 13, the purge valve 14, the compressor 20, the air pressure regulating valve 22, and the output extraction device 30, and the power generation operation of the fuel cell stack 1 is controlled. Do.
  • the hydrogen pressure sensor 41 detects the hydrogen pressure supplied to the fuel cell stack 1.
  • the air pressure sensor 42 detects the pressure of the air supplied to the fuel cell stack 1.
  • the stack temperature sensor 43 detects the temperature of the fuel cell stack 1.
  • the control unit 40 controls the fuel cell system 100 in the following manner. First, the control unit 40 supplies air and hydrogen to the fuel cell stack 1, thereby generating power by the fuel cell stack 1. Each pressure (operating pressure) of air and hydrogen supplied to the fuel cell stack 1 is set in advance as a constant reference value or a variable value corresponding to the operating load regardless of the operating load. Therefore, the control unit 40 generates power in the fuel cell stack 1 by supplying air and hydrogen at a predetermined operating pressure.
  • the control unit 40 when the control unit 40 supplies hydrogen to the fuel electrode 67 of the fuel cell stack 1, the control unit 40 performs pressure variation with a first pressure width (differential pressure).
  • the hydrogen pressure at the fuel electrode 67 of the fuel cell stack 1 is periodically changed based on the pressure fluctuation pattern and the second pressure fluctuation pattern in which the pressure fluctuation is performed with a second pressure width (differential pressure) larger than the first pressure width. Fluctuate.
  • the control unit 40 repeatedly performs the basic control pattern for executing the second pressure fluctuation pattern after executing the first pressure fluctuation pattern a plurality of times.
  • the control unit 40 stops the supply of hydrogen to the fuel cell stack 1, and the hydrogen pressure at the fuel electrode 67 of the fuel cell stack 1 is a predetermined pressure width (first pressure width or second pressure width).
  • the supply of hydrogen to the fuel cell stack 1 is resumed, and the hydrogen pressure at the fuel electrode 67 of the fuel cell stack 1 is returned to the operating pressure.
  • the hydrogen supply to the fuel cell stack 1 can be stopped and restarted by opening / closing the hydrogen pressure regulating valve 11.
  • the hydrogen pressure drop corresponding to the pressure range can be monitored by referring to the detection value of the hydrogen pressure sensor 41.
  • FIG. 1B is a block diagram schematically showing another configuration of the fuel cell system 100 according to the first embodiment of the present invention.
  • the drain valve 13 is eliminated and only the purge valve 14 is used.
  • impurities mainly inert gas such as nitrogen and liquid water
  • unreacted hydrogen gas contained in the fuel electrode off-gas can be discharged by controlling the open / close state of the purge valve 14.
  • FIG. 2A shows a hydrogen stream line in the fuel electrode 67 side gas flow path.
  • the horizontal axis indicates the distance of the gas flow path (in the direction of the gas flow path)
  • the left side of the horizontal axis corresponds to the inlet side of the gas flow path
  • the right side of the horizontal axis corresponds to the outlet side of the gas flow path. It corresponds.
  • the vertical axis indicates the height of the gas flow path
  • the lower side of the vertical axis corresponds to the reaction surface.
  • FIG. 2B shows the hydrogen concentration distribution in the gas passage on the fuel electrode 67 side. Similar to FIG.
  • a region a1 shows a range where the hydrogen concentration is 93% to 100%
  • a region a2 shows a range where the hydrogen concentration is 83% to 93%
  • a region a3 shows a hydrogen concentration of 73%. Shows a range of ⁇ 83%.
  • the region a4 indicates a range where the hydrogen concentration is 63% to 73%
  • the region a5 indicates a range where the hydrogen concentration is 53% to 63%
  • the region a6 indicates a range where the hydrogen concentration ranges from 43% to 53%.
  • Region a7 shows a hydrogen concentration range of 33% to 43%.
  • FIG. 2C shows a hydrogen concentration distribution on the reaction surface on the fuel electrode 67 side.
  • the horizontal axis indicates the distance of the gas flow path
  • the left side of the horizontal axis corresponds to the inlet side of the gas flow path
  • the right side of the horizontal axis corresponds to the outlet side of the gas flow path.
  • the vertical axis represents the hydrogen concentration.
  • the fuel electrode 67 has a portion where the nitrogen concentration is high, that is, a portion where the hydrogen concentration is low. Specifically, in the fuel battery cell, the hydrogen concentration tends to be lower toward the downstream (outlet side) of the gas flow path. Further, if power generation is continued from this state, the concentration of the portion having a low hydrogen concentration is further decreased.
  • FIG. 3 is an explanatory view schematically showing a fuel cell.
  • eight current measurement points # 1 to # 8 are assumed in the power generation surface of the fuel cell along the flow of the reaction gas.
  • FIG. 3B shows a time-series transition of the current distribution at the individual measurement points # 1 to # 8. Specifically, as indicated by broken line arrows, the transition of the current distribution at each of the measurement points # 1 to # 8 transitions from the alternate long and short dash line to the broken line and then to the solid line. That is, at the initial stage of power generation, the hydrogen concentration in the gas flow path is substantially uniform, so that the current values at the measurement points # 1 to # 8 correspond approximately as indicated by the dashed line.
  • FIG. 4 is a cross-sectional view schematically showing the structure of the fuel cell.
  • the fuel cell structure 150 constituting the fuel cell is configured by sandwiching the solid polymer electrolyte membrane 2 between a fuel electrode 67 and an oxidant electrode 34 which are a pair of electrodes (reaction electrodes).
  • the solid polymer electrolyte membrane 2 is composed of, for example, an ion conductive polymer membrane such as a fluororesin ion exchange membrane, and functions as an ion conductive electrolyte when saturated with water.
  • the oxidant electrode 34 includes a platinum-based catalyst layer 3 that supports a catalyst such as platinum, and a gas diffusion layer 4 that is formed of a porous material such as carbon fiber.
  • the fuel electrode 67 includes a platinum-based catalyst layer 6 that supports a catalyst such as platinum, and a gas diffusion layer 7 that is formed of a porous material such as carbon fiber.
  • Gas separators (not shown in FIG. 4) sandwiching the fuel cell structure 150 from both sides are formed with gas flow paths 5 and 8 for supplying a reaction gas (hydrogen or air) to each reaction electrode. Has been.
  • Fuel electrode 67 side O 2 + 4H + + 4e ⁇ ⁇ 2H 2 O
  • Oxidant electrode 34 side C + 2H 2 O ⁇ CO 2 + 4H + + 4e ⁇
  • carbon in the structure of the fuel cell reacts with water generated on the oxidant electrode 34 side, and carbon dioxide is generated on the oxidant electrode 34 side. This means that the structure inside the fuel cell is eroded.
  • An element that forms a gas flow path, a structure that supports a catalyst that causes a reaction, a structure that constitutes a gas diffusion layer 4, and a carbon that is contained in a structure that constitutes a separator is changed to carbon dioxide. Leading to deterioration.
  • the power generation reaction product water moves from the oxidant electrode 34 side to the solid polymer electrolyte membrane 2 by the reverse diffusion phenomenon, or the condensed water in the hydrogen supplied after being humidified is gas. May remain in the flow path.
  • liquid water is present in the form of water droplets in the gas flow path, no particular problem is caused.
  • the liquid water is present in a film shape and covers the gas flow path surface of the gas diffusion layer 7, the supply of hydrogen to the reaction surface is hindered by the liquid water, resulting in a location where the hydrogen concentration is low. . This may lead to deterioration of the fuel cell, similar to the case on the oxidant electrode 34 side.
  • FIG. 5 is an explanatory diagram showing the relationship between the nitrogen partial pressure difference between the oxidant electrode 34 and the fuel electrode 67 and the amount of leaked nitrogen.
  • FIG. 6 is an explanatory diagram showing the relationship between the ambient humidity and the amount of leaked nitrogen according to the ambient temperature. As shown by the broken line arrows, the ambient humidity and the ambient humidity are increased according to the increase in the ambient temperature Temp1, Temp2, Temp3, and Temp4. The value of the relationship with the leak flow rate is relatively large. As shown in FIG. 5, the amount of nitrogen permeated from the oxidizer electrode 34 side to the fuel electrode 67 side (leakage nitrogen amount) increases as the nitrogen partial pressure difference increases, and the humidity at the fuel electrode 67 increases as shown in FIG. The higher the temperature and the higher the temperature.
  • the nitrogen that has permeated the fuel electrode 67 rides on the flow of supplied hydrogen and remains so as to be pushed downstream (outlet side). Therefore, in the first embodiment, the occurrence of such a deficient portion where the hydrogen concentration is locally lowered is suppressed by causing forced convection and stirring hydrogen and nitrogen.
  • FIG. 7 is an explanatory view schematically showing a stirring state of hydrogen and an unreacted gas (mainly nitrogen).
  • an unreacted gas mainly nitrogen.
  • the hydrogen pressure on the fuel electrode 67 side of the fuel cell stack 1 is lowered below the hydrogen supply pressure, and a predetermined differential pressure is created inside and outside the fuel cell stack 1.
  • a large supply amount (flow velocity) of hydrogen flowing into the fuel cell stack 1 is instantaneously ensured.
  • stirring with hydrogen and nitrogen is attained.
  • this agitation effect is increased when turbulent flow is obtained.
  • This differential pressure ⁇ P1 is, for example, about 5 to 8 kPa.
  • the optimum value of the differential pressure ⁇ P1 can be set through experiments and simulations in consideration of the characteristics of the fuel cell stack 1 and the gas agitation characteristics.
  • the differential pressure ⁇ P1 required for gas agitation is set to a small value compared to the differential pressure required for liquid water discharge described later.
  • the above gas agitation can suppress the occurrence of hydrogen-deficient parts, when power generation is continued for a long time, the generated water and condensed water accumulate and block the fuel electrode 67 side gas flow path in the fuel cell. It may end up. Therefore, in the first embodiment, by flowing hydrogen into the fuel electrode 67, liquid water that closes the gas flow path is discharged out of the fuel cell.
  • FIG. 8 is an explanatory view showing a liquid water discharge state.
  • the hydrogen pressure on the fuel electrode 67 side of the fuel cell stack 1 is lowered below the hydrogen supply pressure, and a predetermined differential pressure is created inside and outside the fuel cell stack 1. Then, by releasing this constant differential pressure instantaneously, a large supply amount (flow velocity) of the fuel gas flowing into the fuel cell stack 1 is instantaneously ensured.
  • Fig.8 (a) liquid water can be discharged
  • the differential pressure required for liquid water discharge is required to be larger than the differential pressure required for gas stirring.
  • the frequency at which liquid water discharge is required is lower than the frequency at which gas agitation is required. Therefore, as shown in FIG. 8B, after the pressure fluctuation pattern required for gas stirring is executed a plurality of times, hydrogen supply is stopped by the hydrogen pressure regulating valve 11 at the timing Tm (valve closing operation). Then, a holding time is provided until the predetermined differential pressure (pressure width) ⁇ P2 is reached, thereby ensuring the differential pressure.
  • the differential pressure ⁇ P2 is obtained (timing Tn)
  • hydrogen is supplied by the hydrogen pressure regulating valve 11 (opening operation). As a result, a large flow rate is instantaneously generated and liquid water can be discharged.
  • Such a pressure fluctuation pattern (second pressure fluctuation pattern) is periodically repeated in the same manner as the first pressure fluctuation pattern required for gas stirring.
  • the frequency of execution of the second pressure fluctuation pattern required for liquid water discharge is lower than that of the first pressure fluctuation pattern required for gas stirring.
  • This differential pressure ⁇ P2 is, for example, about 20 to 30 kPa.
  • the optimum value of the differential pressure ⁇ P2 can be set through experiments and simulations in consideration of the characteristics of the fuel cell stack 1 and the liquid water discharge characteristics.
  • the differential pressure ⁇ P2 required for liquid water discharge is set to a larger value than the differential pressure ⁇ P1 required for gas stirring.
  • an operation (valve closing operation) for stopping the supply of hydrogen by the hydrogen pressure regulating valve 11 at the timing Tm is performed. Do. Then, a holding time is provided until a predetermined differential pressure (pressure width) ⁇ P1 is reached, thereby ensuring the differential pressure.
  • a predetermined differential pressure (pressure width) ⁇ P1 is reached, thereby ensuring the differential pressure.
  • an operation (opening operation) of supplying hydrogen by opening the hydrogen pressure regulating valve 11 with a larger opening than at the timing Tm is performed. As a result, the gas is supplied at a pressure higher than the pressure at Tm and reaches a predetermined differential pressure (pressure width) ⁇ P2 (timing To).
  • timing Tp an operation (valve closing operation) for stopping the supply of hydrogen with the hydrogen pressure regulating valve 11 is performed. Then, a holding time is provided until a predetermined differential pressure (pressure width) ⁇ P2 is reached, thereby ensuring the differential pressure.
  • a predetermined differential pressure (pressure width) ⁇ P2 is obtained (timing Tq)
  • an operation (opening operation) of supplying hydrogen with the hydrogen pressure regulating valve 11 is performed. At that time, it is preferable to supply hydrogen at the same opening degree as the timing Tm.
  • the pressure returns to the same pressure as the timing Tm at the timing Tr, and the same pressure fluctuation pattern as before the timing Tm is executed after the timing Tr. Even when such an operation is performed, liquid water can be discharged by generating a large flow rate instantaneously.
  • timing Tp an operation (valve closing operation) for stopping the supply of hydrogen with the hydrogen pressure regulating valve 11 is performed. Then, a holding time is provided until a predetermined differential pressure (pressure width) ⁇ P3 is reached, thereby ensuring the differential pressure.
  • the pressure lower limit value when the differential pressure ⁇ P3 is secured is preferably the pressure lower limit value when the differential pressure ⁇ P1 is secured.
  • timing Tq an operation (opening operation) of supplying hydrogen with the hydrogen pressure regulating valve 11 is performed. At that time, it is preferable to supply hydrogen at the same opening degree as the timing Tm.
  • the pressure returns to the same pressure as the timing Tm at the timing Tr, and the same pressure fluctuation pattern as before the timing Tm is executed after the timing Tr. Even when such an operation is performed, liquid water can be discharged by generating a large flow rate instantaneously.
  • the control unit 40 supplies the hydrogen to the fuel electrode 67 of the fuel cell stack 1 by controlling the fuel gas supply device HS (10, 11, L1), and the first pressure.
  • the hydrogen pressure in the fuel electrode 67 of the fuel cell stack 1 is periodically changed based on the first pressure fluctuation pattern in which the pressure fluctuation is performed with the width ⁇ P1 and the second pressure fluctuation pattern in which the pressure fluctuation is performed with the second pressure width ⁇ P2.
  • the first pressure fluctuation pattern having a small pressure width is included in addition to the second pressure fluctuation pattern, so that the fuel electrode 67 is not subjected to a large stress on the individual fuel cells of the fuel cell stack 1.
  • Side gas can be stirred.
  • the fuel electrode 67 side gas can be made uniform. Therefore, it is possible to suppress the deterioration of the fuel cell stack 1 due to the partial decrease in the hydrogen concentration.
  • by providing the second pressure fluctuation pattern it is possible to discharge liquid water or the like that cannot be discharged by the first pressure fluctuation pattern. Thereby, deterioration of the fuel cell stack 1 due to liquid water can be suppressed.
  • the fuel cell system 100 of the first embodiment employs a closed system in which the fuel electrode off-gas discharged from the fuel electrode 67 side of the fuel cell stack 1 is limited. According to such a configuration, the hydrogen concentration tends to decrease in the fuel electrode 67 side gas flow path due to impurities, but by performing the above control, the fuel electrode 67 side gas can be made uniform.
  • the control unit 40 executes the second pressure fluctuation pattern after executing the first pressure fluctuation pattern a plurality of times. According to such a configuration, it is possible to achieve both gas agitation and liquid water discharge on the fuel electrode 67 side while reducing the frequency with which a large stress is applied to individual fuel cells of the fuel cell stack 1. Moreover, since the execution frequency of the 1st pressure fluctuation pattern which performs gas stirring is high, gas stirring can be performed effectively, even when power generation is performed continuously. As a result, as shown in FIG. 9, even when power generation is continuously performed, the current value in the power generation surface substantially corresponds, and the current value decreases on the outlet side of the gas flow path and on the inlet side of the gas flow path. Current concentration can be suppressed.
  • the control unit 40 stops the supply of hydrogen to the fuel cell stack 1 in a state in which the fuel cell stack 1 generates power by supplying hydrogen at a predetermined operating pressure,
  • the hydrogen pressure at the fuel electrode 67 is changed by restarting the hydrogen supply on condition that the hydrogen pressure at the electrode 67 has decreased by a predetermined pressure range ( ⁇ P1, ⁇ P2).
  • ⁇ P1, ⁇ P2 a predetermined pressure range
  • the fuel cell system 100 of the first embodiment includes the fuel electrode off-gas flow path L2, the volume portion 12, and the purge valve.
  • the volume portion 12 functions as a fuel electrode off-gas from the fuel electrode 67 side, that is, a space for storing nitrogen and liquid water (volume Rs: FIG. 20 described later).
  • impurities such as nitrogen that have risen relatively to the outside by opening the purge valve 14 as necessary. That is, nitrogen leaks occur until the nitrogen partial pressure difference disappears, but when it is desired to keep the hydrogen concentration at a predetermined level or higher on the fuel electrode 67 side, a flow rate corresponding to the leak amount can be discharged to the outside.
  • the flow rate at this time is sufficiently small, there is little influence on the pressure fluctuation required for gas stirring in the fuel electrode 67, and dilution by the oxidant electrode 34 being off can be easily performed.
  • the total pressure on the fuel electrode 67 side may be increased so that power can be generated even when the nitrogen partial pressure is in an equilibrium state. In this case, a simple closed system can be employed.
  • the rate at which the hydrogen pressure in the fuel electrode 67 decreases when the hydrogen supply is stopped is determined by the flow path volume in the fuel cell stack 1.
  • the capacity of the volume portion 12 of the hydrogen supply flow path L1 or the fuel electrode off-gas flow path L2 is changed in the fuel cell stack 1. The pressure change time can be controlled.
  • the fuel cell system 100 according to the second embodiment is different from the fuel cell system 100 of the first embodiment in that hydrogen supplied to the fuel electrode 67 of the fuel cell stack 1 due to pressure fluctuation due to the pressure fluctuation pattern.
  • the amount is set to be variable according to the operation state of the fuel cell system 100. Since the configuration of the fuel cell system 100 is the same as that of the first embodiment, a duplicate description will be omitted, and the following description will focus on the differences.
  • FIG. 10 is a flowchart showing a control method of the fuel cell system 100 according to the second embodiment of the present invention, specifically, a processing procedure of a method of supplying hydrogen to the fuel electrode 67.
  • the control unit 40 executes the process shown in this flowchart.
  • step 1 (S1) the control unit 40 detects the operating state of the fuel cell stack 1.
  • the operating state detected in step 1 includes the operating load of the fuel cell stack 1, the operating temperature of the fuel cell stack 1, and the operating pressure of the fuel cell stack 1 (the operating pressure of the oxidizer electrode 34).
  • the operating load of the fuel cell stack 1 can be calculated by taking into account the vehicle-side required power specified from the vehicle speed and the accelerator opening, the required power of auxiliary equipment, and the like.
  • the operating temperature of the fuel cell stack 1 can be detected by the stack temperature sensor 43.
  • a constant reference value or a variable value corresponding to the operating load is set in advance regardless of the above operating load. Therefore, the operation pressure of the fuel cell stack 1 can be detected by referring to this.
  • step 2 the control unit 40 determines whether or not the operation state detected this time has changed in comparison with the operation state detected in advance. If an affirmative determination is made in this determination, that is, if the operating state has changed, the process proceeds to step 3 (S3). On the other hand, if a negative determination is made in step 2, that is, if the operating state has not changed, the process of step 3 is skipped and the process proceeds to step 4 (S4).
  • step 3 the control unit 40 sets a pressure fluctuation pattern based on the operating state. As shown in the first embodiment, the control unit 40 executes the first pressure fluctuation pattern necessary for gas stirring a plurality of times, and then executes the second pressure fluctuation pattern necessary for liquid water discharge, and sets this one set. As a result, hydrogen supply is performed. By the way, in the supply mode with pressure fluctuation, the amount of hydrogen supplied to the fuel electrode 67 changes pulsatically due to pressure fluctuation, so that a load is repeatedly applied to the solid polymer electrolyte membrane 2 and this acts as stress. .
  • the amount of hydrogen supplied to the fuel electrode 67 due to such pressure fluctuation is reduced to reduce the load on the solid polymer electrolyte membrane 2. It is preferable.
  • pressure fluctuation is actively performed, and the amount of hydrogen supplied to the fuel electrode 67 due to the pressure fluctuation is pulsatically changed to perform gas agitation and liquid water discharge. preferable.
  • the amount of nitrogen that cross leaks is small. Therefore, when the operating state is changed corresponding to any of the above, the amount of hydrogen supplied to the fuel electrode 67 due to pressure fluctuation is reduced.
  • the basic control pattern is corrected as follows.
  • the valve closing time T of the hydrogen pressure regulating valve 11 is set longer than the valve closing time of the basic control pattern.
  • the basic control pattern is corrected so that the execution period of the pressure fluctuation is set to be large.
  • the differential pressures (pressure widths) ⁇ P11, ⁇ P21 of the pressure control pattern are set smaller than the differential pressures (pressure widths) ⁇ P1, ⁇ P2 of the pressure control pattern in the basic control pattern. To do.
  • the execution frequency of the second pressure fluctuation pattern required for liquid water discharge with respect to the first pressure fluctuation pattern required for gas stirring is less than the execution frequency of the basic control pattern.
  • the first to third control methods may be controlled in opposite directions.
  • the control unit 40 corrects the basic control pattern based on any one of the first to third control methods or a combination thereof according to the changed operating state. Then, the control unit 40 sets the corrected control pattern as the current control pattern.
  • step 4 the control unit 40 supplies hydrogen based on the currently set control pattern.
  • step 5 the control unit 40 determines whether or not to end the operation of the fuel cell system 100. Specifically, the control unit 40 determines whether or not an off signal is input from the ignition switch. When an affirmative determination is made in step 5, that is, when the operation of the fuel cell system 100 is terminated, the present control is terminated. On the other hand, if a negative determination is made in step 5, that is, if the operation of the fuel cell system 100 is not terminated, the processing returns to step 1.
  • the amount of hydrogen supplied to the fuel electrode 67 due to pressure fluctuation is set to be small based on the operating state of the fuel cell system 100. According to such a configuration, it is possible to reduce the repeated load on the individual fuel cells of the fuel cell stack 1 while performing gas stirring and liquid water discharge of the fuel electrode 67.
  • the control unit 40 controls the fuel cell system 100 in the following manner.
  • the control unit 40 supplies air and hydrogen to the fuel cell stack 1, thereby generating power by the fuel cell stack 1.
  • the control unit 40 supplies air and hydrogen so that the respective pressures of air and hydrogen supplied to the fuel cell stack 1 become predetermined operating pressures.
  • This operating pressure is set, for example, as a constant reference value regardless of the power generated by the fuel cell stack 1 or as a variable value corresponding to the power generated by the fuel cell stack 1.
  • control unit 40 performs pressure control on the air supply to the oxidant electrode 34 according to a predetermined operating pressure.
  • the control unit 40 controls supply / stop of hydrogen according to a control pattern for increasing / decreasing the pressure within the range between the upper limit pressure P1 and the lower limit pressure P2 for supplying hydrogen to the fuel electrode 67. Then, the control unit 40 repeats the operation according to the control pattern, so that hydrogen is supplied to the fuel electrode 67 while periodically changing the hydrogen pressure at the fuel electrode 67 of the fuel cell stack 1 as shown in FIG. Supply.
  • control unit 40 assumes that the hydrogen pressure of the fuel electrode 67 has reached the upper limit pressure P1, and that a sufficient hydrogen concentration for generating power is secured in the fuel electrode 67.
  • the hydrogen pressure regulating valve 11 is controlled to the minimum opening, and the hydrogen supply to the fuel cell stack 1 is stopped.
  • the control unit 40 continues from the fuel cell stack 1 via the output extraction device 30 to extract the load current corresponding to the required load required for the fuel cell system 100, hydrogen is consumed by the power generation reaction.
  • the hydrogen pressure decreases.
  • the control unit 40 controls the hydrogen pressure regulating valve 11 to the maximum opening and restarts the hydrogen supply to the fuel cell stack 1. . Thereby, the hydrogen pressure in the fuel electrode 67 increases. Then, on the condition that the hydrogen pressure has reached (returned to) the upper limit pressure P1, the control unit 40 stops the hydrogen supply again by controlling the hydrogen pressure regulating valve 11 to the minimum opening. By repeating such a series of processes as a one-cycle control pattern, the control unit 40 supplies hydrogen to the fuel electrode 67 of the fuel cell stack 1 while periodically changing the hydrogen pressure.
  • an upper limit pressure P1 and a lower limit pressure P2 are set based on the specified operating pressure.
  • the hydrogen pressure of the fuel electrode 67 of the fuel cell stack 1 can be monitored. Further, when the pressure is increased, it is desirable that the hydrogen pressure on the upstream side of the hydrogen pressure regulating valve 11 is made sufficiently high to increase the pressure increase rate as much as possible.
  • the pressure increase period from the lower limit pressure P2 to the upper limit pressure P1 is set to about 0.1 to 0.5 seconds.
  • the time from the upper limit pressure P1 to the lower limit pressure P2 is about 1 to 10 seconds, but the upper limit pressure P1, the lower limit pressure P2 and the current value taken out from the fuel cell stack 1, that is, the hydrogen consumption rate, Dependent.
  • the holding time Tp2 can be set as a control pattern.
  • the control unit 40 can arbitrarily set the first holding time Tp1 and the second holding time Tp2 in a range from zero to a predetermined value.
  • the first holding time Tp1 is such that the pressure of the fuel electrode 67 is set to the upper limit pressure P1 before the first step of reducing the pressure of the fuel electrode 67 from the upper limit pressure P1 to the lower limit pressure P2. It is time to hold.
  • the control unit 40 controls the opening degree Ot of the hydrogen pressure regulating valve 11 to the maximum opening degree O1 on the condition that the pressure of the fuel electrode 67 has been reduced to the lower limit pressure P2, and thereby the fuel cell stack.
  • the hydrogen supply to 1 is restarted, and the pressure of the fuel electrode 67 is increased.
  • the control unit 40 reduces the opening degree Ot of the hydrogen pressure regulating valve 11 from the maximum opening degree O1 to a predetermined opening degree on the condition that the pressure of the fuel electrode 67 has reached the upper limit pressure P1, and thereby increases the pressure of the fuel electrode 67. Is maintained at the upper limit pressure P1. Then, the control unit 40 sets the opening degree Ot of the hydrogen pressure regulating valve 11 to the minimum opening degree O2 on the condition that the first holding time Tp1 has elapsed from the timing when the pressure of the fuel electrode 67 reaches the upper limit pressure P1. By controlling, hydrogen supply to the fuel cell stack 1 is stopped.
  • the second holding time Tp2 is the pressure of the fuel electrode 67 before the execution of the second process of increasing the hydrogen pressure of the fuel electrode 67 from the lower limit pressure P2 to the upper limit pressure P1.
  • the control unit 40 controls the opening degree Ot of the hydrogen pressure regulating valve 11 to the minimum opening degree O2 on the condition that the pressure of the fuel electrode 67 has reached the upper limit pressure P1, so that the fuel cell stack 1 The hydrogen supply to is stopped.
  • the control unit 40 increases the opening degree Ot of the hydrogen pressure regulating valve 11 from the minimum opening degree O2 to a predetermined opening degree on the condition that the hydrogen pressure of the fuel electrode 67 has decreased to the lower limit pressure P2.
  • the pressure is kept at the lower limit pressure P2. Then, the control unit 40 sets the opening degree Ot of the hydrogen pressure regulating valve 11 to the maximum opening degree O1 on the condition that the second holding time Tp2 has elapsed from the timing when the pressure of the fuel electrode 67 reaches the lower limit pressure P2. By controlling, the hydrogen supply to the fuel cell stack 1 is restarted, and the pressure of the fuel electrode 67 is increased.
  • FIG. 17 is an explanatory diagram showing the correspondence between the load and each of the first holding time Tp1 and the second holding time Tp2.
  • the first holding time Tp1 and the second holding time Tp2 are respectively It is set to zero.
  • the first holding time Tp1 is set to zero.
  • the second holding time Tp2 is set so that the value increases as the load increases, starting from zero.
  • the first holding time Tp1 increases as the load increases starting from zero.
  • the second holding time Tp2 is set to a constant value.
  • the control unit 40 can determine the first holding time Tp1 and the second holding time Tp2 according to the load state. In other words, whether to hold the pressure of the fuel electrode 67 at the upper limit pressure P1 or the lower limit pressure P2 can be selected according to the load.
  • the control unit 40 is configured such that when the required load is high (when the load current is large), compared to when the required load is low (when the load current is small), The amount of hydrogen supply in the execution period of one control pattern is increased. In the driving scene such as high load, the hydrogen consumption tends to be large. Therefore, there is a possibility that the number of executions of pressure increase / decrease corresponding to one control pattern increases in order to cover the hydrogen supply.
  • the hydrogen supply amount in the execution period of one control pattern is increased, an increase in the number of executions of pressure increase / decrease per unit time can be suppressed. As a result, stress applied to the fuel cell stack 1 and the hydrogen-based parts can be alleviated, so that deterioration of the fuel cell system 100 can be suppressed.
  • the second holding time Tp2 for holding the pressure of the pole 67 at the lower limit pressure P2 can be set in the control pattern. Then, the control unit 40 sets the first holding time Tp1 or the second holding time Tp2 longer as the required load is higher. As the required load increases, the amount of hydrogen consumption increases, and thus the pressure decrease rate in the first process increases. However, according to the third embodiment, as the required load increases, the first holding time Tp1 and the second holding time are increased. Tp2 is set long.
  • the period from the timing when the pressure of the fuel electrode 67 reaches the upper limit pressure P1 to the timing when the pressure of the fuel electrode 67 is returned from the lower limit pressure P2 to the upper limit pressure P1 can be set longer. That is, by setting the first holding time Tp1 and the second holding time Tp2 to be long, the execution period of one control pattern is lengthened, so that the increase in the number of executions of pressure increase / decrease per unit time can be suppressed. As a result, stress applied to the fuel cell stack 1 and the hydrogen-based parts can be alleviated, so that deterioration of the fuel cell system 100 can be suppressed.
  • control unit 40 sets the first holding time Tp1 longer as the required load is higher.
  • the required load increases, it may become difficult to secure the hydrogen partial pressure in the fuel electrode 67. Therefore, by setting the first holding time Tp1 at the upper limit pressure P1 to be long, there is an effect that the hydrogen partial pressure is easily ensured even when the required load is high.
  • the second holding time Tp2 is set longer as the required load increases in the region where the required load is low to medium load (lower side in FIG. 17). From low load to medium load, liquid water tends to accumulate in the fuel electrode 67. By setting the second holding time Tp2 at the lower limit pressure P2 to be long, the execution accuracy of the liquid water discharge process can be increased. Furthermore, it is preferable that the control unit 40 sets the first holding time Tp1 longer as the required load becomes higher in a region where the required load is medium load to high load (upper part of FIG. 17). When the required load increases, it may become difficult to secure the hydrogen partial pressure in the fuel electrode 67. Therefore, by setting the first holding time Tp1 at the upper limit pressure P1 to be long, there is an effect that the hydrogen partial pressure is easily ensured even when the required load is high.
  • the first holding time Tp1 for holding the upper limit pressure P1 is set longer.
  • the hydrogen partial pressure may be secured.
  • the inert gas concentration in the fuel electrode 67 increases as the time from the stop of the fuel cell system 100 to the start-up increases. Therefore, the first holding time Tp1 for holding the upper limit pressure P1 is made variable by measuring the stop period of the fuel cell system 100 or measuring the nitrogen concentration in the fuel electrode 67 when the fuel cell system 100 is activated. May be.
  • the fuel electrode 67 immediately after returning from the idle stop.
  • the nitrogen concentration inside is high. Therefore, the first holding time Tp1 may be set longer in such a scene.
  • the upper limit pressure P1 and the lower limit pressure P2 can be set according to the load current.
  • the control unit 40 determines the target generated power of the fuel cell stack 1 as a required load required for the fuel cell system 100 based on the vehicle speed, the driver's accelerator operation amount, and information on the secondary battery. Based on the target generated power, the control unit 40 calculates a load current, which is a current value extracted from the fuel cell stack 1.
  • FIG. 19 is an explanatory diagram showing a correspondence relationship between the load current Ct and the upper limit pressure P1 and the lower limit pressure P2.
  • the operating pressure Psa for supplying the reaction gas necessary for extracting the load current Ct from the fuel cell stack 1 is determined by considering the characteristics of the fuel cell stack 1 and the fuel cell system 100 such as a hydrogen system and an air system. Can be defined through experiments and simulations.
  • 19 in FIG. 19 represents the rated load current Cr (the same applies to FIG. 20B described later).
  • this operating pressure Psa is set as the target operating pressure.
  • an upper limit pressure P1 and a lower limit pressure P2 are set based on the operating pressure Psa.
  • the upper limit pressure P1 and the lower limit pressure P2 are set so as to increase the differential pressure between the upper limit pressure P1 and the lower limit pressure P2, that is, the pressure fluctuation range during gas supply, as the load current Ct increases.
  • the higher the required load of the scene the greater the amount of hydrogen supply during the execution period of one control pattern can be increased.
  • count of execution of the pressure increase / decrease per unit time can be suppressed.
  • deterioration of the fuel cell system 100 can be suppressed.
  • the upper limit pressure P1 and the lower limit pressure P2 may be set in consideration of the power generation stability of the fuel cell stack 1.
  • the pressure is set to about 50 kPa so that the differential pressure between the upper limit pressure P1 and the lower limit pressure P2 becomes relatively small.
  • the average hydrogen concentration in each fuel cell is about 40%.
  • the load is high, that is, when the load current is large, the power generation efficiency becomes higher when the gas pressure is increased. Therefore, the supply pressure is reduced as a whole on both the oxidant electrode 34 side and the fuel electrode 67 side. increase.
  • the differential pressure between the upper limit pressure P1 and the lower limit pressure P2 is set to about 100 kPa. In this case, the fuel cell stack 1 is operated when the average hydrogen concentration in each fuel cell is about 75%.
  • the atmosphere inside the fuel cell stack 1 (the fuel electrode 67) is in a state where the hydrogen concentration is low at the timing of the lower limit pressure P2, and hydrogen is at the timing of the upper limit pressure P1.
  • the concentration becomes high. That is, by increasing the pressure from the lower limit pressure P 2 to the upper limit pressure P 1, the high hydrogen concentration gas is introduced into the fuel electrode 67, whereby the low hydrogen concentration gas is pushed into the volume portion 12 from the fuel cell stack 1. Further, the gas in the fuel electrode 67 is agitated by the high hydrogen concentration gas.
  • FIG. 20A and 20B are explanatory views schematically showing the fuel electrode 67 side volume Rs and the volume Rt of the volume part 12 in the fuel cell stack 1.
  • the pressure ratio P1 / P2 between the upper limit pressure P1 and the lower limit pressure P2 is approximately 1.33.
  • the volume and volume part of the fuel cell stack 1 is increased by the pressure increase from the lower limit pressure P2 to the upper limit pressure P1. 12), that is, new hydrogen will flow to about 50% of the fuel cell stack 1.
  • this state is expressed as a hydrogen exchange rate of 0.5 ⁇ FIG. )reference) ⁇ .
  • the rate of hydrogen consumption is slow, so that the fuel cell stack 1 can generate power at a hydrogen exchange rate of about this level.
  • the time-averaged hydrogen concentration in the anode off-gas is about 40%.
  • the pressure ratio P1 / P2 (for example, 2 or more) enough to replace the entire fuel electrode 67 of the fuel cell stack 1 with new hydrogen, that is, the hydrogen exchange rate is about 1. It is desirable.
  • the concentration of discharged hydrogen is desired to be kept low, the hydrogen consumption rate is high, so that a hydrogen concentration higher than a predetermined level is necessary for stable power generation (for example, about 75% or more is required).
  • the fuel electrode off-gas flow path L2 is opened by the purge valve 14 in order to adjust the hydrogen concentration.
  • a minute flow rate that does not interfere with hydrogen supply due to periodic pressure fluctuations is discharged from the purge valve 14 continuously or intermittently. Since the gas discharged from the purge valve 14 has a minute flow rate, it is diluted by the cathode side exhaust and safely discharged out of the system.
  • the purge valve 14 is opened to discharge impurities (nitrogen and water vapor) from the fuel electrode 67, but hydrogen is also mixed in the fuel electrode 67. For this reason, it is preferable to effectively discharge impurities while suppressing hydrogen discharge.
  • the purge valve 14 in the hydrogen supply, is controlled to be opened in response to the process of increasing the hydrogen pressure from the lower limit pressure P2 to the upper limit pressure P1 (second process). Release (purge process). Specifically, the control unit 40 monitors the pressure of the fuel electrode 67 of the fuel cell stack 1 and controls the purge valve 14 to be open in response to the timing when the monitored pressure reaches the lower limit pressure P2. The purge valve 14 is controlled to be closed in accordance with the timing at which the monitored pressure reaches the upper limit pressure P1 (basic control pattern).
  • the low hydrogen concentration gas is pushed from the fuel cell stack 1 into the volume portion 12 and before the high concentration hydrogen reaches the purge valve 14, the low hydrogen concentration gas is discharged from the volume portion 12 via the purge valve 14. The Thereby, many impurities can be efficiently discharged.
  • the opening / closing control of the purge valve 14 is not limited to this basic control pattern. If the purge valve 14 is controlled to be in an open state so as to include at least a process of increasing the pressure from the lower limit pressure P2 to the upper limit pressure P1 (second process), the opening / closing control of the purge valve 14 is sufficient. Therefore, the timing for controlling the purge valve 14 to the closed state can be corrected to a timing delayed from the timing at which the hydrogen pressure reaches the upper limit pressure P1 (hereinafter referred to as “reference closing timing”). For example, the boundary between high-concentration hydrogen and low-concentration hydrogen can be determined as a constant surface within a short time range when considering the diffusion rate.
  • the position at which the boundary surface (so-called hydrogen front) reaches in the fuel cell stack 1 and the volume portion 12 at what time is predicted through experiments and simulations.
  • the timing for controlling the purge valve 14 to the closed state can be delayed from the reference closing timing until the boundary surface reaches the purge valve 14.
  • the purge process does not have to be performed for every execution of the control pattern, specifically, for each of the pressure increasing processes (second processes).
  • the purge valve 14 may be opened corresponding to the subsequent pressure increasing process on the condition that the hydrogen concentration in the fuel electrode 67 is equal to or lower than a predetermined determination threshold value.
  • liquid water is also considered as a factor that hinders the power generation reaction, so liquid water can also be discharged.
  • this liquid water discharge process is executed once every multiple times or every fixed time, not every time the pressure increases or decreases periodically. It is preferable to do. Since the liquid water only needs to be removed from the fuel cell stack 1, it is considered that the liquid water is discharged from the fuel cell stack 1 to the volume portion 12. In this case, since it is necessary to increase the flow velocity, it is preferable to set the differential pressure between the upper limit pressure P1 and the lower limit pressure P2 to about 100 kPa.
  • the upper limit pressure P1 and the lower limit pressure P2 can be set in consideration of the following additional method in addition to the method of making variable according to the required load as described above.
  • the upper limit pressure P1 and the lower limit pressure P2 may be set according to the allowable inter-electrode differential pressure between the oxidant electrode 34 and the fuel electrode 67 in the fuel cell.
  • an upper limit is set so as to ensure a minimum pressure for reliably performing the purge.
  • the pressure P1 and the lower limit pressure P2 may be limited.
  • the upper limit pressure P1 is set to a larger value, and the liquid water retention amount or liquid water generation amount in the fuel electrode 67 is larger.
  • the lower limit pressure P2 is set to a small value in a predicted state.
  • the pressure ratio (P1 / P2) between the upper limit pressure P1 and the lower limit pressure P2. ) Is temporarily set to a large value (P1w / P2w), the upper limit pressure P1 and the lower limit pressure P2 are set.
  • the pressure decreases from the upper limit pressure P1 to the lower limit pressure P2 because the hydrogen consumption rate is low in the low load region. Slows down. In this case, since it takes time to reach the lower limit pressure P2, the second process of increasing the pressure from the lower limit pressure P2 to the upper limit pressure P1 may not be executed for a while.
  • the control unit 40 temporarily increases the current taken out from the fuel cell stack 1 to The descending speed may be increased.
  • the time required to decrease from the upper limit pressure P1w to the lower limit pressure P2 is the time Tm2
  • the upper limit pressure P1w is changed to the lower limit pressure P2.
  • the power generation state may be unstable by temporarily increasing the current extracted from the fuel cell stack 1, or the extracted current is stored.
  • the pressure drop rate may be increased by a separate method instead of increasing the extraction current.
  • the pressure decreasing speed may be increased by increasing the volume of the fuel electrode 67.
  • the liquid water management level in the fuel electrode 67 is lowered and the liquid water in the fuel electrode 67 is discharged.
  • the liquid water generation amount is estimated by integrating the load current based on the characteristic that the liquid water generation amount is approximately proportional to the load current. Further, the liquid water retention amount may be estimated based on the elapsed time from the timing of the liquid water discharge performed previously. Further, the voltage of the fuel cell may be measured, and it may be estimated that the liquid water retention amount is large due to the abnormal drop in voltage. Further, when the liquid water retention amount is estimated, it may be corrected by the temperature of the cooling water that cools the fuel cell stack 1. This is because even if the load current is the same, the lower the cooling water temperature, the more liquid water stays. Similarly, the liquid water retention amount can be corrected by the number of pressure pulsations and the cathode air amount.
  • a fuel cell system 100 according to a fifth embodiment of the present invention will be described.
  • the normal operation process for generating power corresponding to the load current in the fuel cell stack 1 has been described.
  • the process at the time of starting and stopping of the fuel cell system 100 is described. To do. Since the configuration of the fuel cell system 100 is the same as that of the first to fourth embodiments, the redundant description will be omitted, and the following description will focus on the differences.
  • the hydrogen pressure regulating valve 11 and the purge valve 14 are controlled to be closed, power is generated, and hydrogen is consumed, so that the hydrogen pressure at the fuel electrode 67 is reduced. Reduce pressure.
  • the hydrogen pressure is increased again to the predetermined starting upper limit pressure. Such pressure increase / decrease is repeated until the concentration of the fuel electrode 67 of the fuel cell stack 1 reaches a predetermined average hydrogen concentration.
  • the output from the mounted secondary battery may be used.
  • the upper limit pressure P1 is set to 200 kPa (absolute pressure) and the lower limit pressure P2 is set to 101.3 kPa, and values sufficient to discharge liquid water from the fuel electrode 67 are set.
  • the number of repetitions is based on the number of times that liquid water can be sufficiently discharged through experiments and simulations. This terminates power generation.
  • the drained water from the fuel cell stack 1 to the volume 12 is drained by controlling the drain valve 13 to be open. Then, a heating device such as a heater is operated after the drainage using the power generated until just before, the purge valve 14 and the drain valve 13 are heated, and the discharged liquid water is dried.
  • a heating device such as a heater is operated after the drainage using the power generated until just before, the purge valve 14 and the drain valve 13 are heated, and the discharged liquid water is dried.
  • the startability at the start-up is achieved by the stop process, and impurities can be preferentially discharged over hydrogen even at the start-up process.
  • the fuel electrode side gas can be agitated by periodically changing the pressure of the fuel gas in the fuel electrode based on the first pressure fluctuation pattern in which the pressure fluctuates in the first pressure range.
  • the fuel electrode side gas can be made uniform.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Fuel Cell (AREA)

Abstract

L’invention concerne un système (100) de pile à combustible, comprenant : une pile à combustible (1) destinée à produire de l’énergie électrique par réaction électrochimique entre un comburant gazeux fourni à une électrode à comburant (34) et un combustible gazeux fourni à une électrode à combustible (67) ; un dispositif d’alimentation en combustible gazeux (HS) destiné à alimenter l’électrode à combustible (67) en combustible gazeux ; et un dispositif de commande (40) destiné à commander le dispositif d’alimentation en combustible gazeux (HS) pour assurer l’alimentation de l’électrode à combustible (67) en combustible gazeux et à modifier la pression du combustible gazeux lorsqu’une sortie côté électrode à combustible (67) est fermée. Le dispositif de commande (40) modifie cycliquement la pression du combustible gazeux dans l’électrode à combustible (67) en fonction d’un premier profil de modification de pression de manière à appliquer un premier écart de pression ΔP1.
PCT/JP2009/069425 2008-11-21 2009-11-16 Système de pile à combustible et procédé de commande associé WO2010058747A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
RU2011125325/07A RU2472256C1 (ru) 2008-11-21 2009-11-16 Система топливного элемента и способ ее контроля
BRPI0921969 BRPI0921969B1 (pt) 2008-11-21 2009-11-16 sistema de célula de combustível e método para controlar o mesmo
EP09827528.2A EP2357699B1 (fr) 2008-11-21 2009-11-16 Système de pile à combustible et procédé de commande associé
US13/129,986 US9786931B2 (en) 2008-11-21 2009-11-16 Fuel cell system and method for controlling same
CA2744304A CA2744304C (fr) 2008-11-21 2009-11-16 Commande de pile a combustible a cycle de pression d'anode
CN200980146527.2A CN102224627B (zh) 2008-11-21 2009-11-16 燃料电池系统及其控制方法
US14/742,113 US20150288008A1 (en) 2008-11-21 2015-06-17 Fuel cell system and method for controlling same

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JP2008298191A JP5228835B2 (ja) 2008-11-21 2008-11-21 燃料電池システム
JP2008-298191 2008-11-21
JP2008302465A JP5428307B2 (ja) 2008-11-27 2008-11-27 燃料電池システム
JP2008-302465 2008-11-27

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US13/129,986 A-371-Of-International US9786931B2 (en) 2008-11-21 2009-11-16 Fuel cell system and method for controlling same
US14/742,113 Division US20150288008A1 (en) 2008-11-21 2015-06-17 Fuel cell system and method for controlling same

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EP2453507A4 (fr) * 2009-07-07 2014-04-02 Nissan Motor Dispositif de contrôle de fonctionnement et procédé de contrôle de fonctionnement pour centrale électrique à pile à combustible
US20130323619A1 (en) * 2011-02-23 2013-12-05 Nissan Motor Co., Ltd. Fuel cell system
US10193168B2 (en) 2011-06-02 2019-01-29 Nissan Motor Co., Ltd. Fuel cell system
US9812718B2 (en) * 2011-06-02 2017-11-07 Nissan Motor Co., Ltd. Fuel cell system
CN103843183A (zh) * 2011-10-04 2014-06-04 日产自动车株式会社 燃料电池系统
CN103959529A (zh) * 2011-11-28 2014-07-30 日产自动车株式会社 燃料电池系统
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US20150004513A1 (en) * 2012-01-05 2015-01-01 Nissan Motor Company, Ltd. Fuel cell system
US20150017562A1 (en) * 2012-02-29 2015-01-15 Nissan Motor Co., Ltd Fuel cell system and control method of fuel cell system
WO2013129553A1 (fr) * 2012-02-29 2013-09-06 日産自動車株式会社 Système de pile à combustible et procédé de commande pour système de pile à combustible
US20150044582A1 (en) * 2012-03-12 2015-02-12 Nissan Motor Co., Ltd. Fuel cell system
US20150030948A1 (en) * 2012-03-13 2015-01-29 Nissan Motor Co., Ltd. Fuel cell system and control method of fuel cell system
JP2013191370A (ja) * 2012-03-13 2013-09-26 Nissan Motor Co Ltd 燃料電池システム
WO2013137275A1 (fr) * 2012-03-13 2013-09-19 日産自動車株式会社 Système de pile à combustibles
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CN105594046A (zh) * 2013-10-08 2016-05-18 日产自动车株式会社 燃料电池系统以及燃料电池系统的控制方法
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CA2744304C (fr) 2013-12-10
EP2357699B1 (fr) 2016-10-12
RU2521471C1 (ru) 2014-06-27
EP2357699A1 (fr) 2011-08-17
CN103401007A (zh) 2013-11-20
RU2012139070A (ru) 2014-05-10
RU2472256C1 (ru) 2013-01-10
CN102224627B (zh) 2015-08-19
BRPI0921969B1 (pt) 2019-12-10
CN103401007B (zh) 2016-01-20
US20110274998A1 (en) 2011-11-10
US9786931B2 (en) 2017-10-10
EP2887436B1 (fr) 2016-09-14
BRPI0921969A2 (pt) 2018-09-11
EP2357699A4 (fr) 2014-05-07
CA2744304A1 (fr) 2010-05-27
US20150288008A1 (en) 2015-10-08
CN102224627A (zh) 2011-10-19
EP2887436A1 (fr) 2015-06-24

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