WO2013103134A1 - 燃料電池システム - Google Patents
燃料電池システム Download PDFInfo
- Publication number
- WO2013103134A1 WO2013103134A1 PCT/JP2012/084072 JP2012084072W WO2013103134A1 WO 2013103134 A1 WO2013103134 A1 WO 2013103134A1 JP 2012084072 W JP2012084072 W JP 2012084072W WO 2013103134 A1 WO2013103134 A1 WO 2013103134A1
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- Prior art keywords
- pressure
- fuel cell
- anode
- anode gas
- upper limit
- Prior art date
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- 239000000446 fuel Substances 0.000 title claims abstract description 115
- 230000010349 pulsation Effects 0.000 claims abstract description 43
- 230000008859 change Effects 0.000 claims abstract description 3
- 238000010248 power generation Methods 0.000 abstract description 9
- 239000007789 gas Substances 0.000 description 205
- 230000001052 transient effect Effects 0.000 description 56
- 230000001105 regulatory effect Effects 0.000 description 23
- 238000010926 purge Methods 0.000 description 19
- 238000010586 diagram Methods 0.000 description 17
- 230000007423 decrease Effects 0.000 description 14
- 239000011261 inert gas Substances 0.000 description 12
- 239000012528 membrane Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- 230000007704 transition Effects 0.000 description 12
- 239000003792 electrolyte Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000009792 diffusion process Methods 0.000 description 8
- 238000003411 electrode reaction Methods 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- 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
- H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
-
- 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
- H01M8/04223—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
-
- 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
- H01M8/04313—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
- H01M8/0444—Concentration; Density
- H01M8/04447—Concentration; Density 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
- H01M8/04—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
- H01M8/04791—Concentration; Density
- H01M8/04798—Concentration; Density 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
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
- H01M8/04664—Failure or abnormal function
- H01M8/04679—Failure or abnormal function of fuel cell stacks
-
- 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.
- JP 2007-517369A is a conventional fuel cell system in which a normally closed solenoid valve is provided in an anode gas supply passage, and a normally open solenoid valve and a buffer tank (recycle tank) are provided in order from the upstream in an anode gas discharge passage.
- a normally closed solenoid valve is provided in an anode gas supply passage
- a normally open solenoid valve and a buffer tank are provided in order from the upstream in an anode gas discharge passage.
- This conventional fuel cell system is an anode gas non-circulation type fuel cell system in which unused anode gas discharged into the anode gas discharge passage is not returned to the anode gas supply passage, and includes a normally closed solenoid valve and a normally open solenoid. By periodically opening and closing the valve, the unused anode gas stored in the buffer tank was made to flow back to the fuel cell stack and reused.
- the present invention has been made paying attention to such problems, and suppresses the pulsation operation in a state where the stagnation point is present in the anode gas flow path, thereby reducing the power generation efficiency and the fuel cell.
- the purpose is to suppress deterioration.
- a control valve for controlling the pressure of the anode gas supplied to the fuel cell, and an operating state of the fuel cell system Pulsating operation means for pulsating the pressure of the anode gas in the fuel cell at a predetermined pressure by controlling the opening of the control valve based on the fuel cell, and the fuel cell based on the pressure change of the anode gas in the fuel cell And a stagnation point judging means for judging whether or not there is a stagnation point where the anode gas concentration is locally low. Then, when it is determined that the stagnation point exists in the fuel cell, the pulsation operation means increases the predetermined pressure and performs the pulsation operation.
- FIG. 1A is a schematic perspective view of a fuel cell according to a first embodiment of the present invention.
- 1B is a cross-sectional view of the fuel cell of FIG. 1A taken along the line BB.
- FIG. 2 is a schematic configuration diagram of the anode gas non-circulating fuel cell system according to the first embodiment of the present invention.
- FIG. 3 is a diagram for explaining pulsation operation during steady operation in which the operation state of the fuel cell system is constant.
- FIG. 4 is a flowchart illustrating pulsation operation control according to the first embodiment of the present invention.
- FIG. 5 is a map for calculating the estimated minimum anode gas concentration Cmin in the flow path based on the anode pressure drop amount ⁇ P and the pre-lowering transient buffer concentration Cbuff.
- FIG. 1A is a schematic perspective view of a fuel cell according to a first embodiment of the present invention.
- 1B is a cross-sectional view of the fuel cell of FIG. 1A taken along the line
- FIG. 6 is a map for calculating the estimated stagnation point distance Lmin based on the anode pressure drop amount ⁇ P and the pre-lowering transient anode pressure Ppre.
- FIG. 7 is a table for calculating the stagnation point discharge anode pressure upper limit value P1 based on the estimated stagnation point distance Lmin.
- FIG. 8 is a diagram for explaining the effect of the pulsation operation control according to the first embodiment of the present invention.
- FIG. 9 is a flowchart illustrating pulsation operation control according to the second embodiment of the present invention.
- FIG. 10 is a flowchart illustrating anode pressure return control according to the third embodiment of the present invention.
- FIG. 11 is a time chart showing changes in the anode pressure when the pressure regulating valve is fully closed and the anode pressure is lowered to the lower limit pressure during the lowered transient operation.
- FIG. 12 is a diagram for explaining the reason why a portion where the anode gas concentration is locally lower than the others is generated inside the anode gas flow path.
- FIG. 13 is a diagram illustrating a problem when the lowering transient operation is performed again after the anode pressure is increased after the lowering transient operation.
- 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).
- FIG. 1A and 1B are diagrams illustrating the configuration of the fuel cell 10 according to the first embodiment of the present invention.
- FIG. 1A is a schematic perspective view of the fuel cell 10.
- FIG. 1B is a BB cross-sectional view of the fuel cell 10 of FIG. 1A.
- the fuel cell 10 includes an anode separator 12 and a cathode separator 13 arranged on both front and back surfaces of a membrane electrode assembly (hereinafter referred to as “MEA”) 11.
- MEA membrane electrode assembly
- the MEA 11 includes an electrolyte membrane 111, an anode electrode 112, and a cathode electrode 113.
- the MEA 11 has an anode electrode 112 on one surface of the electrolyte membrane 111 and a cathode electrode 113 on the other surface.
- the electrolyte membrane 111 is a proton conductive ion exchange membrane formed of a fluorine-based resin.
- the electrolyte membrane 111 exhibits good electrical conductivity in a wet state.
- the anode electrode 112 includes a catalyst layer 112a and a gas diffusion layer 112b.
- the catalyst layer 112a is in contact with the electrolyte membrane 111.
- the catalyst layer 112a is formed of carbon black particles carrying platinum or platinum.
- the gas diffusion layer 112b is provided outside the catalyst layer 112a (on the opposite side of the electrolyte membrane 111) and is in contact with the anode separator 12.
- the gas diffusion layer 112b is formed of a member having sufficient gas diffusibility and conductivity, and is formed of, for example, a carbon cloth woven with yarns made of carbon fibers.
- the cathode electrode 113 includes a catalyst layer 113a and a gas diffusion layer 113b.
- the anode separator 12 is in contact with the gas diffusion layer 112b.
- the anode separator 12 has a plurality of groove-shaped anode gas passages 121 for supplying anode gas to the anode electrode 112 on the side in contact with the gas diffusion layer 112b.
- the cathode separator 13 is in contact with the gas diffusion layer 113b.
- the cathode separator 13 has a plurality of groove-like cathode gas flow paths 131 for supplying cathode gas to the cathode electrode 113 on the side in contact with the gas diffusion layer 113b.
- the anode gas flowing through the anode gas channel 121 and the cathode gas flowing through the cathode gas channel 131 flow in the same direction in parallel with each other. You may make it flow in the opposite direction in parallel with each other.
- FIG. 2 is a schematic configuration diagram of the anode gas non-circulating fuel cell system 1 according to the first embodiment of the present invention.
- the fuel cell system 1 includes a fuel cell stack 2, an anode gas supply device 3, and a controller 4.
- the fuel cell stack 2 is formed by stacking a plurality of fuel cells 10, generates electric power by receiving supply of anode gas and cathode gas, and generates electric power necessary for driving a vehicle (for example, electric power necessary for driving a motor). ).
- the cathode gas supply / discharge device for supplying and discharging the cathode gas to / from the fuel cell stack 2 and the cooling device for cooling the fuel cell stack 2 are not the main part of the present invention, and are not shown for the sake of easy understanding. did. In this embodiment, air is used as the cathode gas.
- the anode gas supply device 3 includes a high-pressure tank 31, an anode gas supply passage 32, a pressure regulating valve 33, a pressure sensor 34, an anode gas discharge passage 35, a buffer tank 36, a purge passage 37, and a purge valve 38. .
- the high pressure tank 31 stores the anode gas supplied to the fuel cell stack 2 in a 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 2, and has one end connected to the high-pressure tank 31 and the other end of the fuel cell stack 2. Connected to the anode gas inlet hole 21.
- the pressure regulating valve 33 is provided in the anode gas supply passage 32.
- the pressure regulating valve 33 adjusts the anode gas discharged from the high-pressure tank 31 to a desired pressure and supplies it to the fuel cell stack 2.
- the pressure regulating valve 33 is an electromagnetic valve whose opening degree can be adjusted continuously or stepwise, and the opening degree is controlled by the controller 4.
- the pressure sensor 34 is provided in the anode gas supply passage 32 downstream of the pressure regulating valve 33.
- the pressure sensor 34 detects the pressure of the anode gas flowing through the anode gas supply passage 32 downstream of the pressure regulating valve 33.
- the pressure of the anode gas detected by the pressure sensor 34 is the pressure of the entire anode system including the anode gas flow paths 121 and the buffer tanks 36 inside the fuel cell stack (hereinafter referred to as “anode pressure”). As a substitute.
- the anode gas discharge passage 35 has one end connected to the anode gas outlet hole 22 of the fuel cell stack 2 and the other end connected to the upper portion of the buffer tank 36.
- the anode gas discharge passage 35 has a mixed gas of excess anode gas that has not been used for the electrode reaction and an inert gas such as nitrogen or water vapor that has permeated from the cathode side to the anode gas flow path 121 (hereinafter, “ Anode off gas ”) is discharged.
- the buffer tank 36 temporarily stores the anode off gas flowing through the anode gas discharge passage 35. A part of the water vapor in the anode off gas is condensed in the buffer tank 36 to become liquid water and separated from the anode off gas.
- One end of the purge passage 37 is connected to the lower part of the buffer tank 36.
- the other end of the purge passage 37 is an open end.
- the anode off gas and liquid water stored in the buffer tank 36 are discharged from the opening end to the outside air through the purge passage 37.
- the purge valve 38 is provided in the purge passage 37.
- the purge valve 38 is an electromagnetic valve whose opening degree can be adjusted continuously or stepwise, and the opening degree is controlled by the controller 4.
- the opening degree of the purge valve 38 is adjusted so that the anode gas concentration in the buffer tank 36 increases as the target output calculated according to the operating state of the fuel cell system 1 increases. If the operating state of the fuel cell system 1 is the same, the concentration of the inert gas in the buffer tank 36 decreases and the anode gas concentration increases as the opening of the purge valve 38 is increased.
- 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 41 that detects the output current of the fuel cell stack 2 and a temperature of cooling water that cools the fuel cell stack 2 (hereinafter referred to as “cooling water temperature”).
- the fuel cell system 1 includes a temperature sensor 42 to detect, a voltage sensor 43 to detect the output voltage of the fuel cell stack 2, and an accelerator stroke sensor 44 to detect an accelerator pedal depression amount (hereinafter referred to as “accelerator operation amount”).
- a signal for detecting the operating state is input.
- the controller 4 periodically opens and closes the pressure regulating valve 33 based on these input signals, performs pulsation operation to periodically increase and decrease the anode pressure, and adjusts the opening degree of the purge valve 38 from the buffer tank 36.
- the flow rate of the anode off gas to be discharged is adjusted, and the anode gas concentration in the buffer tank 36 is controlled to a desired concentration.
- the fuel cell stack 2 In the case of the anode gas non-circulation type fuel cell system 1, if the anode gas continues to be supplied from the high-pressure tank 31 to the fuel cell stack 2 while the pressure regulating valve 33 is kept open, the fuel cell stack 2 is not discharged. Since the anode off gas including the used anode gas is continuously discharged from the buffer tank 36 through the purge passage 37 to the outside air, it is wasted.
- the pulsation operation is performed in which the pressure regulating valve 33 is periodically opened and closed to increase and decrease the anode pressure periodically.
- the anode off gas accumulated in the buffer tank 36 can be caused to flow back to the fuel cell stack 2 when the anode pressure is reduced.
- the anode gas in the anode off-gas can be reused, so that the amount of the anode gas discharged to the outside air can be reduced and waste can be eliminated.
- FIG. 3 is a diagram for explaining pulsation operation during steady operation in which the operation state of the fuel cell system 1 is constant.
- the controller 4 calculates the target output of the fuel cell stack 2 based on the operating state of the fuel cell system 1 (the load of the fuel cell stack), and sets the anode pressure according to the target output. Set the upper and lower limits.
- the width from the lower limit pressure to the upper limit pressure (hereinafter referred to as “pulsation width”) increases as the target output increases.
- the anode pressure is periodically increased or decreased between the upper limit value and the lower limit value of the set anode pressure.
- the pressure regulating valve 33 is opened to an opening at which the anode pressure can be increased to at least the upper limit value.
- the anode gas is supplied from the high-pressure tank 31 to the fuel cell stack 2 and discharged to the buffer tank 36.
- the pressure regulating valve 33 When the anode pressure reaches the upper limit at time t2, the pressure regulating valve 33 is fully closed as shown in FIG. 3B, and the supply of anode gas from the high-pressure tank 31 to the fuel cell stack 2 is stopped. Then, since the anode gas left in the anode gas flow path 121 inside the fuel cell stack is consumed over time due to the electrode reaction of (1) described above, the anode pressure is reduced by the amount of consumption of the anode gas.
- the pressure in the buffer tank 36 temporarily becomes higher than the pressure in the anode gas flow path 121, so that the anode gas flow path 121 extends from the buffer tank 36.
- the anode off-gas flows back into.
- the anode gas left in the anode gas channel 121 and the anode gas in the anode off-gas that has flowed back to the anode gas channel 121 are consumed over time, and the anode pressure further decreases.
- the pressure regulating valve 33 When the anode pressure reaches the lower limit at time t3, the pressure regulating valve 33 is opened in the same manner as at time t1. When the anode pressure reaches the upper limit again at time t4, the pressure regulating valve 33 is fully closed.
- FIG. 11 is a time chart showing changes in the anode pressure when the pressure regulating valve 33 is fully closed and the anode pressure is lowered to the lower limit pressure during the lowered transient operation.
- the upper limit value and the lower limit pressure of the anode pressure corresponding to the decreased target output are set as shown in FIG. Is done. Further, as shown in FIG. 11A, the pulsation width after the target output reduction is smaller than the pulsation width before the target output reduction.
- FIG. 12 is a diagram for explaining the reason why a portion where the anode gas concentration is locally lower than the others is generated inside the anode gas passage 121.
- FIG. 12A is a diagram showing the flow of the anode gas and the anode off-gas in the anode gas flow path 121 when the pressure regulating valve 33 is fully closed during the down transition operation.
- FIG. 12B is a diagram showing the concentration distribution of the anode gas in the anode gas flow passage 121 as time elapses when the pressure regulating valve 33 is fully closed during the down transition operation.
- the anode gas remaining in the anode gas flow path 121 is caused by the pressure difference caused by the consumption of the anode gas. Flows to the side.
- the pressure in the buffer tank 36 temporarily becomes higher than the pressure in the anode gas flow path 121, so that the anode gas flow path from the buffer tank 36 side.
- the anode off gas flows backward to 121.
- the anode gas concentration at this stagnation point is referred to as “the minimum anode gas concentration in the flow path” as necessary.
- the stagnation point exists in the anode gas flow path 121, and a portion in which the anode gas concentration is locally lower than the others is generated in the anode gas flow path 121. .
- the pressure regulating valve 33 is opened and the anode pressure is increased.
- the stagnation point exists in the anode gas channel 121, That is, the pulsation operation is performed in a state where there is a portion where the anode gas concentration is locally lower than the others in the anode gas flow path 121.
- FIG. 13 is a diagram for explaining a problem when the lowered transient operation is performed again after the anode pressure is increased after the lowered transient operation.
- FIG. 13 (A) is a diagram showing the transition of the stagnation point in the anode gas flow passage 121 when the anode pressure is increased after the lowered transient operation and then the lowered transient operation is performed again.
- FIG. 13B is a diagram illustrating a transition of the concentration distribution of the anode gas in the anode gas flow passage 121 when the anode pressure is increased after the lowered transient operation and then the lowered transient operation is performed again.
- the alternate long and short dash line A is a line indicating the concentration distribution of the anode gas after the end of the first lowered transient operation.
- a broken line B is a line showing the concentration distribution of the anode gas after the anode pressure is raised after the lowered transient operation.
- a solid line C is a line showing the concentration distribution of the anode gas after the anode pressure is raised and then lowered and the transient operation is performed.
- FIG. 13A When the first transitional down operation is completed, as shown in FIG. 13A, a stagnation point exists in the anode gas flow path 121. Further, as indicated by a one-dot chain line A in FIG. 13B, a portion where the anode gas concentration is locally lower than the others is generated inside the anode gas channel 121.
- the pressure regulating valve 33 is opened and the anode gas is supplied from the high pressure tank 31 side to the anode gas flow path 121.
- the stagnation point moves to the buffer tank 36 side.
- the increase width of the anode pressure at this time is small, the stagnation point cannot be moved to the outside of the anode gas channel 121 as shown in FIG.
- the stagnation point remains. That is, as indicated by a broken line B in FIG. 13B, even after the anode pressure is increased, a portion where the anode gas concentration is locally lower than the others remains in the anode gas flow path 121. Become.
- the minimum anode gas concentration in the flow path is further lowered. If it does so, possibility that the minimum anode gas density
- the upper limit value of the anode pressure is set so that the stagnation point moves to the outside of the anode gas flow path 121.
- FIG. 4 is a flowchart illustrating pulsation operation control according to the present embodiment.
- step S1 the controller 4 reads detection signals from various sensors and detects the operating state of the fuel cell system 1.
- step S2 the controller 4 determines whether or not the lowering transient operation is being performed.
- the controller 4 performs the process of step S3 if it is during the lowered transient operation, otherwise ends the current process.
- step S3 the controller 4 determines the difference between the anode pressure Ppre immediately before entering the lowered transient operation (hereinafter referred to as “anode pressure before lowered transient”) Ppre and the current anode pressure Pnow (hereinafter referred to as “anode pressure drop amount”). .) ⁇ P is calculated.
- step S4 the controller 4 refers to a map of FIG. 5 to be described later, and the anode pressure drop amount ⁇ P and the anode gas concentration in the buffer tank 36 immediately before entering the lowering transient operation (hereinafter referred to as “the buffer concentration before the lowering transient”). .) Calculate the minimum anode gas concentration Cmin in the estimated flow path based on Cbuff_pre.
- step S5 the controller 4 refers to a map of FIG. 6 to be described later, and based on the anode pressure drop amount ⁇ P and the pre-transition anode pressure Ppre, the end of the anode gas flow path 121 on the buffer tank 36 side.
- the estimated distance from the stagnation point to the stagnation point (hereinafter referred to as “estimated stagnation point distance”) Lmin is calculated.
- step S6 the controller 4 determines whether or not there is an anode pressure increase command.
- the controller 4 determines that there is a command to increase the anode pressure, for example, when the anode pressure is reduced to the lower limit value or when the accelerator pedal is depressed before the anode pressure is reduced to the lower limit value. If there is a command to increase the anode pressure, the controller 4 performs the process of step S7, and if not, ends the current process.
- step S ⁇ b> 7 the controller 4 is based on the target output of the fuel cell stack 2, and the normal anode pressure upper limit value (hereinafter referred to as “normal anode pressure upper limit value”) set when performing steady operation at the target output. P is calculated.
- the normal anode pressure upper limit P increases as the target output of the fuel cell stack 2 increases.
- step S8 the controller 4 determines whether or not the lowest anode gas concentration Cmin in the estimated flow path is smaller than the determination value C0. If the minimum anode gas concentration in the flow path becomes lower than that, the determination value C0 may be lowered again after the anode pressure is increased and the transient anode operation is performed again. It is a characteristic value. If the estimated minimum anode gas concentration Cmin in the estimated flow path is greater than or equal to the determination value C0, the controller 4 performs the process of step S9. On the other hand, if the estimated minimum anode gas concentration Cmin in the flow path is smaller than the determination value C0, the process of step S10 is performed.
- step S9 the controller 4 controls the pressure regulating valve 33 so that the upper limit value of the anode pressure after the lowered transient operation is the normal anode pressure upper limit value P and the anode pressure increases to the normal anode pressure upper limit value P.
- step S10 the controller 4 refers to a table of FIG. 7 to be described later, and based on the estimated stagnation point distance Lmin, the anode pressure upper limit value P1 that can move the stagnation point to the outside of the anode gas flow path 121. Is calculated.
- the upper limit value P1 of the anode pressure calculated based on the estimated stagnation point distance Lmin is referred to as “stagnation point discharge anode pressure upper limit value P1”.
- step S11 the controller 4 determines whether the stagnation point discharge anode pressure upper limit value P1 is larger than the normal anode pressure upper limit value P. If the stagnation point discharge anode pressure upper limit value P1 is larger than the normal anode pressure upper limit value P, the controller 4 performs the process of step S12. On the other hand, if the stagnation point discharge anode pressure upper limit value P1 is equal to or less than the normal anode pressure upper limit value P, the process of step S9 is performed.
- step S12 the controller 4 sets the upper limit value of the anode pressure after the lowered transient operation to the stagnation point discharge anode pressure upper limit value P1, and controls the pressure regulating valve 33 so that the anode pressure increases to the stagnation point discharge anode pressure upper limit value P1.
- the anode pressure is increased in a state where the pulsation width is increased as compared with the case where the anode pressure is increased by setting the upper limit pressure to the normal anode pressure upper limit value P.
- the pulsation width after the lowered transient operation is larger than the normal pulsation width set according to the target output.
- the anode pressure is increased in the increased state.
- FIG. 5 is a map for calculating the estimated minimum anode gas concentration Cmin in the flow path based on the anode pressure drop amount ⁇ P and the pre-lowering transient buffer concentration Cbuff_pre.
- the lowest anode gas concentration Cmin in the estimated flow path during the lowered transient operation becomes lower as the anode pressure drop ⁇ P becomes larger and as the pre-lower transient buffer concentration Cbuff_pre becomes lower.
- FIG. 6 is a map for calculating the estimated stagnation point distance Lmin based on the anode pressure drop amount ⁇ P and the pre-lowering transient anode pressure Ppre.
- the estimated stagnation point distance Lmin during the lowered transient operation increases as the anode pressure drop amount ⁇ P increases and as the anode pressure Ppre before the lowered transient decreases.
- FIG. 7 is a table for calculating the stagnation point discharge anode pressure upper limit value P1 based on the estimated stagnation point distance Lmin.
- the stagnation point discharge anode pressure upper limit P1 increases as the estimated stagnation point distance Lmin increases.
- FIG. 8 is a diagram for explaining the effect of the pulsation operation control according to the present embodiment.
- FIG. 8A is a diagram showing the transition of the stagnation point in the anode gas flow path 121 when the anode pressure is increased to the stagnation point discharge anode upper limit value P1 after the transient operation for lowering.
- FIG. 8B is a diagram showing a transition of the concentration distribution of the anode gas in the anode gas flow passage 121 when the anode pressure is increased to the stagnation point discharge anode upper limit value P1 after the transitional down operation.
- the broken line is a line showing the concentration distribution of the anode gas after the lowered transient operation.
- the solid line is a line showing the concentration distribution of the anode gas when the anode pressure is raised to the stagnation point discharge anode upper limit value P1 after the transitional down operation.
- the stagnation point can be moved to the outside of the anode gas flow path 121 by raising the anode pressure to the stagnation point discharge anode upper limit value P1 after the lowered transient operation.
- a portion where the anode gas concentration is locally lower than the others can not be left in the anode gas flow path 121. .
- the normal anode pressure upper limit value P is basically set according to the operating state of the fuel cell system 1.
- the anode pressure is decreased to the lower limit value during the subsequent decrease transient operation as the normal anode pressure upper limit value P increases.
- the time required for the reduction is reduced. Therefore, if the stagnation point remains in the anode gas flow path 121 when the anode pressure is increased to the normal anode pressure upper limit value P, the minimum anode gas concentration in the flow path becomes the allowable limit during the lowering transient operation again. The risk of lowering the concentration increases.
- the determination value C0 is increased as the normal anode pressure upper limit P is higher.
- the pulsation operation control according to this embodiment will be described.
- FIG. 9 is a flowchart for explaining the pulsation operation control according to the present embodiment.
- step S21 the controller 4 sets the determination value C0 based on the normal anode pressure upper limit P. Specifically, the determination value C0 is increased as the normal anode pressure upper limit value P is increased.
- the determination value C0 is increased as the normal anode pressure upper limit P is higher, the estimated minimum anode gas concentration Cmin in the estimated flow path is lower than that in the first embodiment. Even if it is relatively high, the stagnation point discharge anode pressure upper limit value P1 is calculated based on the estimated stagnation point distance Lmin. Then, the upper limit value of the anode pressure when the anode pressure is increased after the lowering transient operation is set to be higher than at least the stagnation point discharge anode pressure upper limit value P1.
- the stagnation point does not remain in the anode gas flow path 121 after the anode pressure has been increased, the minimum anode gas concentration in the flow path during the lower transient operation can be increased even if the time for the lower transient operation becomes longer. Can be kept below the allowable limit concentration. Therefore, the power generation efficiency can be stabilized and the deterioration of the fuel cell 10 can be suppressed.
- the controller 4 adjusts the opening degree of the purge valve 38 according to the operating state of the fuel cell system 1, and the buffer concentration (anode gas concentration in the buffer tank 36) Cbuff is the operating state of the fuel cell system 1. In order to achieve a desired management density according to the control.
- the buffer concentration Cbuff When the buffer concentration Cbuff is lower than this control concentration, the anode gas supplied from the buffer tank 36 to the anode gas flow path 121 during the pulsation operation decreases, and the anode gas used for the electrode reaction becomes insufficient, resulting in a decrease in power generation efficiency. There is a risk.
- the buffer concentration Cbuff may be lower than the management concentration.
- the opening degree of the purge valve 38 is the same, the flow rate of the anode off-gas discharged to the outside of the fuel cell system 1 via the purge valve 38 when the anode pressure is increased is higher when the upper limit value of the anode pressure is higher. Become. That is, if the opening degree of the purge valve 38 is the same, the buffer concentration Cbuff can be increased by increasing the upper limit value of the anode pressure.
- the upper limit value of the anode pressure is kept until the buffer concentration Cbuff becomes equal to or higher than the control concentration.
- the stagnation point discharge anode pressure upper limit value P1 is maintained.
- the upper limit value of the anode pressure is returned to the normal anode pressure upper limit value P1.
- FIG. 10 is a flowchart illustrating the anode pressure return control according to this embodiment.
- step S31 the controller 4 estimates the buffer concentration Cbuff.
- the buffer concentration Cbuff after the increase of the Ano pressure is estimated as follows.
- the buffer concentration Cbuff is controlled to be a desired management concentration according to the operation state of the fuel cell system 1 during steady operation. Then, when the transition to the down transition operation is started, the pressure gradually decreases according to the load of the fuel cell stack 2, and when the anode pressure is increased, the inert gas flows into the buffer tank 36 from the anode gas flow path 121. So it drops further.
- the amount of the inert gas that flows into the buffer tank 36 when the anode pressure is increased flows from the buffer tank 36 into the anode gas flow path 121 during the lowering transient operation before increasing the anode pressure, and enters the anode gas flow path 121.
- the amount of inert gas that has flowed from the buffer tank 36 into the anode gas flow path 121 and accumulated in the anode gas flow path 121 during the lowered transient operation is created in advance by experiments or the like according to the anode pressure drop amount ⁇ P. It can be calculated by referring to the map or the like.
- the amount of inert gas that flows from the buffer tank 36 into the anode gas flow path 121 and accumulates in the anode gas flow path 121 during the lowering transient operation increases as the anode pressure drop amount ⁇ P increases.
- the amount of inert gas permeating into the anode gas flow path 121 from the cathode side during the lowered transient operation is determined in advance according to the permeability of the electrolyte membrane and the differential pressure between the cathode pressure and the anode pressure. It can be calculated by referring to a map or the like created by.
- the permeability of the electrolyte membrane is a physical property value determined by the membrane pressure of the electrolyte membrane, etc. As the cathode pressure is higher than the anode pressure, the permeability through the anode gas passage 121 from the cathode side during the lowered transient operation becomes lower. The amount of active gas increases.
- the buffer concentration Cbuff at the time of increasing the anode pressure can be estimated according to the buffer concentration Cbuff at the time of steady operation and the amount of inert gas flowing into the buffer tank 36 when the anode pressure is increased.
- the buffer concentration Cbuff can be estimated according to the opening degree and elapsed time of the purge valve 38 determined according to the operating state of the fuel cell system 1.
- step S32 the controller 4 determines whether or not the upper limit value of the anode pressure is set to the stagnation point discharge anode pressure upper limit value P1. If the upper limit value of the anode pressure is set to the stagnation point discharge anode pressure upper limit value P1, the controller 4 performs the process of step S33, and otherwise ends the current process.
- step S33 the controller 4 determines whether or not the buffer density Cbuff is equal to or higher than the management density. If the buffer density Cbuff is lower than the management density, the controller 4 performs the process of step S34. On the other hand, if the buffer density Cbuff is equal to or higher than the management density, the process of step S35 is performed.
- step S34 the controller 4 performs the pulsation operation while maintaining the upper limit value of the anode pressure at the stagnation point discharge anode pressure upper limit value P1.
- step S35 the controller 4 returns the upper limit value of the anode pressure to the normal anode pressure upper limit value P and performs the pulsation operation.
- the upper limit value of the anode pressure when the upper limit value of the anode pressure is set to the stagnation point discharge anode pressure upper limit value P1, the upper limit value of the anode pressure is set to the normal anode value after the buffer concentration Cbuff becomes equal to or higher than the control concentration.
- the pulsation operation was carried out by returning to the pressure upper limit P.
- the upper limit value of the anode pressure when the upper limit value of the anode pressure is set to the stagnation point discharge anode pressure upper limit value P1, the upper limit value of the anode pressure is set to the normal anode pressure after the buffer concentration Cbuff becomes equal to or higher than the control concentration. The value was returned to the upper limit value P.
- the upper limit value of the anode pressure may be gradually returned from the stagnation point discharge anode pressure upper limit value P1 to the normal anode pressure upper limit value P as the buffer concentration increases after the anode pressure is increased. Even if it does in this way, the effect similar to 3rd Embodiment can be acquired.
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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)とで挟み、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、判定値C0を通常アノード圧上限値Pが高いときほど大きくする点で第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。
次に、本発明の第3実施形態について説明する。本実施形態は、下げ過渡運転後にアノード圧を淀み点排出アノード圧上限値P1まで昇圧させたときに、バッファタンク36内のアノードガス濃度に基づいて、アノード圧を通常アノード圧上限値Pに戻す点で第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。
Claims (7)
- 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、
前記燃料電池に供給するアノードガスの圧力を制御する制御弁と、
前記燃料電池システムの運転状態に基づいて、前記制御弁の開度を制御することによって、所定の圧力で前記燃料電池内のアノードガスの圧力を脈動させる脈動運転手段と、
前記燃料電池内のアノードガスの圧力変化に基づいて、前記燃料電池内で局所的にアノードガス濃度が低くなっている淀み点が存在するかを判断する淀み点判断手段と、
を備え、
前記脈動運転手段は、
前記燃料電池内に淀み点が存在すると判断したときは、前記所定の圧力を増大して脈動運転を行う、
燃料電池システム。 - 前記燃料電池から排出されるアノードオフガスを蓄えるバッファ部と、
前記燃料電池内の淀み点位置を推定する淀み点位置推定手段と、
を備え、
前記脈動運転手段は、
前記淀み点位置が前記バッファ部から遠くなるほど、前記所定の圧力を増大して脈動運転を行う、
請求項1に記載の燃料電池システム。 - 前記燃料電池内の淀み点位置における最低アノードガス濃度を推定する最低アノードガス濃度推定手段を備え、
前記脈動運転手段は、
前記最低アノードガス濃度が所定の判定値よりも低ければ、前記淀み点が前記燃料電池内から前記バッファ部へと排出されるように前記所定の圧力を増大させる、
請求項2に記載の燃料電池システム。 - 前記脈動運転手段は、
前記燃料電池の負荷に応じて、アノードガスの圧力の基本上限圧を算出する基本上限圧算出手段と、
前記燃料電池内の淀み点位置に応じて、その淀み点を前記燃料電池内から前記バッファ部へと排出することができるアノードガスの圧力の上限圧である淀み点排出上限圧を算出する淀み点排出上限圧算出手段と、
を備え、
前記基本上限圧と前記淀み点排出上限圧とのうちの大きいほうを、アノードガスの圧力の上限圧として脈動運転を実施する、
請求項3に記載の燃料電池システム。 - 前記脈動運転手段は、
前記基本上限圧が高いときほど前記判定値を大きくする、
請求項4に記載の燃料電池システム。 - 前記バッファ部内のアノードガスの濃度を推定するバッファ部アノードガス濃度推定手段を備え、
前記脈動運転手段は、
淀み点排出上限圧をアノードガスの圧力の上限圧とした場合は、前記バッファ部内のアノードガス濃度が所定の管理濃度以上になったときに、アノードガスの圧力の上限圧を前記基本上限圧に戻す、
請求項4又は請求項5に記載の燃料電池システム。 - 前記バッファ部内のアノードガスの濃度を推定するバッファ部アノードガス濃度推定手段を備え、
前記脈動運転手段は、
淀み点排出上限圧をアノードガスの圧力の上限圧とした場合に前記バッファ部のアノードガス濃度が所定の管理濃度よりも低いときは、前記バッファ部のアノードガス濃度の増加に併せて段階的にアノードガスの圧力の上限圧を前記基本上限圧まで戻す、
請求項4又は請求項5に記載の燃料電池システム。
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CA2860492A CA2860492A1 (en) | 2012-01-05 | 2012-12-28 | Fuel cell with buffered reactant supply and control |
JP2013552427A JP5871014B2 (ja) | 2012-01-05 | 2012-12-28 | 燃料電池システム |
US14/370,917 US20150004513A1 (en) | 2012-01-05 | 2012-12-28 | Fuel cell system |
CN201280066153.5A CN104040770A (zh) | 2012-01-05 | 2012-12-28 | 燃料电池系统 |
EP12864644.5A EP2802032A4 (en) | 2012-01-05 | 2012-12-28 | FUEL CELL SYSTEM |
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CN104040770A (zh) | 2014-09-10 |
CA2860492A1 (en) | 2013-07-11 |
EP2802032A4 (en) | 2015-09-02 |
JPWO2013103134A1 (ja) | 2015-05-11 |
EP2802032A1 (en) | 2014-11-12 |
JP5871014B2 (ja) | 2016-03-01 |
US20150004513A1 (en) | 2015-01-01 |
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