WO2018029859A1 - 触媒劣化回復装置及び触媒劣化回復方法 - Google Patents
触媒劣化回復装置及び触媒劣化回復方法 Download PDFInfo
- Publication number
- WO2018029859A1 WO2018029859A1 PCT/JP2016/073786 JP2016073786W WO2018029859A1 WO 2018029859 A1 WO2018029859 A1 WO 2018029859A1 JP 2016073786 W JP2016073786 W JP 2016073786W WO 2018029859 A1 WO2018029859 A1 WO 2018029859A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- anode
- oxygen
- gas
- fuel cell
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 227
- 238000011084 recovery Methods 0.000 title claims abstract description 147
- 230000006866 deterioration Effects 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims description 24
- 239000007789 gas Substances 0.000 claims abstract description 183
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 122
- 239000001301 oxygen Substances 0.000 claims abstract description 122
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 122
- 239000000446 fuel Substances 0.000 claims abstract description 114
- 239000012528 membrane Substances 0.000 claims abstract description 84
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 73
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 73
- 239000003792 electrolyte Substances 0.000 claims abstract description 70
- 238000001179 sorption measurement Methods 0.000 claims abstract description 6
- 239000000498 cooling water Substances 0.000 claims description 43
- 239000002737 fuel gas Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 230000035699 permeability Effects 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 230000007246 mechanism Effects 0.000 claims description 6
- 239000012466 permeate Substances 0.000 claims description 6
- 230000005540 biological transmission Effects 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 47
- 239000001257 hydrogen Substances 0.000 description 46
- 229910052739 hydrogen Inorganic materials 0.000 description 46
- 231100000572 poisoning Toxicity 0.000 description 32
- 230000000607 poisoning effect Effects 0.000 description 32
- 238000006243 chemical reaction Methods 0.000 description 16
- 238000010586 diagram Methods 0.000 description 14
- 238000009792 diffusion process Methods 0.000 description 10
- 230000004907 flux Effects 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 230000007423 decrease Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 238000003411 electrode reaction Methods 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 230000001276 controlling effect Effects 0.000 description 5
- 239000002826 coolant Substances 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 238000010248 power generation Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000010926 purge Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 238000011144 upstream manufacturing Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000003247 decreasing effect Effects 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
- 230000006870 function Effects 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000010365 information processing Effects 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000002195 synergetic effect Effects 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
- H01M8/04223—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
-
- 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
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0258—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant
-
- 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
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0267—Collectors; Separators, e.g. bipolar separators; Interconnectors having heating or cooling means, e.g. heaters or coolant flow channels
-
- 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
-
- 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
- H01M8/04701—Temperature
-
- 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
- H01M8/04701—Temperature
- H01M8/04723—Temperature of the coolant
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
- H01M8/04828—Humidity; Water content
- H01M8/0485—Humidity; Water content of the electrolyte
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
-
- 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 an electrode degradation recovery apparatus and degradation recovery method used in a fuel cell system.
- CO carbon monoxide
- Japanese Patent Application Laid-Open No. 2005-25985 and Japanese Patent No. 5008319 disclose that the fuel gas supplied to the fuel electrode contains oxygen.
- a method of oxidizing CO and releasing it from the electrode catalyst is disclosed.
- the catalyst recovery processing of the fuel electrode has a description related to Japanese Patent No. 3536645, Japanese Patent No. 4969955, and Japanese Patent No. 5151035.
- the electrolyte membrane may be deteriorated by reaction heat generated by the reaction between hydrogen and oxygen on the electrode catalyst.
- an object of the present invention is to provide an apparatus and a method capable of performing catalyst recovery processing while suppressing deterioration of an electrolyte membrane.
- a membrane electrode assembly including an electrolyte membrane, and an anode catalyst and a cathode catalyst sandwiching the electrolyte membrane from both sides, an anode separator and a cathode provided with an anode gas channel
- a catalyst deterioration recovery device that recovers the performance of a fuel cell system having a fuel cell sandwiched by a cathode-side separator having a gas flow path due to the adsorption of carbon monoxide on an anode catalyst.
- the catalyst deterioration recovery apparatus includes a recovery control unit that supplies at least a part of oxygen supplied to the cathode gas flow path to the anode catalyst via the electrolyte membrane.
- an apparatus and a method that can perform a catalyst recovery process while suppressing deterioration of an electrolyte membrane.
- FIG. 1 is a perspective view of a fuel cell.
- 2 is a cross-sectional view taken along the line II-II in FIG.
- FIG. 3 is an example of a configuration diagram of the fuel cell system.
- FIG. 4 is a diagram showing a reaction in an anode catalyst in a state where no CO poisoning occurs.
- FIG. 5 is a diagram showing a reaction in an anode catalyst in a state where CO poisoning occurs.
- FIG. 6 is a diagram for explaining a conventional way of thinking about recovery from CO poisoning.
- FIG. 7 is a diagram for explaining new knowledge about recovery from CO poisoning.
- FIG. 8 is a diagram showing the relationship between the oxygen partial pressure and the recovery rate from CO poisoning.
- FIG. 1 is a perspective view of a fuel cell.
- 2 is a cross-sectional view taken along the line II-II in FIG.
- FIG. 3 is an example of a configuration diagram of the fuel cell system.
- FIG. 4 is a diagram showing a reaction
- FIG. 9 is a graph showing the relationship between the oxygen permeation amount of the electrolyte membrane and the effective surface area recovery rate of the anode catalyst.
- FIG. 10 is a flowchart showing a control routine of the catalyst recovery process.
- FIG. 11 is another example of a configuration diagram of the fuel cell system.
- FIG. 12 is a diagram showing the relationship between the oxygen permeability coefficient, the electrolyte membrane temperature, and the water content.
- FIG. 13 is a graph showing the relationship between the catalyst recovery processing speed and the stack temperature.
- FIG. 14 is a diagram showing the relationship between the catalyst recovery processing speed and the relative humidity in the stack.
- FIG. 15 is a flowchart showing a control routine of the catalyst recovery process.
- FIG. 1 and 2 are views for explaining the configuration of a fuel cell 10 according to a position embodiment of the present invention.
- 1 is a perspective view of the fuel cell 10
- FIG. 2 is a cross-sectional view taken along the line II-II of the fuel cell 10 of FIG.
- the fuel cell 10 includes a membrane electrode assembly (MEA) 11, and an anode separator 12 and a cathode separator 13 disposed so as to sandwich the 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 side of the electrolyte membrane 111 and a cathode electrode 113 on the other surface side.
- 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 112 ⁇ / b> A is a member formed of platinum or carbon black particles carrying platinum or the like, and is provided in contact with the electrolyte membrane 111.
- the gas diffusion layer 112B is disposed outside the catalyst layer 112A.
- the gas diffusion layer 112B is a member formed of carbon cloth having gas diffusibility and conductivity, and is provided in contact with the catalyst layer 112A and the anode separator 12.
- the cathode electrode 113 includes a catalyst layer 113A and a gas diffusion layer 113B.
- the catalyst layer 113A is disposed between the electrolyte membrane 111 and the gas diffusion layer 113B, and the gas diffusion layer 113B is disposed between the catalyst layer 113A and the cathode separator 13.
- the anode separator 12 is disposed outside the gas diffusion layer 112B.
- the anode separator 12 includes a plurality of anode gas passages 121 for supplying anode gas (hydrogen gas) to the anode electrode 112.
- the anode gas flow path 121 is formed as a groove-shaped passage.
- the cathode separator 13 is disposed outside the gas diffusion layer 113B.
- the cathode separator 13 includes a plurality of cathode gas passages 131 for supplying cathode gas (air) to the cathode electrode 113.
- the cathode gas channel 131 is formed as a groove-shaped passage.
- Such a fuel cell 10 When such a fuel cell 10 is used as a power source, it is used as a fuel cell stack in which a plurality of fuel cells 10 are stacked according to the required power.
- the fuel cell stack is composed of several hundred fuel cells 10. Then, a fuel cell system that supplies the anode gas and the cathode gas to the fuel cell stack is configured, and electric power according to demand is taken out.
- FIG. 3 is a schematic diagram of a fuel cell system 100 according to an embodiment of the present invention.
- the fuel cell system 100 includes a fuel cell stack 1, a cathode gas supply / discharge device 2, an anode gas supply / discharge device 3, a cooling water circulation device 4, a combustor 5, and a controller 6 as a recovery control unit. .
- the fuel cell stack 1 is a stacked battery in which a plurality of fuel cells 10 (unit cells) are stacked.
- the fuel cell stack 1 generates power by receiving supply of anode gas and cathode gas.
- the fuel cell stack 1 has an anode electrode side terminal and a cathode electrode side terminal as output terminals for extracting electric power.
- the cathode gas supply / discharge device 2 supplies the cathode gas to the fuel cell stack 1 and supplies the cathode off-gas discharged from the fuel cell stack 1 to the combustor 5.
- the cathode gas supply / discharge device 2 includes a cathode gas supply passage 21, a cathode bypass passage 22, and a cathode gas discharge passage 23.
- an air flow meter 26, a compressor 27, and a cathode pressure sensor 51 are arranged in the cathode gas supply passage 21.
- One end of the cathode gas supply passage 21 is connected to the cathode gas inlet of the fuel cell stack 1.
- the air flow meter 26 detects the flow rate of the cathode gas supplied to the fuel cell stack 1.
- the compressor 27 is disposed in the cathode gas supply passage 21 on the downstream side of the air flow meter 26. The operation of the compressor 27 is controlled by the controller 6, and the cathode gas in the cathode gas supply passage 21 is pumped and supplied to the fuel cell stack 1.
- the cathode pressure sensor 51 is disposed in the cathode gas supply passage 21 on the downstream side of the branch portion with the cathode bypass passage 22.
- the cathode pressure sensor 51 detects the pressure of the cathode gas supplied to the fuel cell stack 1.
- the cathode gas pressure detected by the cathode pressure sensor 51 represents the pressure of the entire cathode system including the cathode gas flow path and the like of the fuel cell stack 1.
- the cathode gas discharge passage 23 is a passage through which the cathode off gas discharged from the fuel cell stack 1 flows.
- the cathode off gas is a mixed gas containing cathode gas and water vapor generated by electrode reaction.
- One end of the cathode gas discharge passage 23 is connected to the cathode gas outlet of the fuel cell stack 1, and the other end is connected to the inlet of the combustor 5.
- a water separator 24 for separating water vapor from the cathode off gas is disposed in the cathode gas discharge passage 23.
- an air regulating valve 62 for adjusting the flow rate of the cathode off gas is disposed on the cathode gas discharge passage 23 downstream of the water separator 24 and upstream of the combustor 5.
- the cathode bypass passage 22 is a passage that branches from the cathode gas supply passage 21 and joins the upstream side of the water separator 24 in the cathode gas discharge passage 23. That is, the cathode bypass passage 22 is a passage for supplying the cathode gas to the combustor 5 without passing through the fuel cell stack 1.
- a cathode bypass valve 61 is disposed in the cathode bypass passage 22. The cathode bypass valve 61 is controlled to be opened and closed by the controller 6 and adjusts the flow rate of the cathode gas passing through the cathode bypass passage 22.
- the anode gas supply / discharge device 3 supplies anode gas to the fuel cell stack 1 and also supplies anode off-gas discharged from the fuel cell stack 1 to the combustor 5.
- the anode gas supply / discharge device 3 includes a hydrogen tank 35, an anode gas supply passage 31, a hydrogen supply valve 63, a hydrogen flow meter 36, an anode gas discharge passage 32, an anode gas circulation passage 33, and a hydrogen circulation pump 37. And a purge valve 64.
- the hydrogen tank 35 is a container that stores the anode gas supplied to the fuel cell stack 1 while maintaining a high pressure state.
- the anode gas supply passage 31 is a passage for supplying the anode gas discharged from the hydrogen tank 35 to the fuel cell stack 1. One end of the anode gas supply passage 31 is connected to the hydrogen tank 35, and the other end is connected to the anode gas inlet of the fuel cell stack 1.
- the hydrogen supply valve 63 is disposed in the anode gas supply passage 31 downstream of the hydrogen tank 35.
- the hydrogen supply valve 63 is controlled to be opened and closed by the controller 6 and adjusts the pressure of the anode gas supplied to the fuel cell stack 1.
- the hydrogen flow meter 36 is provided in the anode gas supply passage 31 downstream from the hydrogen supply valve 63.
- the hydrogen flow meter 36 detects the flow rate of the anode gas supplied to the fuel cell stack 1.
- the flow rate detected by the hydrogen flow meter 36 represents the flow rate of the entire anode system including the anode gas flow path of the fuel cell stack 1.
- a hydrogen pressure gauge may be arranged. In this case, the pressure wave detected by the hydrogen pressure gauge and the pressure of the whole anode system are represented.
- the anode gas discharge passage 32 is a passage through which the anode off gas discharged from the fuel cell stack 1 flows. One end of the anode gas discharge passage 32 is connected to the anode gas outlet of the fuel cell stack 1, and the other end is connected to the anode gas inlet of the combustor 5.
- the anode off gas includes an anode gas that has not been used in the electrode reaction, an impurity gas such as nitrogen that has leaked from the cathode gas channel 131 to the anode gas channel 121, moisture, and the like.
- a water separator 38 for separating moisture from the anode off gas is disposed in the anode gas discharge passage 32 in the anode gas discharge passage 32.
- a purge valve 64 is provided in the anode gas discharge passage 32 downstream of the water separator 38. The purge valve 64 is controlled to be opened and closed by the controller 6 and adjusts the flow rate of the anode gas supplied from the anode gas discharge passage 32 to the combustor 5.
- the anode gas circulation passage 33 branches from the anode gas discharge passage 32 on the downstream side of the water separator 38 and merges with the anode gas supply passage 31 downstream from the hydrogen flow meter 36.
- a hydrogen circulation pump 37 is disposed in the anode gas circulation passage 33. The operation of the hydrogen circulation pump 37 is controlled by the controller 6.
- the purge valve 64 is controlled to be opened and closed by the controller 6 and controls the flow rate of the anode off gas supplied to the combustor 5.
- the cooling water circulation device 4 includes a cooling water discharge passage 41, a cooling water pump 45, a radiator 46, a cooling water supply passage 42, a cooling water temperature sensor 54, a cooling water bypass passage 43, a cooling water bypass valve 65, Is provided.
- the cooling water discharge passage 41 is a passage through which the cooling water discharged from the fuel cell stack 1 is passed. One end of the cooling water discharge passage 41 is connected to the cooling water outlet of the fuel cell stack 1, and the other end is connected to the inlet of the radiator 46.
- the operation of the cooling water pump 45 is controlled by the controller 6 to adjust the circulation amount of the cooling water.
- the radiator 46 cools the cooling water that has received heat from the fuel cell stack 1 and has risen in temperature by heat exchange with the atmosphere.
- the air-cooled radiator 46 that cools the cooling water by heat exchange with the atmosphere is used, but the liquid-cooled radiator 46 that cools the cooling water by heat exchange with the cooling medium may also be used. Good.
- the cooling water bypass passage 43 branches from the cooling water discharge passage 41 downstream of the cooling water pump 45 and upstream of the radiator 46 and joins the cooling water supply passage 42 downstream of the radiator 46.
- a cooling water bypass valve 65 is provided at the junction of the cooling water bypass passage 43 and the cooling water supply passage 42.
- the cooling water bypass valve 65 is controlled to be opened and closed by the controller 6 and adjusts the flow rate of the cooling water passing through the radiator 46.
- the cooling water temperature sensor 54 is disposed in the cooling water discharge passage 41 upstream from the cooling water pump 45.
- the fuel cell stack 1 is provided with a voltage sensor 52 and a current sensor 53.
- the voltage sensor 52 detects the output voltage of the fuel cell stack 1, that is, the inter-terminal voltage between the anode electrode side terminal and the cathode electrode side terminal.
- the voltage sensor 52 may be configured to detect a voltage for each of the fuel cells 10 or may be configured to detect a voltage for each of the plurality of fuel cells 10.
- the current sensor 53 detects an output current taken out from the fuel cell stack 1.
- the combustor 5 is for obtaining heat by reacting oxygen in the cathode gas and hydrogen in the anode off gas using, for example, a platinum catalyst.
- the controller 6 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). It is also possible to configure the controller 6 with a plurality of microcomputers.
- the controller 6 receives signals from the air flow meter 26, the hydrogen flow meter 36, the coolant temperature sensor 54, the voltage sensor 52, the current sensor 53, and the like.
- CO adsorbed on the anode catalyst is contained in the anode gas or generated by the anode electrode 112.
- a catalyst recovery process for recovering from CO poisoning is to supply an anode gas containing oxygen to the anode catalyst so that the CO adsorbed on the anode catalyst is oxidized and desorbed from the anode catalyst. Yes.
- FIG. 6 is a diagram for explaining the conventional concept of the catalyst recovery process.
- the inventors of the present invention have found that even when the potential of the anode electrode is low, CO and oxygen react directly as shown in FIG. 7, and CO is desorbed from the anode catalyst.
- the amount of oxygen contained in the anode gas can be reduced in order to suppress the heat generation that causes catalyst deterioration.
- the ratio of the amount of oxygen necessary for recovery from poisoning to the amount of anode gas is as low as several percent or less, and it is difficult to adjust the amount of oxygen to be contained. Therefore, adjustment is more difficult to further reduce the amount of oxygen to be contained. That is, in the method of containing oxygen in the anode gas, it is difficult to suppress the performance deterioration of the anode electrode and the fuel cell 10 due to the catalyst recovery process.
- FIG. 8 is a diagram showing an experimental result as a basis for the above-described new knowledge.
- the vertical axis represents the effective surface area ratio of the anode catalyst, and the horizontal axis represents time.
- the effective surface area ratio is the ratio of the area contributing to the electrode reaction in the surface area of platinum as the anode catalyst. That is, the effective surface area ratio in the state where CO is not adsorbed is 100%.
- the effective surface area ratio can be estimated based on the voltage of the fuel cell 10, for example.
- the experimental procedure is as follows. First, the anode catalyst is poisoned with CO so that the effective surface area ratio becomes 0%. Then, hydrogen is supplied to the anode and a mixed gas of oxygen and nitrogen is supplied to the cathode, and the state of no power generation (OCV) is maintained to monitor the change in the effective surface area ratio.
- FIG. 8 shows experimental results of two patterns with different oxygen partial pressures on the cathode side. The oxygen partial pressure is P O2 _high> P O2 _low.
- the effective surface area ratio which was 0% at the start of the experiment, gradually increases with time. From this, it can be seen that CO is oxidized and separated from the anode catalyst by oxygen that cross leaks from the cathode side to the anode side.
- FIG. 8 shows that the higher the oxygen partial pressure on the cathode side, the greater the increase rate of the effective surface area ratio.
- a permeation flux F represented by Expression (4) is known as an index for evaluating the permeation performance of a membrane. The larger the permeation flux F, the greater the amount of permeation.
- Permeation flux F Permeation coefficient k x Partial pressure difference dP (4)
- the high oxygen partial pressure on the cathode side means that the partial pressure difference dP in equation (4) is large. Therefore, it can be seen that the greater the oxygen permeation flux F, that is, the greater the amount of oxygen that cross-leaks, the quicker recovery from CO poisoning.
- the vertical axis in FIG. 9 is the effective surface area recovery rate, that is, the degree of recovery from CO poisoning, and the horizontal axis is the oxygen permeation amount of the electrolyte membrane 111. As shown in FIG. 9, the effective surface area recovery rate increases as the oxygen permeation amount of the electrolyte membrane 111 increases.
- some of the cross leaked oxygen reacts with hydrogen and may be consumed without being subjected to CO oxidation.
- the less the hydrogen on the anode side the greater the amount of oxygen that is subjected to CO oxidation. From this, it is understood that the same effect as that of increasing the amount of oxygen that cross-leaks can be obtained by reducing the hydrogen partial pressure on the anode side.
- the catalyst recovery process uses oxygen that has been cross leaked from the cathode side to the anode side, the probability that hydrogen and oxygen react on the anode catalyst is lower than when oxygen is included in the anode gas. Degradation of the electrolyte membrane due to heat generated by reaction with oxygen can be suppressed.
- the cathode gas flow rate or the cathode pressure may be increased.
- the cathode gas flow rate or the pressure on the cathode side can be adjusted by using an oxygen-containing gas adjusting device including an air flow meter 26, a compressor 27, a cathode pressure sensor 51, and a cathode bypass valve 61. Therefore, the cathode gas flow rate or the cathode pressure is increased by increasing the rotational speed of the compressor 27 or closing the cathode bypass valve 61 to increase the cathode pressure so that the flow rate detected by the air flow meter 26 increases. Increase.
- the anode gas flow rate or the anode pressure may be reduced.
- the anode gas flow rate or the anode-side pressure can be adjusted by using a fuel gas adjusting device including the hydrogen flow meter 36 and the hydrogen supply valve 63. Therefore, the anode gas flow rate or the anode pressure is reduced by closing the hydrogen supply valve 63 so that the flow rate detected by the hydrogen flow meter 36 is reduced.
- the anode catalyst can be recovered from CO poisoning, but the operating efficiency of the fuel cell system 100 is improved. Will decline. Therefore, recovery from CO poisoning and maintenance of the operation efficiency of the fuel cell system 100 can both be achieved if the catalyst recovery process is executed only when performance degradation due to CO poisoning occurs.
- FIG. 10 is a flowchart showing a control routine based on the contents described above.
- step S100 the controller 6 determines whether or not the ignition switch (IGN) is ON. If it is ON, the power generation control is executed in step S110, and if it is OFF, this routine is terminated.
- step S120 the controller 6 determines whether or not the anode catalyst has deteriorated. If the anode catalyst has deteriorated, the process of step S130 is executed, and if not deteriorated, this routine ends.
- the deterioration of the anode catalyst is a decrease in performance due to CO poisoning.
- Whether the anode catalyst is deteriorated may be acquired (detected) directly or indirectly (estimated).
- the relationship between the current value and the voltage value of the fuel cell stack 1 is acquired in advance, and the voltage value detected by the voltage sensor 52 is assumed from the current value detected by the current sensor 53. There is a method of determining that the battery has deteriorated when the voltage value is lower than the applied voltage value.
- the performance of the fuel cell stack 1 deteriorates over time according to the usage time. Therefore, when the voltage drop amount over time from the unused state is acquired in advance, and the voltage drop amount for the unused state of the voltage value detected by the voltage sensor 52 is larger than the voltage drop amount over time acquired in advance. It can also be determined that it has deteriorated.
- an indirect acquisition method for example, there is a method in which it is considered that the anode gas has deteriorated when the accumulated consumption of the anode gas reaches a predetermined amount. This is a method based on the assumption that the CO concentration in the anode gas is assumed in advance, and that when a predetermined amount of the anode gas is consumed, the contained CO is adsorbed on the anode catalyst.
- Other indirect acquisition methods include a method of determining that the anode catalyst has deteriorated during the first calculation after the start of this control routine. This is a method based on the fact that it can be considered that CO adsorbed during the previous operation remains in the anode catalyst when the fuel cell system 100 is started. In this case, depending on the previous operation time and the time from the end of the previous operation to the start of the current operation, it is determined whether or not to determine that the anode catalyst is deteriorated at the first calculation after the system is started. Also good. There is also a method of determining that the anode catalyst has deteriorated when the accumulated amount of electric power generated in the fuel cell stack 1 reaches a predetermined value.
- step S130 the controller 6 executes a catalyst recovery process.
- the catalyst recovery process is a process of cross leaking oxygen from the cathode side to the anode side by increasing the oxygen partial pressure or decreasing the hydrogen partial pressure.
- step S140 the controller 6 determines whether or not to end the catalyst recovery process. If it is determined that the catalyst recovery process is to be terminated, this routine is terminated. If not, the process of step S130 is continued.
- the controller 6 When the performance of the fuel cell 10 has increased to an assumed value based on the voltage value or the current value, for example, when the voltage value has increased to the assumed voltage value described above, the controller 6 performs CO poisoning. It is determined that the catalyst recovery process is finished as a recovery from the above. Note that if the voltage value stops increasing during the catalyst recovery process, it can be considered that the catalyst has recovered from CO poisoning.
- the catalyst recovery process may be terminated when the execution time of the catalyst recovery process reaches a predetermined time.
- the state in which CO is adsorbed on the anode catalyst is unstable, and has a characteristic that CO is easily detached when the temperature of the anode catalyst rises. That is, if the temperature of the anode catalyst is raised when the catalyst recovery process is performed, the effect of the catalyst recovery process can be further enhanced.
- raising the temperature of an anode catalyst here means raising from the management temperature of the anode catalyst in the state (normal operation state) which does not perform a catalyst recovery process.
- FIG. 11 is a configuration diagram of a system capable of increasing the temperature of the anode catalyst when the catalyst recovery process is executed. The difference from FIG. 3 is that a heating passage 44 and a flow rate adjusting valve 66 for adjusting the flow rate of the heating passage 44 are provided.
- the heating passage 44 is arranged so that the cooling water can exchange heat with the combustor 5.
- the flow rate adjustment valve 66 is controlled to be opened and closed by the controller 6, and the cooling water passes through the heating passage 44 when the catalyst recovery process is executed.
- the controller 6 When executing the catalyst recovery process, the controller 6 opens the flow rate adjustment valve 66 so that the coolant passes through the coolant bypass passage 43 without passing through the radiator 46. Then, the controller 6 supplies the anode off gas and the cathode gas to the combustor 5 for combustion, and raises the cooling water temperature by the combustion heat. Thereby, the temperature of the fuel cell stack 1 rises.
- the increase in the temperature of the fuel cell stack 1 naturally increases the temperature of the MEA 11 and the temperature of the anode catalyst included in the MEA 11. That is, according to the configuration of FIG. 11, by controlling the cooling water temperature, the temperature of the anode catalyst can be controlled, and a state in which CO is easily detached can be created.
- the effect of the catalyst recovery process can be further enhanced by increasing the cooling water temperature when the catalyst recovery process is executed.
- the cooling water temperature can be adjusted by controlling the opening degree of the flow rate adjusting valve 66, deterioration of the anode catalyst due to heat can be avoided.
- the heat source is not limited to the combustor 5.
- a heater for heating may be newly provided. In this case, since it is not necessary to consider the positional relationship with the combustor 5, the layout of the cooling water circulation device 4 is improved.
- the catalyst deterioration recovery apparatus of the present embodiment recovers the performance that has been reduced by the adsorption of carbon monoxide of the anode catalyst 112 of the fuel cell 10, and at least part of the oxygen supplied to the cathode gas flow path 131 is A recovery control unit that supplies the anode catalyst 112 via the electrolyte membrane 111 is provided.
- the fuel cell 10 includes an electrolyte membrane 111, electrode catalyst layers 112A and 113A provided on both surfaces of the electrolyte membrane 111, and a gas diffusion layer provided on the surface of the electrode catalyst layers 112A and 113A opposite to the electrolyte membrane 111.
- a membrane electrode assembly (MEA) 11 configured to include 112B and 113B is sandwiched between an anode separator 12 including an anode gas channel 121 and a cathode separator 13 including a cathode gas channel 131.
- the controller 6 as a recovery control unit recovers the performance of the anode catalyst 112 by controlling the amount of oxygen that permeates the electrolyte membrane 111.
- the CO adsorbed on the anode catalyst can be oxidatively released without increasing the potential of the anode electrode 112. That is, it is possible to recover from CO poisoning while suppressing the deterioration of the electrolyte membrane due to the exothermic reaction on the electrode catalyst.
- the catalyst deterioration recovery method of the present embodiment supplies oxygen to the anode catalyst 112 in order to oxidize and desorb the carbon monoxide adsorbed on the anode catalyst 112 of the fuel cell system 100 described above. At least a part of oxygen supplied to the cathode gas channel 131 is supplied to the anode catalyst 112 through the electrolyte membrane 111. Thereby, like the catalyst deterioration recovery apparatus described above, it is possible to recover from CO poisoning while suppressing deterioration of the electrolyte membrane due to an exothermic reaction on the electrode catalyst.
- the fuel cell system 100 of this embodiment includes a fuel gas adjusting device that reduces at least one of the flow rate or pressure of the fuel gas supplied to the anode gas flow path 121.
- the fuel gas adjusting device includes a hydrogen flow meter 36 and a hydrogen supply valve 63.
- the controller 6 controls the opening degree of the hydrogen supply valve 63 so that the flow rate detected by the hydrogen flow meter 36 decreases.
- the hydrogen concentration on the anode side decreases, and the direct reaction between oxygen that has cross-leaked from the cathode side and CO adsorbed on the anode catalyst can be promoted, and the anode catalyst can be recovered from CO poisoning.
- the fuel cell system 100 of this embodiment includes an oxygen-containing gas regulator that increases at least one of the flow rate or pressure of the oxygen-containing gas supplied to the cathode gas channel 131 instead of the fuel gas regulator described above. Also good.
- the oxygen-containing gas adjusting device includes a compressor 27, an air flow meter 26, a cathode pressure sensor 51, and a cathode bypass valve 61. Then, the controller 6 increases the rotational speed of the compressor 27 so that the flow rate detected by the air flow meter 26 increases, or closes the cathode bypass valve 61 so that the pressure detected by the cathode pressure sensor 51 increases.
- the oxygen concentration and oxygen partial pressure on the cathode side increase to increase the amount of oxygen that cross-leaks from the cathode side, promoting the direct reaction between CO adsorbed on the anode catalyst and oxygen, and making the anode catalyst CO Can recover from poisoning.
- the fuel cell system 100 may include at least one of a fuel gas adjusting device and an oxygen-containing gas adjusting device.
- the fuel cell system 100 may further include a temperature control mechanism that controls the temperature of the membrane electrode assembly (MEA) 11.
- the controller 6 raises the temperature of the MEA 11 by the temperature control mechanism when executing the catalyst recovery process.
- the temperature control mechanism includes the combustor 5, the heating passage 44, and a flow rate adjusting valve 66 that adjusts the flow rate of the heating passage 44.
- Increasing the temperature of MEA 11 also increases the temperature of the anode catalyst.
- the CO adsorbed on the anode catalyst is in an unstable state, and is easily detached when the temperature of the anode catalyst rises. Therefore, according to this embodiment, the catalyst recovery process can be further promoted.
- the information processing apparatus further includes a determination unit that determines whether to perform the catalyst recovery process. Specifically, the determination unit is included in the controller 6. The determination unit obtains whether or not the performance of the anode catalyst is degraded due to CO poisoning, and determines that the catalyst recovery process is executed when the performance is degraded. When the catalyst recovery process is executed, the operation efficiency of the fuel cell system 100 may be reduced. However, according to the present embodiment, the performance of the anode catalyst can be recovered while suppressing a decrease in the operation efficiency.
- the determination unit detects or estimates whether or not the performance of the anode catalyst is degraded due to CO poisoning based on the state of the fuel cell 10. Thereby, it can be appropriately determined whether or not the performance deterioration due to CO poisoning occurs.
- the determination unit determines that the catalyst recovery process is stopped when the performance of the anode catalyst is recovered. That is, after starting the catalyst recovery process, the controller 6 ends the catalyst recovery process when the anode catalyst recovers from the CO poisoning. As a result, the catalyst recovery process is not continuously performed in vain, so that the catalyst recovery process can be executed efficiently.
- the permeation flux F of oxygen is increased by increasing the partial pressure difference dP of oxygen.
- the oxygen permeation flux F is increased by increasing the oxygen permeation coefficient k.
- FIG. 12 shows the relationship between the oxygen permeability coefficient of the electrolyte membrane 111 and the temperature and water content of the electrolyte membrane 111. As shown in FIG. 12, the oxygen permeability coefficient of the electrolyte membrane 111 increases as the temperature increases. Further, as shown in FIG. 12, the electrolyte membrane 111 has a larger oxygen permeability coefficient as the moisture content increases, that is, as the humidity increases.
- the temperature of the electrolyte membrane 111 may be increased or the humidity of the electrolyte membrane 111 may be increased.
- the cooling water temperature may be increased by the configuration of FIG. 11 described in the first embodiment. If the coolant temperature rises, the temperature of the fuel cell stack 1 also rises. The increase in the temperature of the fuel cell stack 1 naturally increases the temperature of the MEA 11 and the temperature of the electrolyte membrane 111 included in the MEA 11.
- FIG. 13 is a diagram showing the relationship between the temperature of the fuel cell stack 1 (stack temperature) and the catalyst recovery processing speed.
- the left vertical axis indicates the catalyst recovery processing speed
- the right vertical axis indicates the CO oxidation reaction speed and the oxygen amount permeating the electrolyte membrane 111
- the horizontal axis indicates the stack temperature.
- the temperature of the anode catalyst increases and the CO is easily oxidized. That is, as shown in FIG. 13, the higher the temperature of the fuel cell stack 1, the higher the CO oxidation reaction rate. Further, as the temperature of the fuel cell stack 1 increases, the temperature of the electrolyte membrane 111 also increases, and the permeation flux of the electrolyte membrane 111 increases as described above. That is, as shown in FIG. 13, as the temperature of the fuel cell stack 1 increases, the amount of oxygen that passes through the electrolyte membrane 111 increases.
- the catalyst recovery processing rate increases as the temperature of the fuel cell stack 1 increases due to the synergistic effect of the increase in the amount of oxygen permeating the electrolyte membrane 111 and the increase in the CO oxidation reaction rate at the anode catalyst.
- the humidification amount of the fuel cell stack 1 may be increased.
- the humidification amount can be adjusted, for example, by controlling the circulation amount of the anode off gas in the configuration of FIG. That is, by increasing the rotation speed of the hydrogen circulation pump 37 and increasing the circulation amount of the anode off gas, diffusion of the produced water into the anode gas at the anode electrode is promoted, and as a result, the humidity of the electrolyte membrane 111 increases. To do.
- the humidity control of the electrolyte membrane 111 by circulating the anode off gas is generally performed in order to obtain a suitable power generation state. That is, the system itself for circulating the anode off gas is a general one. Therefore, if this system is used for the catalyst recovery process, it is possible to adjust the humidity for the catalyst recovery process without providing a new humidity adjusting device.
- FIG. 14 is a graph showing the relationship between the humidity of the fuel cell stack 1 (relative humidity in the stack) and the catalyst recovery processing speed.
- the left vertical axis indicates the catalyst recovery processing speed
- the right vertical axis indicates the amount of oxygen that permeates the electrolyte membrane 111
- the horizontal axis indicates the relative humidity in the stack.
- the oxygen permeability coefficient increases as described above, so that the amount of oxygen that permeates the electrolyte membrane 111 increases as shown in FIG. For this reason, as shown in FIG. 14, the catalyst recovery processing speed increases as the humidity of the fuel cell stack 1 increases.
- At least one of the temperature and the humidity of the fuel cell stack 1 is controlled as the catalyst recovery process.
- a cathode gas oxygen-containing gas
- oxygen-containing gas oxygen-containing gas
- the controller 6 may execute the catalyst recovery process only when the deterioration of the anode catalyst is detected.
- FIG. 15 is a flowchart of these control routines.
- FIG. 15 is obtained by adding Step S125 between Step S120 and Step S130 in the flowchart of FIG. Moreover, the processing content of step S130 differs from 1st Embodiment.
- step S125 the controller 6 supplies a cathode gas (oxygen-containing gas) containing oxygen at a ratio higher than the stoichiometric ratio (high stoichiometric ratio). Supply to the cathode electrode 113.
- a cathode gas oxygen-containing gas
- controller 6 performs a catalyst recovery process in step S130.
- a catalyst recovery process in step S130.
- at least one of the temperature and humidity of the fuel cell stack 1 is raised.
- the catalyst recovery process for increasing the oxygen permeation flux in step S130 is performed. The effect is further promoted. Further, by executing the catalyst recovery process only when the catalyst deterioration is detected, the amount of hydrogen consumed by the catalyst recovery process can be suppressed.
- step S120 when the controller 6 determines in step S120 that the catalyst has deteriorated, it starts supplying a cathode gas (oxygen-containing gas) containing oxygen in a high stoichiometric ratio in step S125, and in step S130, the catalyst Recovery processing has started.
- the controller 6 when the temperature of the fuel cell stack 1 is increased as the catalyst recovery process, the controller 6 does not permit the catalyst recovery process when the combustor 5 cannot generate the amount of heat necessary for the catalyst recovery process.
- the controller 6 performs the catalyst recovery process when sufficient anode gas cannot be circulated to achieve the humidity required for the catalyst recovery process. Is not allowed.
- the fuel cell system 100 includes a permeability coefficient control device that controls the oxygen permeability coefficient of the electrolyte membrane 111.
- the permeation coefficient control device is a device that controls the oxygen permeation coefficient by controlling at least one of the temperature and the water content of the MEA 11. If the controller 6 increases the oxygen permeation coefficient using the permeation coefficient control device, the amount of oxygen that cross leaks increases, so that the catalyst recovery process can be promoted.
- the permeation coefficient control device is a device that adjusts the temperature of cooling water, for example.
- the permeation coefficient control device includes the combustor 5, the heating passage 44, and a flow rate adjusting valve 66 that adjusts the flow rate of the heating passage 44.
- the controller 6 controls the temperature of the MEA 11 by adjusting the temperature of the cooling water, but essentially controls the temperature of the electrolyte membrane 111. If the temperature of the electrolyte membrane 111 is raised, the oxygen permeation coefficient increases, the amount of cross leaking oxygen increases, and the catalyst recovery process is promoted.
- the transmission coefficient control device may be a device that adjusts the humidification amount of the fuel cell 10.
- the device includes an anode gas discharge passage 32, an anode gas circulation passage 33, a hydrogen circulation pump 37, and a purge valve 64, and circulates off-gas discharged from the anode electrode to the anode electrode. is there. If the humidity of the electrolyte membrane 111 is increased using this device, the oxygen permeation coefficient increases, the amount of cross leaking oxygen increases, and the catalyst recovery process is promoted.
- a cathode gas oxygen-containing gas
- oxygen-containing gas oxygen-containing gas
- the permeation flux of the formula (4) is increased, and the catalyst recovery process is promoted.
Abstract
Description
図1及び図2は、本発明の位置実施形態による燃料電池10の構成を説明するための図である。図1は燃料電池10の斜視図であり、図2は図1の燃料電池10のII-II断面図である。
そして、式(2)の反応によりアノード電極の電位が上昇すると、式(3)の反応によってアノード触媒に吸着しているCOが酸化される。
この式(3)によるCOの酸化反応は、アノード電極の電位が上昇し、かつアノード触媒上の水素がすべて消費されてから起こると考えられていた。このため、従来はCOの酸化反応が生じる電位までアノード電極の電位を上昇させるのに十分な量の酸素を供給していた。しかし、電位を上昇させるための式(2)の反応は発熱反応であるため、反応により発生した熱により電解質膜が劣化し、燃料電池10の性能低下を招来することになる。
本実施形態は、酸素をアノード側にクロスリークさせるという触媒回復処理の基本的な考え方は第1実施形態と同様であるが、酸素をクロスリークさせるための処理が異なる。
Claims (16)
- 電解質膜と、前記電解質膜を両面から挟むアノード触媒及びカソード触媒と、を含んで構成される膜電極接合体を、アノードガス流路を備えるアノードセパレータ及びカソードガス流路を備えるカソードセパレータで挟持してなる燃料電池を備える燃料電池システムの、アノード触媒の一酸化炭素の吸着により低下した性能を回復させる触媒劣化回復装置において、
前記カソードガス流路に供給される酸素の少なくとも一部を、前記電解質膜を介してアノード触媒へ供給する回復制御部を備える触媒劣化回復装置。 - 請求項1に記載の触媒劣化回復装置において、
前記回復制御部は、前記電解質膜を透過する酸素量を制御することにより前記アノード触媒の性能を回復させる触媒劣化回復装置。 - 請求項2に記載の触媒劣化回復装置において、
前記燃料電池システムは、前記カソードガス流路に供給される酸素含有ガスの流量または圧力を調整する酸素含有ガス調整装置をさらに備え、
前記回復制御部は、前記酸素含有ガス調整装置を用いて前記カソードガス流路に供給される酸素含有ガスの流量または圧力の少なくとも一方を上昇させることにより前記電解質膜を透過する酸素量を制御する触媒劣化回復装置。 - 請求項2に記載の触媒劣化回復装置において、
前記燃料電池システムは、前記アノードガス流路に供給される燃料ガスの流量または圧力を調整する燃料ガス調整装置をさらに備え、
前記回復制御部は、前記燃料ガス調整装置を用いて前記アノードガス流路に供給される燃料ガスの流量または圧力の少なくとも一方を低下させることにより前記電解質膜を透過する酸素量を制御する触媒劣化回復装置。 - 請求項2に記載の触媒劣化回復装置において、
前記燃料電池システムは、前記アノードガス流路に供給される燃料ガスの流量または圧力を調整する燃料ガス調整装置と、前記カソードガス流路に供給される酸素含有ガスの流量または圧力を調整する酸素含有ガス調整装置と、をさらに備え、
前記回復制御部は、前記燃料ガス調整装置を用いて前記アノードガス流路に供給される燃料ガスの流量または圧力の少なくとも一方を低下させるか、前記酸素含有ガス調整装置を用いて前記カソードガス流路に供給される酸素含有ガスの流量または圧力の少なくとも一方を上昇させるか、の少なくともいずれか一方を実行することにより前記電解質膜を透過する酸素量を制御する触媒劣化回復装置。 - 請求項1から5のいずれかに記載の触媒劣化回復装置において、
前記燃料電池システムは、前記膜電極接合体の温度を制御する温度制御機構をさらに備え、
前記回復制御部は、前記アノード触媒の性能を回復させる場合に、前記温度制御機構により前記膜電極接合体の温度を上昇させる触媒劣化回復装置。 - 請求項2に記載の触媒劣化回復装置において、
前記回復制御部は、前記電解質膜の酸素透過係数を制御することにより前記電解質膜を透過する酸素量を制御する触媒劣化回復装置。 - 請求項7に記載の触媒劣化回復装置において、
前記燃料電池システムは、前記膜電極接合体の温度または含水量の少なくとも一方を制御する透過係数制御装置をさらに備え、
前記回復制御部は、前記透過係数制御装置を用いて前記酸素透過係数を制御する触媒劣化回復装置。 - 請求項8に記載の触媒劣化回復装置において、
前記燃料電池システムは、前記透過係数制御装置として冷却水を加熱する装置をさらに備え、
前記回復制御部は、冷却水の温度を上昇させることにより前記膜電極接合体の温度を制御する触媒劣化回復装置。 - 請求項8に記載の触媒劣化回復装置において、
前記燃料電池システムは、前記透過係数制御装置としてアノード極から排出されたオフガスをアノード極に循環させる循環装置をさらに備え、
前記回復制御部は、前記オフガスの循環量を制御することにより前記膜電極接合体の含水量を増加させる触媒劣化回復装置。 - 請求項7から10のいずれかに記載の触媒劣化回復装置において、
前記回復制御部は、前記透過係数制御装置を作動させる際に化学量論比より高い比率の酸素を含有する前記酸素含有ガスをカソード極に供給する触媒劣化回復装置。 - 請求項1から11のいずれかに記載の触媒劣化回復装置において、
前記回復制御部は、カソードガス流路に供給される酸素の少なくとも一部を、前記電解質膜を介してアノード触媒へ供給するか否かを判断する判断部をさらに備える触媒劣化回復装置。 - 請求項12に記載の触媒劣化回復装置において、
前記判断部は、前記アノード触媒が一酸化炭素吸着により性能低下しているか否かを取得し、性能低下している場合に、前記電解質膜を介して前記アノード触媒へ供給すると判断する触媒劣化回復装置。 - 請求項13に記載の触媒劣化回復装置において、
前記判断部は、前記アノード触媒が一酸化炭素吸着により性能低下しているか否かを、前記燃料電池の状態に基づいて検知または推定する触媒劣化回復装置。 - 請求項13または14に記載の触媒劣化回復装置において、
前記判断部は、前記電解質膜を介した前記アノード触媒への酸素供給を開始した後、前記アノード触媒の性能が回復したら前記酸素供給を停止させる触媒劣化回復装置。 - 電解質膜と、前記電解質膜を両面から挟むアノード触媒及びカソード触媒と、を含んで構成される膜電極接合体を、アノードガス流路を備えるアノードセパレータ及びカソードガス流路を備えるカソードセパレータで挟持してなる燃料電池を有する燃料電池システムの、アノード触媒に吸着した一酸化炭素を酸化させて前記アノード触媒から脱離させるために前記アノード触媒に酸素を供給する触媒劣化回復方法において、
前記カソードガス流路に酸素を供給し、
前記酸素の少なくとも一部を、前記電解質膜を介してアノード側の前記電極触媒層へ供給する触媒劣化回復方法。
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP16912739.6A EP3499619B1 (en) | 2016-08-12 | 2016-08-12 | Catalyst deterioration recovery device and catalyst deterioration recovery method |
KR1020197004522A KR102068947B1 (ko) | 2016-08-12 | 2016-08-12 | 촉매 열화 회복 장치 및 촉매 열화 회복 방법 |
US16/323,077 US10756374B2 (en) | 2016-08-12 | 2016-08-12 | Catalyst deterioration recovery device and catalyst deterioration recovery method |
PCT/JP2016/073786 WO2018029859A1 (ja) | 2016-08-12 | 2016-08-12 | 触媒劣化回復装置及び触媒劣化回復方法 |
CN201680088387.8A CN109643811B (zh) | 2016-08-12 | 2016-08-12 | 催化剂劣化恢复装置以及催化剂劣化恢复方法 |
JP2018533402A JP6699732B2 (ja) | 2016-08-12 | 2016-08-12 | 触媒劣化回復装置及び触媒劣化回復方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/JP2016/073786 WO2018029859A1 (ja) | 2016-08-12 | 2016-08-12 | 触媒劣化回復装置及び触媒劣化回復方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2018029859A1 true WO2018029859A1 (ja) | 2018-02-15 |
Family
ID=61163215
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2016/073786 WO2018029859A1 (ja) | 2016-08-12 | 2016-08-12 | 触媒劣化回復装置及び触媒劣化回復方法 |
Country Status (6)
Country | Link |
---|---|
US (1) | US10756374B2 (ja) |
EP (1) | EP3499619B1 (ja) |
JP (1) | JP6699732B2 (ja) |
KR (1) | KR102068947B1 (ja) |
CN (1) | CN109643811B (ja) |
WO (1) | WO2018029859A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111261899A (zh) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | 恢复高温质子交换膜燃料电池性能的方法和电池运行方法 |
CN113675438A (zh) * | 2020-05-15 | 2021-11-19 | 丰田自动车株式会社 | 燃料电池系统 |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2020030974A (ja) * | 2018-08-23 | 2020-02-27 | 本田技研工業株式会社 | 燃料ガス供給システム |
CN111193052B (zh) * | 2019-12-31 | 2021-05-18 | 潍柴动力股份有限公司 | 控制燃料电池发动机活化的方法及装置 |
JP7331825B2 (ja) * | 2020-12-10 | 2023-08-23 | トヨタ自動車株式会社 | 燃料電池システム |
KR102648904B1 (ko) | 2021-08-11 | 2024-03-18 | (주)원익머트리얼즈 | 암모니아 연료용 고체산화물 연료전지 |
CN113809372A (zh) * | 2021-09-02 | 2021-12-17 | 北京化工大学 | 一种利用压差渗氧有效缓解质子交换膜燃料电池阳极中毒的方法 |
CN114447380B (zh) * | 2022-01-18 | 2024-04-26 | 同济大学 | 一种恢复质子交换膜燃料电池电堆性能的方法 |
Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS508319B1 (ja) | 1970-01-13 | 1975-04-03 | ||
JPS536645B2 (ja) | 1972-08-25 | 1978-03-10 | ||
JP2004146209A (ja) * | 2002-10-24 | 2004-05-20 | Aisin Seiki Co Ltd | 燃料電池発電システム |
JP2005025985A (ja) | 2003-06-30 | 2005-01-27 | Osaka Gas Co Ltd | 燃料電池発電装置 |
JP2005235522A (ja) * | 2004-02-18 | 2005-09-02 | Matsushita Electric Ind Co Ltd | 高分子電解質型燃料電池及びその運転方法 |
JP2005310464A (ja) * | 2004-04-20 | 2005-11-04 | Honda Motor Co Ltd | 燃料電池システム |
JP2008041478A (ja) * | 2006-08-08 | 2008-02-21 | Toyota Motor Corp | 燃料電池システム及び燃料電池システムの異常電位制御方法 |
JP2008293701A (ja) * | 2007-05-22 | 2008-12-04 | Toyota Motor Corp | 燃料電池システム |
JP4969955B2 (ja) | 2006-09-08 | 2012-07-04 | 東芝燃料電池システム株式会社 | 燃料電池システム及びその発電停止方法 |
WO2012176528A1 (ja) * | 2011-06-21 | 2012-12-27 | 日産自動車株式会社 | 燃料電池システム |
JP5151035B2 (ja) | 2006-02-03 | 2013-02-27 | 日産自動車株式会社 | 燃料電池システム |
JP2016066407A (ja) * | 2014-09-22 | 2016-04-28 | 日産自動車株式会社 | 燃料電池の特性回復方法および燃料電池システム |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07105967A (ja) | 1993-09-30 | 1995-04-21 | Aisin Aw Co Ltd | 燃料電池 |
JP3536645B2 (ja) | 1998-01-30 | 2004-06-14 | 株式会社豊田中央研究所 | 燃料電池の運転制御方法 |
DE10221146A1 (de) * | 2002-05-13 | 2003-12-04 | Daimler Chrysler Ag | Verfahren zum Betreiben eines wenigstens eine diskontinuierlich betriebene Brennstoffzelle aufweisenden Brennstoffzellensystems |
US7976972B2 (en) * | 2004-06-14 | 2011-07-12 | Panasonic Corporation | Method of preserving polymer electrolyte fuel cell stack and preservation assembly of polymer electrolyte fuel cell stack |
JP4908778B2 (ja) * | 2004-06-30 | 2012-04-04 | キヤノン株式会社 | 固体高分子型燃料電池の触媒層の製造方法および固体高分子型燃料電池の製造方法 |
JP5008319B2 (ja) | 2006-03-15 | 2012-08-22 | 大阪瓦斯株式会社 | 固体高分子形燃料電池システムおよびその制御方法 |
JP5164348B2 (ja) * | 2006-08-03 | 2013-03-21 | 日本ゴア株式会社 | 膜電極組立体およびその製造方法ならびにそれを用いた固体高分子形燃料電池 |
KR100849127B1 (ko) | 2006-11-28 | 2008-07-31 | (주)퓨얼셀 파워 | 연료전지스택 및 그 촉매재생 운전방법 |
JP2009048931A (ja) * | 2007-08-22 | 2009-03-05 | Toshiba Corp | 膜電極複合体の製造方法およびこの方法によって製造された膜電極複合体を用いた燃料電池 |
-
2016
- 2016-08-12 WO PCT/JP2016/073786 patent/WO2018029859A1/ja unknown
- 2016-08-12 KR KR1020197004522A patent/KR102068947B1/ko active IP Right Grant
- 2016-08-12 EP EP16912739.6A patent/EP3499619B1/en active Active
- 2016-08-12 US US16/323,077 patent/US10756374B2/en active Active
- 2016-08-12 JP JP2018533402A patent/JP6699732B2/ja active Active
- 2016-08-12 CN CN201680088387.8A patent/CN109643811B/zh active Active
Patent Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS508319B1 (ja) | 1970-01-13 | 1975-04-03 | ||
JPS536645B2 (ja) | 1972-08-25 | 1978-03-10 | ||
JP2004146209A (ja) * | 2002-10-24 | 2004-05-20 | Aisin Seiki Co Ltd | 燃料電池発電システム |
JP2005025985A (ja) | 2003-06-30 | 2005-01-27 | Osaka Gas Co Ltd | 燃料電池発電装置 |
JP2005235522A (ja) * | 2004-02-18 | 2005-09-02 | Matsushita Electric Ind Co Ltd | 高分子電解質型燃料電池及びその運転方法 |
JP2005310464A (ja) * | 2004-04-20 | 2005-11-04 | Honda Motor Co Ltd | 燃料電池システム |
JP5151035B2 (ja) | 2006-02-03 | 2013-02-27 | 日産自動車株式会社 | 燃料電池システム |
JP2008041478A (ja) * | 2006-08-08 | 2008-02-21 | Toyota Motor Corp | 燃料電池システム及び燃料電池システムの異常電位制御方法 |
JP4969955B2 (ja) | 2006-09-08 | 2012-07-04 | 東芝燃料電池システム株式会社 | 燃料電池システム及びその発電停止方法 |
JP2008293701A (ja) * | 2007-05-22 | 2008-12-04 | Toyota Motor Corp | 燃料電池システム |
WO2012176528A1 (ja) * | 2011-06-21 | 2012-12-27 | 日産自動車株式会社 | 燃料電池システム |
JP2016066407A (ja) * | 2014-09-22 | 2016-04-28 | 日産自動車株式会社 | 燃料電池の特性回復方法および燃料電池システム |
Non-Patent Citations (1)
Title |
---|
See also references of EP3499619A4 |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111261899A (zh) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | 恢复高温质子交换膜燃料电池性能的方法和电池运行方法 |
CN111261899B (zh) * | 2018-11-30 | 2021-04-13 | 中国科学院大连化学物理研究所 | 恢复高温质子交换膜燃料电池性能的方法和电池运行方法 |
CN113675438A (zh) * | 2020-05-15 | 2021-11-19 | 丰田自动车株式会社 | 燃料电池系统 |
CN113675438B (zh) * | 2020-05-15 | 2024-02-20 | 丰田自动车株式会社 | 燃料电池系统 |
Also Published As
Publication number | Publication date |
---|---|
KR20190026026A (ko) | 2019-03-12 |
KR102068947B1 (ko) | 2020-01-21 |
US10756374B2 (en) | 2020-08-25 |
CN109643811B (zh) | 2019-12-17 |
US20200185746A1 (en) | 2020-06-11 |
EP3499619A1 (en) | 2019-06-19 |
JPWO2018029859A1 (ja) | 2019-06-06 |
JP6699732B2 (ja) | 2020-05-27 |
EP3499619A4 (en) | 2019-08-07 |
CN109643811A (zh) | 2019-04-16 |
EP3499619B1 (en) | 2020-07-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2018029859A1 (ja) | 触媒劣化回復装置及び触媒劣化回復方法 | |
JP4468994B2 (ja) | 燃料電池システム | |
KR102092516B1 (ko) | 연료 전지 시스템, 및 연료 전지 시스템의 제어 방법 | |
JP2009016170A (ja) | 燃料電池システムおよび燃料電池システムの制御装置 | |
JP2008198439A (ja) | 燃料電池システム | |
JP6133365B2 (ja) | 燃料電池システムの運転方法 | |
JP2005032652A (ja) | 燃料電池システム | |
WO2014103101A1 (ja) | 燃料電池システム及び燃料電池システムにおける燃料電池の発電性能回復方法 | |
JP4661055B2 (ja) | 燃料電池システムおよび運転方法 | |
JP2007141744A (ja) | 燃料電池システム | |
JP2008269911A (ja) | 燃料電池システムおよび燃料電池システムにおけるガス圧力調節方法 | |
JP5140958B2 (ja) | 燃料電池システムおよびこの制御方法 | |
JP5872315B2 (ja) | 燃料電池システムの起動方法および起動装置 | |
JP5187477B2 (ja) | 燃料電池システム | |
JP5073448B2 (ja) | 固体高分子型燃料電池の運転方法 | |
JP4772293B2 (ja) | 燃料電池システム | |
JP6315714B2 (ja) | 燃料電池システムの運転制御方法 | |
JP2005174757A (ja) | 燃料電池システム | |
JP5279005B2 (ja) | 燃料電池システム | |
JP2009134977A (ja) | 燃料電池システム | |
JP2023166706A (ja) | 燃料電池システム | |
JP2016058294A (ja) | 燃料電池システム | |
JP2008159548A (ja) | 燃料電池システム | |
JP2012169150A (ja) | 燃料電池システム | |
JP2011060776A (ja) | 燃料電池システムおよび運転方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 16912739 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2018533402 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20197004522 Country of ref document: KR Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 2016912739 Country of ref document: EP Effective date: 20190312 |