WO2022201484A1 - Procédé de vieillissement d'une pile à combustible - Google Patents

Procédé de vieillissement d'une pile à combustible Download PDF

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Publication number
WO2022201484A1
WO2022201484A1 PCT/JP2021/012827 JP2021012827W WO2022201484A1 WO 2022201484 A1 WO2022201484 A1 WO 2022201484A1 JP 2021012827 W JP2021012827 W JP 2021012827W WO 2022201484 A1 WO2022201484 A1 WO 2022201484A1
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Prior art keywords
aging
fuel cell
ultra
water
ufb
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PCT/JP2021/012827
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English (en)
Japanese (ja)
Inventor
佐藤浩一郎
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本田技研工業株式会社
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Application filed by 本田技研工業株式会社 filed Critical 本田技研工業株式会社
Priority to PCT/JP2021/012827 priority Critical patent/WO2022201484A1/fr
Priority to CN202180096228.3A priority patent/CN117099229A/zh
Priority to JP2023508364A priority patent/JP7500862B2/ja
Publication of WO2022201484A1 publication Critical patent/WO2022201484A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/043—Processes for controlling fuel cells or fuel cell systems applied during specific periods
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
    • H01M8/04858—Electric variables
    • 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]
    • 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
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • 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
    • 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 aging method.
  • a fuel cell comprises a membrane-electrode assembly (MEA) having an electrolyte membrane and a pair of electrodes laminated on each side of the electrolyte membrane, and a pair of separators ( bipolar plate).
  • MEA membrane-electrode assembly
  • a plurality of these fuel cells are stacked to form a fuel cell stack.
  • aging is performed after assembly in order to bring out the power generation performance of the fuel cell.
  • Japanese Patent Application Laid-Open No. 2020-57572 discloses aging in which a manufactured fuel cell stack is housed in an aging booth and an aging device (power generation device) is used to generate power.
  • one aspect of the present invention is a method for aging a fuel cell having an electrolyte membrane and a pair of electrodes provided on both sides of the electrolyte membrane, comprising: Hydrogen ultra-fine bubble water containing hydrogen as ultra-fine bubbles is supplied to one electrode of the fuel cell, and ultra-fine bubble aging is performed by moving the protons from the one electrode through the electrolyte membrane to the other electrode.
  • the fuel cell aging method described above makes it possible to further promote humidification of the electrolyte membrane, thereby improving the efficiency of aging.
  • FIG. 1 is an explanatory diagram showing the overall configuration of an aging device that performs an aging method for a fuel cell according to one embodiment of the present invention
  • 1 is a perspective view showing the configuration of a fuel cell
  • FIG. 3A is an explanatory diagram showing a first pattern of UFB aging (concentration cell).
  • FIG. 3B is an explanatory diagram showing a second pattern of UFB aging (concentration cell).
  • FIG. 4 is an enlarged cross-sectional view showing the action of the fuel cell in the first pattern of the concentration cell;
  • FIG. 4 is an enlarged cross-sectional view showing the action of a fuel cell in a second pattern of concentration cells;
  • FIG. 1 is an explanatory diagram showing the overall configuration of an aging device that performs an aging method for a fuel cell according to one embodiment of the present invention
  • 1 is a perspective view showing the configuration of a fuel cell
  • FIG. 3A is an explanatory diagram showing a first pattern of UFB aging (concentration cell).
  • FIG. 6A is a flow chart showing a fuel cell aging method according to the first embodiment.
  • FIG. 6B is a flowchart showing the processing flow of UFB aging. It is a partial explanatory view showing an aging device according to a modification.
  • FIG. 8A is an explanatory diagram showing the configuration of the first supply processing section of the aging device.
  • FIG. 8B is an explanatory diagram showing the configuration of the second supply processing section of the aging device.
  • FIG. 9A is an explanatory diagram showing the first pattern of the fuel cell aging method (UFB aging: hydrogen pump) according to the second embodiment.
  • FIG. 9B is an explanatory diagram showing a second pattern of UFB aging (hydrogen pump).
  • the aging method for the fuel cell 10 according to the first embodiment of the present invention uses the aging device 50 shown in FIG.
  • a fuel cell stack 12 in which a plurality of fuel cells 10 that are unit power generation cells are stacked is set in the aging device 50 .
  • the aging device 50 performs ultra-fine bubble aging in which a liquid having ultra-fine bubbles (hereinafter sometimes abbreviated as UFB) is supplied to the fuel cell stack 12, thereby improving the power generation performance of the fuel cell stack 12. Increase.
  • UFB ultra-fine bubble aging
  • UFB ultra-fine bubble aging
  • the configuration of the fuel cell stack 12 will be described first.
  • the fuel cell stack 12 is configured by housing a stack 14 in which a plurality of fuel cells 10 are stacked in a stack case (not shown).
  • the fuel cell 10 includes a membrane-electrode assembly 18 (hereinafter referred to as MEA 18) having a resin frame 19 on its outer periphery, and a first separator 20a and a second separator 20a laminated on both sides of the MEA 18, respectively. and a separator 20b.
  • MEA 18 membrane-electrode assembly 18
  • an anode gas such as hydrogen flows between the first separator 20a and the MEA 18, while a cathode gas (oxidant gas) such as oxygen flows between the second separator 20b and the MEA 18.
  • the MEA 18 has an electrolyte membrane 22 , an anode electrode 24 provided on one side of the electrolyte membrane 22 , and a cathode electrode 26 provided on the other side of the electrolyte membrane 22 .
  • the electrolyte membrane 22 for example, a solid polymer electrolyte membrane (cation exchange membrane), which is a thin film of perfluorosulfonic acid containing water, is applied.
  • the electrolyte membrane 22 can use an HC (hydrocarbon)-based electrolyte in addition to the fluorine-based electrolyte.
  • Each of the anode electrode 24 and the cathode electrode 26 includes catalyst layers 24a and 26a bonded to the electrolyte membrane 22, dense carbon layers 24b and 26b stacked on the catalyst layers 24a and 26a, and dense carbon layers 24b and 26b. and gas diffusion layers 24c, 26c (see FIG. 4).
  • the catalyst layers 24a and 26a are formed by, for example, uniformly coating the surface of carbon paper, carbon cloth, or the like with porous carbon particles having platinum alloys supported on their surfaces together with an ion-conductive polymer binder. .
  • the catalyst layers 24a and 26a have a plurality of pores with an average diameter (average pore diameter) of about 50 to 80 nm.
  • the dense carbon layers 24b, 26b are made of carbon paper, carbon cloth, or the like, and have an average pore diameter of about 400 to 600 nm.
  • the gas diffusion layer 24c is made of carbon paper, carbon cloth, or the like, and has an average pore diameter of about 30 to 50 ⁇ 10 3 nm.
  • the first separator 20a and the second separator 20b are formed by pressing a steel plate, a stainless steel plate, an aluminum plate, a plated steel plate, or a metal plate whose metal surface is subjected to anticorrosive surface treatment to form an uneven cross section, for example.
  • a junction separator is formed by joining the outer peripheries of the first separator 20a of one fuel cell 10 and the second separator 20b of the other fuel cell 10, and this junction separator and the MEA 18 are laminated. By doing so, the laminate 14 is constructed.
  • the first separator 20a has an anode flow channel 30 for flowing anode gas on the surface facing the anode electrode 24 of the MEA 18 .
  • the anode channel 30 is configured by linear channel grooves (or wavy channel grooves) formed between a plurality of ridges 31 extending in the longitudinal direction of the first separator 20a.
  • the second separator 20b has a cathode flow channel 32 through which the cathode gas flows on the surface facing the cathode electrode 26 of the MEA 18 (in FIG. 2, the flow direction of the cathode gas is illustrated on the cathode electrode 26 for convenience). ing).
  • the cathode channel 32 is composed of linear channel grooves (or wavy channel grooves) formed between a plurality of ridges 33 extending in the longitudinal direction of the second separator 20b.
  • a coolant channel 34 through which coolant (for example, water) flows is formed between the contact surfaces of the first separator 20a and the second separator 20b.
  • the coolant channel 34 is formed by overlapping the shape of the back surface of the anode channel 30 of the first separator 20a and the shape of the back surface of the cathode channel 32 of the second separator 20b.
  • the fuel cell 10 has a plurality of fluid communication holes 36 for circulating the anode gas, the cathode gas, and the coolant in the stacking direction of the stack 14 .
  • One anode gas inlet communication hole 38a, two cathode gas outlet communication holes 40b, and a coolant inlet communication hole 42a are provided as fluid communication holes 36 at one edge in the long side direction of the fuel cell 10.
  • the anode gas inlet communication hole 38 a communicates with the anode channel 30 of the first separator 20 a to allow the anode gas to flow into the anode channel 30 .
  • the two coolant inlet communication holes 42 a communicate with the coolant channel 34 between the first and second separators 20 a and 20 b to allow the coolant to flow into the coolant channel 34 .
  • the two cathode gas outlet communication holes 40b communicate with the cathode flow channel 32 of the second separator 20b to allow the cathode gas to flow out from the cathode flow channel 32. As shown in FIG.
  • fluid communication holes 36 are provided with one cathode gas inlet communication hole 40a, two anode gas outlet communication holes 38b, and two coolant outlet communication holes 42b. be done.
  • the cathode gas inlet communication hole 40 a communicates with the cathode channel 32 of the second separator 20 b to allow the cathode gas to flow into the cathode channel 32 .
  • the two coolant outlet communication holes 42 b communicate with the coolant channel 34 between the first and second separators 20 a and 20 b to allow the coolant to flow out of the coolant channel 34 .
  • the two anode gas outlet communication holes 38 b communicate with the anode flow channel 30 of the first separator 20 a to allow the anode gas to flow out from the anode flow channel 30 .
  • the position, number, shape, etc. of the fluid communication holes 36 may be appropriately set according to the required specifications.
  • a terminal plate 44a, an insulator 46a and an end plate 48a are stacked outward in this order.
  • a terminal plate 44b, an insulator 46b and an end plate 48b are sequentially stacked outward.
  • Each end plate 48a, 48b forms part of a stack case.
  • Each of the fluid communication holes 36 is also formed through one end (or both ends) of the laminate 14 in the stacking direction, and communicates with each pipe (not shown) attached to the outer surface of the end plate 48a.
  • the aging device 50 includes an arrangement section 52 for arranging the fuel cell stack 12, a first circulation section 60 and a second circulation section 70 for circulating the liquid to the fuel cell stack 12, and a voltage applying section for applying a potential to the fuel cell stack 12. a portion 80;
  • the aging device 50 also includes a control unit 54 that controls the operation of the entire device.
  • the placement section 52 has a space in which the fuel cell stack 12 can be set, and has a plurality of pipes (not shown) that can be connected to the respective fluid communication holes 36 of the set fuel cell stack 12 (end plate 48a). .
  • the aging device 50 also connects the pair of terminal plates 44 a and 44 b of the fuel cell stack 12 set in the placement section 52 and the voltage application section 80 with a pair of harnesses 56 .
  • the first circulation section 60 has a liquid first circulation path 61 connected to a predetermined pipe of the placement section 52 .
  • the first circulation path 61 is composed of a metal pipe or the like having a flow path inside, and is connected to the anode gas inlet communication hole 38 a and the anode gas outlet communication hole 38 b of the fuel cell stack 12 set in the placement section 52 . That is, the first circulation path 61 circulates the liquid to the anode electrodes 24 of the fuel cells 10 in the fuel cell stack 12 .
  • the first circulation unit 60 circulates, as a liquid, ultra-fine bubble water (UFB water) in which ultra-fine bubbles (UFB) are mixed with water to the anode electrode 24 . Therefore, the first circulation section 60 has a first ultra-fine bubble generation section (first UFB generation section 62 ) at a predetermined position in the first circulation path 61 .
  • UFB water ultra-fine bubble water
  • first UFB generation section 62 first ultra-fine bubble generation section
  • UFB refers to bubbles whose bubble diameter is smaller than that of microbubbles (for example, bubbles whose bubble diameter is smaller than 10 3 nm).
  • the first UFB generator 62 according to the present embodiment generates UFB with an average bubble diameter of approximately 100 nm to 150 nm.
  • UFB is negatively charged as a negative colloid even in a liquid, and there is no bonding between UFBs, and it is difficult to float, so it is possible to stay in the liquid for a long time without reducing the bubble number density.
  • the first UFB generation unit 62 includes a mixing unit 63 that mixes UFB with the water circulating in the first circulation path 61, and two types of gas sources (H 2 gas source 64, H2 gas source 64, N2 gas source 65).
  • the first UFB generation unit 62 supplies one of the two types of gas sources to the mixing unit 63, and the mixing unit 63 generates UFB water having the UFB of the supplied gas. That is, the first UFB generation unit 62 generates hydrogen ultra-fine bubble water (H 2 UFB water) having hydrogen UFB (H 2 UFB) and nitrogen ultra-fine bubble water (N 2 UFB) having nitrogen UFB (N 2 UFB).
  • UFB water can be selectively generated.
  • the mixing section 63 of the first UFB generation section 62 is provided near the supply port 52a that supplies UFB water to the arrangement section 52, and operates appropriately under the control of the control section .
  • the configuration of the mixing section 63 is not particularly limited, and a well-known device capable of generating UFB water from supplied gas and water can be applied.
  • the mixing unit 63 can apply a pressurized dissolution method in which a solution obtained by dissolving gas in water under pressure is repeatedly ejected and circulated under low pressure.
  • the first circulation unit 60 includes, in addition to the first UFB generation unit 62, a first pump 66 that circulates the liquid and a first valve 67 that opens and closes the flow path of the first circulation path 61. Prepare for 61.
  • the rotation speed of the first pump 66 is controlled by the control unit 54 to circulate the liquid at an appropriate flow speed.
  • the opening of the first valve 67 is changed under the control of the control unit 54 to adjust the pressure of the liquid in the first circulation path 61 and block the flow of the liquid in the closed state.
  • the first circulation path 61 is provided with a plurality of sensors (not shown) that detect information related to the circulation state of the liquid, and each sensor is connected to the control section 54 so as to be able to communicate information.
  • the plurality of sensors include a pressure sensor that detects the pressure in the first circulation path 61, a flow rate sensor that detects the flow rate of liquid, and a bubble sensor or concentration sensor that detects the amount of UFB.
  • the first circulation path 61 is connected to a first water supply section 68 that supplies water to the first circulation path 61 and a first discharge path 69 that discharges liquid from the first circulation path 61.
  • the first water supply unit 68 is connected to city water, for example, and includes a water treatment unit that removes impurities, a tank, a valve (both not shown), etc. Under the control of the control unit 54, the first circulation route 61 is supplied with water.
  • the first discharge path 69 is provided with a first discharge valve 69a that opens and closes under the control of the control unit 54. When the first discharge valve 69a is closed, discharge of the liquid in the first circulation path 61 is blocked, and the first discharge The liquid in the first circulation path 61 is discharged while the valve 69a is open.
  • the second circulation section 70 has a second liquid circulation path 71 connected to a predetermined pipe of the placement section 52 .
  • the second circulation path 71 is composed of a metal pipe or the like having a flow path inside, and is connected to the cathode gas inlet communication hole 40 a and the cathode gas outlet communication hole 40 b of the fuel cell stack 12 set in the placement section 52 . That is, the second circulation path 71 circulates liquid to the cathode electrodes 26 of the fuel cells 10 in the fuel cell stack 12 .
  • the second circulation path 71 includes a second UFB generator 72 having a mixing part 73, an H2 gas source 74, and an N2 gas source 75, a second pump 76, and a second A valve 77 and a plurality of sensors (not shown) are provided.
  • the second circulation path 71 is also connected to a second water supply section 78 and a second discharge path 79 having a second discharge valve 79a.
  • the same configuration as that of the first circulation section 60 can be applied to each configuration of the second circulation section 70 , and the second circulation section 70 operates under the control of the control section 54 . Therefore, a detailed description is omitted.
  • the voltage applying section 80 of the aging device 50 is electrically connected to the pair of terminal plates 44a and 44b of the fuel cell stack 12 arranged in the arrangement section 52 via a harness 56, and is connected to the control section 54. Communicatively connected.
  • the voltage applying section 80 applies an appropriate potential to the anode electrode 24 and the cathode electrode 26 of each fuel cell 10 under the control of the control section 54 .
  • the voltage application section 80 has a power supply section 82 , a switch section 84 and a voltage control section 86 .
  • the power source unit 82 and the switch unit 84 constitute an equivalent circuit in which the positive and negative electrodes of the two power sources 82a and 82b connected in parallel are opposite to each other, and which can switch between energization and cutoff of each power source. . Therefore, in the voltage application section 80, one power supply 82a applies a negative potential to the anode electrode 24 of the fuel cell 10 compared to the other poles while the switch section 84 is switched by the control section 54, and the cathode electrode 26 is positively applied. Apply a potential. Conversely, in the voltage application section 80, the other power supply 82b applies a positive potential to the anode electrode 24 and a negative potential to the cathode electrode 26 compared with the other poles while the switch section 84 is switched by the control section 54.
  • the voltage control section 86 of the voltage application section 80 adjusts the voltage output to the fuel cell stack 12 while the power supply section 82 is in an energized state.
  • the voltage value may be set to an appropriate value according to the number of stacked fuel cells 10.
  • the voltage per unit fuel cell one cell is set to be in the range of several mV to about 1V. .
  • the aging device 50 is electrically connected to the pair of terminal plates 44a and 44b of the fuel cell stack 12 via a harness 56, and is also connected to the control section 54 so as to be communicable with an electronic load section (electronic load section). device: not shown).
  • the electronic load section is particularly used for applying a large current between the anode and cathode during power generation (power generation aging or power generation for characteristic evaluation). Appropriate current is applied to
  • the aging device 50 supplies coolant (water) to the coolant outlet communication hole 42b, the coolant inlet communication hole 42a, and the coolant channel 34 of the fuel cell stack 12 arranged in the arrangement portion 52.
  • coolant water
  • a refrigerant circulation part for circulating may be provided.
  • the control unit 54 of the aging device 50 has one or more processors, memories, input/output interfaces and electronic circuits (both not shown).
  • a program (not shown) stored in the memory is executed by one or more processors, so that a plurality of functional blocks for controlling each configuration of the fuel cell system are formed within the control unit 54 .
  • At least part of each functional block may be configured by an electronic circuit including an integrated circuit such as an ASIC (Application Specific Integrated Circuit), an FPGA (Field-Programmable Gate Array), or a discrete device.
  • Memory may also be associated with a processor, integrated circuit, or the like.
  • the aging method of the fuel cell 10 utilizes the principle of a concentration cell to allow protons (H + ) to pass through the MEA 18 during UFB aging.
  • the concentration cell uses the H 2 UFB water supplied to the fuel cell 10 to create a hydrogen (H 2 ) concentration difference between the anode electrode 24 and the cathode electrode 26 of the MEA 18 , promotes concentration equilibrium in the MEA 18 , and proton to move.
  • the control unit 54 controls the operations of the first distribution unit 60, the second distribution unit 70, and the voltage application unit 80, so that two patterns of UFB aging (concentration cell ) can be implemented.
  • the first pattern H 2 UFB water is supplied to the anode electrode 24 and a negative potential is applied compared to the other electrodes, while N 2 UFB water is supplied to the cathode electrode 26 and a positive potential is applied.
  • N 2 UFB water is supplied to the anode electrode 24 and a positive potential is applied, while H 2 UFB water is supplied to the cathode electrode 26 and a negative potential is applied compared to the other electrodes.
  • the aging device 50 uses an electronic load unit (not shown) instead of the voltage application unit 80 to apply a current to either the anode or the cathode (or alternately), so that the voltage application unit 80 and the It is also possible to apply a similar potential difference.
  • control unit 54 may implement the first pattern or the second pattern alone, or alternately implement the first pattern and the second pattern every predetermined period.
  • the operation of the fuel cell 10 by supplying UFB water in the first pattern and the second pattern will be described below.
  • the MEA 18 has a high H 2 concentration on the anode electrode 24 side and a low H 2 concentration on the cathode electrode 26 side. Therefore, in the MEA 18, a motion is created in which protons flow from the anode electrode 24 to the cathode electrode 26 through the electrolyte membrane 22 so that the H2 concentration difference is balanced. Further, as described above, since the surface potential of H 2 UFB is negatively charged, the H 2 UFB in the anode electrode 24 is positively applied by power supply from the voltage applying section 80 to the terminal plates 44a and 44b. It is possible to encourage movement toward the cathode electrode 26 side.
  • the H 2 UFB supplied to the anode channel 30 has a bubble diameter smaller than the average pore diameters of the gas diffusion layer 24c and dense carbon layer 24b. Therefore, the H 2 UFB moves in the gas diffusion layer 24c and the dense carbon layer 24b without breaking bubbles.
  • the average pore diameter is smaller than the bubble diameter of H 2 UFB, so that H 2 UFB easily bursts into H 2 molecules. That is, UFB aging can sufficiently spread both H 2 molecules and water molecules (H 2 O) over the catalyst layer 24a.
  • the H 2 that has moved to the catalyst layer 24a reacts with the platinum catalyst and ionizes into protons (H + ) and electrons (e ⁇ ).
  • the ionized protons move in the MEA 18 from the anode side to the cathode side along with the electroosmotic water.
  • electrons move to the first separator 20a in contact with the anode electrode 24, and move to the second separator 20b via the harness 56 and the voltage applying section 80.
  • the N 2 UFB supplied to the cathode electrode 26 is dispersed in the gas diffusion layer 26c, the dense carbon layer 26b and the catalyst layer 26a.
  • This N 2 UFB suppresses unnecessary reactions (reactions by oxygen, protons, and electrons) in the catalyst layer 26a by not reacting with the platinum catalyst.
  • the protons transferred through the MEA 18 and the electrons of the cathode electrode 26 react with the platinum catalyst of the catalyst layer 26a to form H 2 molecules.
  • the H 2 molecules produced at the cathode electrode 26 are discharged from the fuel cell 10 together with the N 2 UFB water.
  • the aging device 50 may perform control to make the pressure on the anode electrode 24 side higher than the pressure on the cathode electrode 26 side when the first pattern is performed.
  • the control unit 54 reduces the opening degree of the first valve 67 to be smaller than the opening degree of the second valve 77, is greater than the amount of water supplied from the second water supply unit 78 and the rotation speed of the second pump 76 .
  • the aging device 50 makes the water pressure in the first circulation path 61 and the fuel cell stack 12 (anode flow path 30) higher than the water pressure in the second circulation path 71 and the fuel cell stack 12 (cathode flow path 32). can be higher.
  • the aging device 50 increases the pressure (differential pressure) on the anode electrode 24 side with respect to the pressure on the cathode electrode 26 side by approximately 50 kPa to 150 kPa. In this way, since the pressure on the side supplying H 2 UFB is high, the H 2 UFB in the H 2 UFB water supplied to the anode electrode 24 side more easily moves to the catalyst layer 24a. Protons can be efficiently generated.
  • the H 2 UFB supplied to the cathode channel 32 moves to the catalyst layer 26a through the gas diffusion layer 26c and the dense carbon layer 26b, and bursts at the catalyst layer 26a.
  • Two molecules diffuse easily.
  • the H 2 molecules in the catalyst layer 26a react with the platinum catalyst and ionize into protons (H + ) and electrons (e ⁇ ).
  • the ionized protons move in the MEA 18 from the cathode side to the anode side along with the electroosmotic water.
  • electrons move to the second separator 20b in contact with the cathode electrode 26, and move to the first separator 20a via the harness 56 and the voltage application section 80.
  • the protons and electrons of the anode electrode 24 that have migrated via the MEA 18 react with the platinum catalyst of the catalyst layer 24a to form H 2 molecules.
  • the H2 molecules produced at the anode electrode 24 are discharged together with the N2 UFB water.
  • the aging device 50 preferably controls the pressure on the cathode electrode 26 side to be higher than the pressure on the anode electrode 24 side. That is, the control unit 54 makes the degree of opening of the second valve 77 smaller than the degree of opening of the first valve 67, and reduces the amount of water supplied from the second water supply unit 78 and the rotational speed of the second pump 76 to the second 1 Increase the amount of water supplied from the water supply unit 68 and the rotational speed of the first pump 66 .
  • the pressure (differential pressure) on the side of the cathode electrode 26 with respect to the pressure on the side of the anode electrode 24 (differential pressure) becomes sufficiently high, and protons are efficiently directed from the catalyst layer 26a of the cathode electrode 26 to the electrolyte membrane 22. can dodge.
  • control unit 54 when the control unit 54 alternately performs the first pattern and the second pattern and performs control to create a differential pressure between the pair of electrodes, the control unit 54 changes the electrolyte membrane 22 when switching between the first pattern and the second pattern. It is preferable to carry out a conditioning step in order to suppress the overload of the . In this conditioning step, in order to reduce (or zero) the differential pressure between the pair of electrodes, purge control is performed to discharge H 2 UFB water from the circulation path on the supply side of H 2 UFB water with high pressure.
  • N 2 supply control it is preferable to perform N 2 supply control to supply N 2 UFB water to the electrode on the supply side of H 2 UFB water.
  • control unit 54 performs N2 supply control while performing purge control, thereby efficiently eliminating the differential pressure and removing residual hydrogen from the electrodes. .
  • the aging device 50 is basically configured as described above, and the method for aging the fuel cell 10 will be described below with reference to FIG. 6A. Specifically, the aging method of the fuel cell 10 sequentially performs UFB aging (step S1), N2 purge (step S2), CV aging (step S3), and performance evaluation (step S4).
  • the UFB aging in step S1 is mainly a process of increasing the wettability of the electrolyte membrane 22 to facilitate the movement of protons.
  • UFB water H 2 UFB, N 2 UFB
  • the gas diffusibility in the anode electrode 24 and the cathode electrode 26 is improved, and the wettability of the electrolyte membrane 22 can be efficiently enhanced.
  • the aging device 50 alternately performs the first pattern (supply application pattern) and the second pattern (reverse supply application pattern).
  • the control unit 54 performs the first pattern (step S1-1), determines the end of the first pattern (step S1-2), performs the conditioning step (step S1-3), The execution of two patterns (step S1-4), the end determination of the second pattern (step S1-5), and the conditioning step (step S1-6) are repeated until the UFB aging is completed.
  • the control unit 54 controls the first pump 66 and the first water supply unit 68 of the first circulation unit 60, and the second pump 76 and the second water supply unit 78 of the second circulation unit 70. to circulate water to the anode electrode 24 and the cathode electrode 26 . Then, the control unit 54 controls the first UFB generation unit 62 to supply H 2 from the H 2 gas source 64, thereby generating H 2 UFB in the mixing unit 63, and controlling the second UFB generation unit 72. By supplying N 2 from the N 2 gas source 75 , N 2 UFB is generated in the mixing section 73 . Thereby, the aging device 50 supplies H 2 UFB water to the anode electrode 24 and N 2 UFB water to the cathode electrode 26 .
  • the control unit 54 controls the first pump 66, the first water supply unit 68, and the first valve 67 of the first circulation unit 60 to increase the pressure on the side of the anode electrode 24 that supplies the H 2 UFB water to The pressure is made higher than the pressure on the side of the cathode electrode 26 that supplies N 2 UFB water. Accordingly, a large amount of H 2 UFB smoothly moves to the catalyst layer 24 a of the anode electrode 24 . Further, the control unit 54 may stop the circulation of the H 2 UFB water by stopping the first pump 66 and closing the first valve 67 when the pressure on the anode electrode 24 side is increased. This stop ensures that the H 2 UFB water stays on the anode electrode 24 .
  • the control unit 54 causes the voltage application unit 80 to apply a negative potential to the anode electrode 24 and a positive potential to the cathode electrode 26 compared to the other electrodes. do.
  • a large amount of H 2 UFB explodes into H 2 molecules within the catalyst layer 24a of the anode electrode 24 of the MEA 18 .
  • the H 2 molecules react with the platinum catalyst and are ionized into protons and electrons, and the protons pass through the electrolyte membrane 22 together with the electroosmotic water, thereby moving to the cathode electrode 26 .
  • the protons and electrons that have moved through the electrolyte membrane 22 react with the platinum catalyst to form H2 molecules.
  • the control unit 54 determines whether the supply of H 2 UFB water to the anode electrode 24 has been performed for a predetermined supply period (including a period during which circulation is stopped), and determines whether the supply period has not elapsed, keep using the same H 2 UFB water. That is, the controller 54 continuously circulates the H 2 UFB water between the fuel cell stack 12 and the first circulation path 61 . Conversely, when the predetermined supply period has elapsed, the H 2 UFB water is drained from the first circulation path 61 and new H 2 UFB water is supplied to the first circulation path 61 .
  • the aging device 50 discharges the H 2 UFB water generated by the first UFB generation unit 62 through the first circulation path 61 after the H 2 UFB water generated by the first UFB generation unit 62 is sufficiently reused, thereby reducing the consumption of H 2 . .
  • the control unit 54 determines whether or not the first pattern has been performed for a predetermined period (step S1-2), and if it has not been performed for a predetermined period (step S1-2: NO), While one pattern is continued, if it is performed for a predetermined period (step S1-2: YES), the process proceeds to the conditioning step (step S1-3).
  • the control unit 54 fully opens the first valve 67 and opens the first discharge valve 69a of the first discharge path 69 to discharge H 2 UFB on the anode electrode 24 side.
  • the cathode electrode 26 side maintains the circulation of the second circulation path 71 (or the circulation is stopped by closing the second valve 77) by not opening the second discharge valve 79a. As a result, the water pressure of the H 2 UFB water on the anode electrode 24 side is reduced, and the differential pressure with the cathode electrode 26 side is reduced.
  • the control unit 54 operates the first UFB generation unit 62 and the first pump 66 of the first circulation unit 60 to operate the anode electrode 24 side. is supplied with N 2 UFB water.
  • N 2 UFB water By supplying the N 2 UFB water, the H 2 molecules remaining on the anode electrode 24 are discharged while the electrolyte membrane 22 and the catalyst layer 24a are kept moist.
  • the control unit 54 implements the second pattern (step S1-4).
  • the control unit 54 controls the first UFB generation unit 62 to supply N 2 from the N 2 gas source 65 to generate N 2 UFB in the mixing unit 63, and the second UFB generation unit 72 is controlled to supply H 2 from the H 2 gas source 74 to generate H 2 UFB in the mixing section 73 .
  • the aging device 50 supplies N 2 UFB water to the anode electrode 24 and H 2 UFB water to the cathode electrode 26 .
  • the controller 54 makes the pressure on the side of the cathode electrode 26 supplying H 2 UFB water higher than the pressure on the side of the anode electrode 24 supplying N 2 UFB water.
  • control unit 54 may stop the circulation of the H 2 UFB water by stopping the second pump 76 and closing the second valve 77 when the pressure on the cathode electrode 26 side is increased. This stop ensures that the high pressure H 2 UFB water stays on the cathode electrode 26 .
  • the control unit 54 applies a negative potential to the cathode electrode 26 and a positive potential to the anode electrode 24 by the voltage application unit 80 compared to the other electrodes. .
  • a large amount of protons reacted with the platinum catalyst at the cathode electrode 26 permeate the electrolyte membrane 22 together with the electroosmotic water.
  • the protons and electrons react with the platinum catalyst to form H 2 molecules.
  • control unit 54 determines whether or not the supply of H 2 UFB water to the cathode electrode 26 has been performed for a predetermined supply period (including the period during which circulation is stopped), and determines whether the supply period If not, continue to use H 2 UFB water. Conversely, when the predetermined supply period has elapsed, the H 2 UFB water is discharged from the second circulation path 71 and new H 2 UFB water is supplied to the second circulation path 71 .
  • control unit 54 determines whether or not the second pattern has been performed for a predetermined period (step S1-5), and if it has not been performed for a predetermined period (step S1-5: NO), While the two patterns are continued, if the predetermined period is performed (step S1-5: YES), the conditioning step is performed (step S1-6). In this conditioning step, control is performed in reverse to the conditioning step of step S1-3.
  • control unit 54 discharges the H 2 UFB on the cathode electrode 26 side, reduces the water pressure of the H 2 UFB water on the cathode electrode 26 side, and reduces the pressure difference with the cathode electrode 26 side. Further, the control unit 54 supplies N 2 UFB water to the cathode electrode 26 side while discharging the H 2 UFB water from the second circulation path 71 . By supplying the N 2 UFB water, H 2 molecules remaining on the cathode electrode 26 can be discharged while the electrolyte membrane 22 and the catalyst layer 26a are kept moist. After performing the above conditioning process for a set period (or until the differential pressure between the cathode electrode 26 and the anode electrode 24 becomes equal to or less than a predetermined pressure), the control unit 54 ends the conditioning process.
  • the aging device 50 ends the UFB aging by continuing the above processing flow for the set number of repetitions or for the set period. After the UFB aging is finished, the aging method of the fuel cell 10 performs the next N2 purge (step S2 in FIG. 6A). This N2 purge process may use the aging device 50 used in UFB aging, or may apply another device.
  • the N2 purge is performed by supplying N2 gas, which is an inert gas, to the anode flow channel 30 and the cathode flow channel 32 of the fuel cell stack 12 after UFB aging.
  • N2 gas which is an inert gas
  • This is the process of discharging the
  • the same aging device 50 after discharging the water in the first circulation path 61 and the second circulation path 71, , and N 2 gas is supplied from the N 2 gas source 75 of the second UFB generator 72 to the second circulation path 71 .
  • the humidity of the electrolyte membrane 22 is adjusted and the flooding of the anode electrode 24 and the cathode electrode 26 is prevented.
  • the aging device 50 may supply super-humidified N2 gas in which the N2 gas is in a super-humidified state in the N2 purge.
  • CV aging voltage fluctuation aging
  • step S3 uses the aging device 50 used in the UFB aging described above, or uses a CV aging device (not shown). Varying voltage is applied to This CV aging removes the film oxidized on the surface of the catalyst, removes organic contaminants adhering to the catalyst, etc., and increases the catalyst effective area of the MEA 18 . As a result, the reaction of H 2 ⁇ 2H + +e ⁇ and the reaction of O 2 +4H + +4e ⁇ ⁇ 2H 2 O during power generation of the fuel cell 10 are promoted.
  • UFB aging is performed first, protons can easily move in the electrolyte membrane 22 during CV aging. Therefore, CV aging can shorten the implementation time.
  • step S4 the power generation performance of the fuel cell stack 12 (fuel cell 10) after CV aging is analyzed by an appropriate evaluation method.
  • the cell voltage and current during power generation are detected by performing power generation processing of the fuel cell stack 12 .
  • the concentration overvoltage of the IV curve is reduced and the activation overvoltage is also reduced. Therefore, the power generation performance of the fuel cell stack 12 is significantly improved.
  • the supply of UFB water (H 2 UFB water, N 2 UFB water) in UFB aging (concentration cell) causes movement of H 2 molecules in the anode electrode 24 and the cathode electrode 26.
  • properties (diffusibility) and wettability are improved.
  • the implementation of UFB aging increases the diffusion coefficient of protons in the MEA 18 , and accordingly increases the amount of electroosmotic water when protons move through the electrolyte membrane 22 . Therefore, the water content of the MEA 18 (electrolyte membrane 22) can be efficiently increased.
  • the aging device 50 is not limited to performing UFB aging on the fuel cell stack 12 having a plurality of fuel cells 10, but may be configured to perform UFB aging on the fuel cell 10, which is a unit power generation cell, by appropriately modifying it. There may be. Further, for example, in the aging method of the fuel cell 10, the CV aging (step S3) may be omitted when the power generation performance of the fuel cell 10 is sufficiently improved by performing the UFB aging.
  • the supply of UFB is not limited to when UFB aging is performed on the fuel cell 10, but can also be applied when the fuel cell stack 12 (fuel cell 10) generates power.
  • a fuel cell system (not shown) with fuel cell stack 12 or aging device 50 supplies H 2 UFB water containing H 2 UFB to anode electrode 24 while O 2 to cathode electrode 26 .
  • O 2 UFB water containing molecular UFB Provide O 2 UFB water containing molecular UFB.
  • the aging device 50 is provided with the H 2 gas sources 64, 74 and the N 2 gas sources 65, 75 in the first UFB generation section 62 and the second UFB generation section 72, respectively.
  • the H 2 gas sources 64, 74 and the N 2 gas sources 65, 75 may be shared.
  • 7, 8A and 8B exemplify modifications of the aging method in which O 2 UFB water is supplied, and H 2 gas sources 64, 74 and N 2 gas sources 65, 75 are shared. do.
  • the aging device 50A supplies selected fluids (H 2 UFB water, (N 2 UFB water, O 2 UFB water, humidified H 2 gas, humidified N 2 gas, humidified O 2 gas), and treats each fluid discharged from the fuel cell stack 12 . and a discharge processing unit 92 .
  • the supply processing unit 90 includes a first supply processing unit 94 that supplies O 2 (air in this modification) and N 2 , a second supply processing unit 96 that supplies H 2 , the fuel cell stack 12 and the first supply unit 94 . and a supply channel switching unit 98 that switches the fluid channel between the processing unit 94 and the second supply processing unit 96 .
  • the emission processing unit 92 includes a first emission processing unit 100 that processes O 2 and N 2 emissions, a second emission processing unit 102 that processes H 2 emissions, the fuel cell stack 12 and the first emission processing unit 100 . and a discharge channel switching unit 104 for switching the fluid channel between the second discharge processing unit 102 and the second discharge processing unit 102 .
  • a first circulation path 106 for circulating the fluid in the first discharge processing section 100 is connected between the first supply processing section 94 and the first discharge processing section 100 .
  • a second circulation path 108 for circulating the fluid in the second discharge processing section 102 is connected between the second supply processing section 96 and the second discharge processing section 102 .
  • the first supply processor 94 includes an air source 110, an air UFB generator 112, an air UFB tank 114, a bubbler tank 116, an N2 gas source 118, and an N2 UFB generator.
  • a part 120 and an N 2 UFB tank 122 are provided.
  • a water supply unit 124 is connected to each of the air UFB generation unit 112 , the bubbler tank 116 and the N 2 UFB generation unit 120 .
  • the air UFB generator 112 appropriately mixes air supplied from the air source 110 and water supplied from the water supply unit 124 to generate air UFB water.
  • the air UFB tank 114 stores the generated air UFB water and also stores the air UFB water circulated from the first discharge processing unit 100 .
  • the N 2 UFB generator 120 appropriately mixes the N 2 gas supplied from the N 2 gas source 118 and the water supplied from the water supply 124 to generate N 2 UFB water.
  • the N 2 UFB tank 122 stores the generated N 2 UFB water and stores the N 2 UFB water circulated from the first discharge processing unit 100 .
  • the bubbler tank 116 is connected to the air source 110, the N 2 gas source 118, and the water supply unit 124, and supplies air or N 2 gas to the water stored in the tank to bubble the humidified air. Or generate humidified N2 gas. Also, the bubbler tank 116 controls the temperature and humidity of the gas by adjusting the temperature with a temperature adjusting unit (not shown).
  • the first supply processor 94 selectively supplies the air from the air source 110 to the air UFB generator 112 and the bubbler tank 116, and the N2 gas from the N2 gas source 118 to the N2 UFB generator 120 and the bubbler tank. 116 with valves 126a, 126b, 126c, 126d for selectively feeding 116; Further, the first supply processing unit 94 has a pump 128a and a valve 130a between the air UFB tank 114 and the output terminal 94a of the first supply processing unit 94, and between the bubbler tank 116 and the output terminal 94a.
  • the first supply processing unit 94 has a path for supplying N 2 UFB water as a coolant to the fuel cell stack 12, and this path also has a pump 128d and a valve 130d.
  • the first supply processing unit 94 configured as described above supplies N 2 UFB water, O 2 UFB water, humidified N 2 gas, and humidified O 2 gas from the output terminal 94a to the downstream supply flow path switching unit. 98.
  • the second supply processing unit 96 includes an H 2 gas source 132, an H 2 UFB generation unit 134, an H 2 UFB tank 136, and an H 2 bubbler tank 138, as shown in FIG. 8B.
  • a water supply unit 124 is connected to each of the H 2 UFB generation unit 134 and the H 2 bubbler tank 138 .
  • the H 2 UFB generation unit 134 appropriately mixes the H 2 gas supplied from the H 2 gas source 132 and the water supplied from the water supply unit 124 to generate H 2 UFB water.
  • the H 2 UFB tank 136 stores the generated H 2 UFB water and also stores the H 2 UFB water circulated from the second discharge processing unit 102 .
  • the H 2 bubbler tank 138 is connected to the H 2 gas source 132 and the water supply unit 124, and supplies H 2 gas to the water stored in the tank to bubble it, thereby generating humidified H 2 gas. do.
  • the H2 bubbler tank 138 also controls the temperature and humidity of the gas by adjusting the temperature with a temperature control unit (not shown).
  • the second supply processing unit 96 has valves 140a and 140b for selectively supplying the H2 gas from the H2 gas source 132 to the H2UFB generation unit 134 and the H2 bubbler tank 138, and further H2UFB .
  • a pump 142a and a valve 144a are provided between the fuel tank 136 and the output terminal 96a of the second supply processing section 96, and a pump 142b and a valve 144b are provided between the H2 bubbler tank 138 and the output terminal 96a.
  • the second supply processing section 96 configured as described above can output the H 2 UFB water and the humidified H 2 gas from the output terminal 96 a to the downstream supply channel switching section 98 .
  • the supply channel switching unit 98 includes a plurality of pipes 150 between the first supply processing unit 94 and the fuel cell stack 12 and between the second supply processing unit 96 and the fuel cell stack 12 . Further, each of the plurality of pipes 150 is provided with a plurality of valves 152 (valves 152a, 152b, 152c, 152d). The supply channel switching unit 98 configured in this way supplies the fluid of the first supply processing unit 94 to one of the anode electrode 24 and the cathode electrode 26 under the switching of the plurality of valves 152, while supplying the anode electrode 24 and the cathode electrode 26 with the fluid. The fluid of the second supply processing section 96 is supplied to the other of the cathode electrodes 26 .
  • the discharge channel switching unit 104 includes a plurality of pipes 160 between the first discharge processing unit 100 and the fuel cell stack 12 and between the second discharge processing unit 102 and the fuel cell stack 12 . Further, each of the plurality of pipes 160 is provided with a plurality of valves 162 (valves 162a, 162b, 162c, 162d). The discharge channel switching unit 104 configured in this way discharges the fluid from one of the anode electrode 24 and the cathode electrode 26 to the first discharge processing unit 100 under the switching of the plurality of valves 162, and The fluid is discharged from the other cathode electrode 26 to the second discharge processing section 102 .
  • the first discharge treatment unit 100 has a first recovery tank 170 that recovers N 2 UFB water, O 2 UFB water, N 2 gas, and O 2 gas. Also, the first circulation path 106 is connected between the input terminal 100 a of the first discharge processing section 100 and the first recovery tank 170 . A valve 172 a is provided between the input terminal 100 a and the first collection tank 170 , and a valve 172 b is also provided in the first circulation path 106 .
  • the first discharge processing unit 100 configured as described above discharges the N 2 UFB water, the O 2 UFB water, the N 2 gas, and the O 2 gas to the first recovery tank 170 by switching the valves 172a and 172b. , and the first circulation path 106 .
  • the second discharge treatment unit 102 has a second recovery tank 174 for recovering H2UFB water and H2 gas.
  • the second circulation path 108 is connected between the input terminal 102 a of the second discharge processing section 102 and the second recovery tank 174 .
  • a valve 176 a is provided between the input terminal 102 a and the second collection tank 174
  • a valve 176 b is also provided in the second circulation path 108 .
  • the second discharge processing unit 102 configured in this way discharges the H 2 UFB water and H 2 gas to the second recovery tank 174 under switching of the valves 176a and 176b, and circulates them through the second circulation path 108. can be made
  • the aging apparatus 50A configured as described above supplies H 2 UFB water to the anode electrode 24, supplies N 2 UFB water to the cathode electrode 26, and applies a potential by the voltage applying unit 80 (see FIG. 1).
  • the first pattern described above can be implemented.
  • the aging device 50A supplies N 2 UFB water to the anode electrode 24, supplies H 2 UFB water to the cathode electrode 26, and applies a potential by the voltage application unit 80, thereby executing the second pattern. can be done.
  • the above-described purge control and N2 supply control are performed by appropriately switching the pipes 150 and 160 by the supply channel switching unit 98 and the discharge channel switching unit 104. be able to.
  • the first supply processing unit 94 can easily supply humidified N2 gas to the fuel cell stack 12 in N2 supply control.
  • the aging device 50A supplies H 2 UFB water to the anode electrode 24 and O 2 UFB water to the cathode electrode 26 so that the fuel cell stack 12 can generate power.
  • the aging device 50A can supply O 2 UFB water to the anode electrode 24 and H 2 UFB water to the cathode electrode 26 to generate power in the fuel cell stack 12 .
  • the power generation of the fuel cell stack 12 may be performed by combining the first pattern and the second pattern during UFB aging, or may be performed after UFB aging.
  • the separators (the first separator 20a and the second separator 20b) that constitute the fuel cell 10 are configured to prevent gas and liquid from leaking from the flow path to the outside between adjacent separators.
  • a seal (not shown) may be provided to prevent this.
  • the water repellent substance such as siloxane may scatter and adhere to the surface facing the power generation portion. Therefore, it is preferable to wash the separator with UFB water when manufacturing the separator (before or during the UFB aging treatment). As a result, the UFB water enters into minute gaps in the separator, and the water-repellent substance adhered during manufacturing can be removed.
  • the hydrophilicity of the surface of the separator can be increased by washing with UFB water, and by configuring the fuel cell 10 with this separator, it is expected that the aging time of the fuel cell 10 will be shortened or the variation in cell voltage will be improved. can do.
  • the fuel cell 10 aging method according to the second embodiment utilizes the principle of a hydrogen pump to pass protons (H + ) through the MEA 18 during UFB aging.
  • a direct-current power supply connected to the fuel cell 10 forms an electron flow, thereby moving protons in the direction in which more electrons exist within the MEA 18 . That is, it is a method of moving (pumping) protons by electric current.
  • the same device as the aging device 50 according to the first embodiment can also be applied to UFB aging using the principle of this hydrogen pump.
  • the control unit 54 of the aging device 50 controls the operations of the first circulation unit 60, the second circulation unit 70, and the voltage application unit 80, thereby performing As shown, two patterns are implemented.
  • the anode electrode 24 is supplied with H 2 UFB water and a positive potential is applied, while the cathode electrode 26 is supplied with N 2 UFB water and compared with the other electrodes.
  • the second pattern shown in FIG. 9B supplies N 2 UFB water to the anode electrode 24 and applies a negative potential compared to the other electrodes, while supplying H 2 UFB water to the cathode electrode 26, This is a reverse supply application pattern for applying a positive potential.
  • the control unit 54 can perform the first pattern or the second pattern independently, or alternately perform the first pattern and the second pattern every predetermined period. can be done.
  • the aging device 50 uses an electronic load unit (not shown) instead of the voltage application unit 80 to apply current to either the anode or the cathode (or alternately). By doing so, it is possible to apply a potential difference similar to that of the voltage applying section 80 .
  • the aging device 50 supplies H 2 UFB water to the anode flow channel 30 and the anode electrode 24 through the first circulation part 60, and supplies H 2 UFB water to the cathode flow channel 32 through the second circulation part 70. and N 2 UFB water to the cathode electrode 26 .
  • H 2 UFB moves to the catalyst layer 24a through the gas diffusion layer 24c and the dense carbon layer 24b due to the hydraulic pressure (water flow) of the H 2 UFB water at the anode electrode 24, and bursts at the catalyst layer 24a to produce H 2 molecules. becomes.
  • control unit 54 controls the pressure on the anode electrode 24 side to be higher than the pressure on the cathode electrode 26 side, thereby facilitating movement of the H 2 UFB toward the catalyst layer 24a.
  • the H 2 molecule then reacts with the platinum catalyst and ionizes into protons (H + ) and electrons (e ⁇ ).
  • the voltage application section 80 applies a positive potential to the anode electrode 24 and a negative potential to the cathode electrode 26 compared to the other electrodes.
  • the ionized electrons move to the first separator 20 a of the anode electrode 24 and move to the second separator 20 b of the cathode electrode 26 via the harness 56 and the voltage applying section 80 .
  • the cathode electrode 26 attracts protons as more electrons move. Therefore, the protons in the catalyst layer 24a of the anode electrode 24 move inside the MEA 18 along with the electroosmotic water.
  • the protons and electrons that have moved to the catalyst layer 26a of the cathode electrode 26 react with the platinum catalyst to form H 2 molecules, and these H 2 molecules are discharged from the fuel cell 10 together with N 2 UFB water.
  • the aging device 50 reverses the supply target electrode of UFB water (H 2 UFB water, N 2 UFB water) from the first pattern, and also switches the voltage application target electrode to the first pattern. Reverse the pattern.
  • UFB water H 2 UFB water, N 2 UFB water
  • the fuel cell 10 moves protons from the cathode electrode 26 toward the anode electrode 24 via the electrolyte membrane 22, and humidification with electroosmotic water can be performed from the cathode electrode 26 side ( A detailed description of the action of the fuel cell 10 is omitted).
  • the aging method of the fuel cell 10 can obtain the same effects as in the first embodiment even with UFB aging using the principle of a hydrogen pump. That is, in this aging method, the diffusion coefficient of protons in the MEA 18 increases, and the amount of electroosmotic water accompanying the proton transfer also increases, so that the water content of the MEA 18 (electrolyte membrane 22) can be efficiently increased.
  • UFB aging using the principle of a hydrogen pump can further increase proton transfer efficiency by transferring electrons by applying a DC voltage.
  • the aging method for the fuel cell 10 according to the third embodiment is configured such that CV aging is performed simultaneously with UFB aging. different from the aging method of Note that the same aging device 50 as in the first and second embodiments can be applied to the aging device 50 that performs UFB aging.
  • step S11 UFB+CV aging
  • step S12 N2 purge
  • step S13 CV aging
  • step S14 performance evaluation
  • the control unit 54 varies the voltage applied to the anode electrode 24 and the cathode electrode 26 by the voltage application unit 80 while performing UFB aging using the principle of a concentration cell or hydrogen pump.
  • the fuel cell 10 subjected to UFB+CV aging has an increased water content in the electrolyte membrane 22 and an improved catalyst effective area.
  • the aging method can further shorten the implementation time in CV aging (step S13) after N2 purge (step S12). Even if UFB+CV aging is performed in this way and the CV aging is shortened, the power generation performance of the fuel cell stack 12 can be significantly improved.
  • CV aging may of course be omitted if the power generation performance of the fuel cell 10 is sufficiently enhanced by performing UFB+CV aging. .
  • One aspect of the present invention is a method for aging a fuel cell 10 having an electrolyte membrane 22 and a pair of electrodes (an anode electrode 24 and a cathode electrode 26) provided on both sides of the electrolyte membrane 22, wherein Hydrogen ultra-fine bubble water (H 2 UFB water) containing hydrogen as ultra-fine bubbles (UFB) is supplied to one electrode of the fuel cell 10, and protons are transferred from one electrode to the other electrode through the electrolyte membrane 22. Carry out moving ultra-fine bubble aging.
  • Hydrogen ultra-fine bubble water H 2 UFB water
  • UFB ultra-fine bubbles
  • the aging method of the fuel cell 10 can favorably move the H 2 UFB water supplied to the fuel cell 10 to the catalyst layer 24a (or the catalyst layer 26a) of one electrode.
  • protons ionized from hydrogen in the catalyst layer 24a (or catalyst layer 26a) move through the electrolyte membrane 22 with the electroosmotic water, thereby further promoting humidification of the electrolyte membrane 22. That is, ultra-fine bubble aging using H 2 UFB water can improve the efficiency of aging of the fuel cell 10 .
  • CV aging voltage variation aging
  • a voltage that varies in a predetermined voltage width is applied to a pair of electrodes (anode electrode 24 and cathode electrode 26).
  • CV aging can be performed on the fuel cell 10 whose gas diffusibility has been enhanced by humidification of the electrolyte membrane 22, and the catalyst effective area can be secured in a short time by this CV aging. becomes possible.
  • ultra-fine bubble aging hydrogen ultra-fine bubbled water is supplied to the anode electrode 24, which is a pair of electrodes, and a negative potential is applied compared to the other electrode, while the cathode electrode 26, which is a pair of electrodes, is supplied with hydrogen ultra-fine bubble water.
  • a supply application pattern of supplying nitrogen ultra-fine bubble water having nitrogen as ultra-fine bubbles and applying a positive potential can move protons between electrodes using the principle of a concentration cell, and can perform UFB aging well.
  • the supply application pattern and the anode electrode 24 are supplied with nitrogen ultra-fine bubble water and a positive potential is applied, while the cathode electrode 26 is supplied with hydrogen ultra-fine bubble water. , and a reverse supply application pattern in which a negative potential is applied compared to the other electrodes, are alternately performed.
  • the electrolyte membrane 22 can be humidified from both the anode electrode 24 and the cathode electrode 26, and the UFB aging can be made more efficient.
  • hydrogen ultra-fine bubble water is supplied to the anode electrode 24, which is a pair of electrodes
  • oxygen ultra-fine bubble water containing oxygen as ultra-fine bubbles is supplied to the cathode electrode 26, which is a pair of electrodes, to generate power. conduct.
  • hydrogen ultra-fine bubbled water is supplied to the anode electrode 24, which is a pair of electrodes, and a positive potential is applied, and nitrogen ultra-fine bubbled water having nitrogen as ultra-fine bubbles is applied to the cathode electrode 26, which is a pair of electrodes. is supplied, and a supply application pattern is performed in which a negative potential is applied compared to the other electrodes.
  • the aging method of the fuel cell 10 makes it possible to move protons between the electrodes using the principle of a hydrogen pump, so that UFB aging can be performed satisfactorily.
  • the supply application pattern and the nitrogen ultra-fine bubble water are supplied to the anode electrode 24, a negative potential is applied compared to the other electrodes, and the hydrogen ultra-fine bubble water is applied to the cathode electrode 26.
  • a reverse supply application pattern in which the voltage is supplied and a positive potential is applied is alternately performed. Even when the principle of the hydrogen pump is used in this way, the electrolyte membrane 22 can be humidified from both the anode electrode 24 and the cathode electrode 26, and the UFB aging can be made more efficient.
  • the pressure on the side supplying the hydrogen ultra-fine bubbled water is made higher than the pressure on the side supplying the nitrogen ultra-fine bubbled water. This allows UFB aging to more efficiently transfer the H 2 UFB to the catalyst layers 24a, 26a within the electrodes.
  • the pressure on the side supplying the hydrogen ultra-fine bubbled water is lowered, thereby reducing the pressure difference from the pressure on the side supplying the nitrogen ultra-fine bubbled water.
  • the aging method of the fuel cell 10 can suppress an overload or the like on the electrolyte membrane 22 due to a sudden change in pressure at the end of the supply application pattern or the reverse supply application pattern.
  • the aging method of the fuel cell 10 can easily discharge the hydrogen remaining in the electrodes.
  • the applied voltage is varied within a predetermined voltage width.
  • the aging method of the fuel cell 10 can be performed together with the UFB aging and the CV aging, thereby further shortening the aging time.
  • the hydrogen ultra-fine bubbled water is drained.
  • the aging method of the fuel cell 10 can sufficiently use up the hydrogen ultra-fine bubbles, thereby suppressing the consumption of hydrogen.
  • the fuel cell 10 has a pair of separators (a first separator 20a and a second separator 20b) installed on each of the electrode surfaces of the pair of electrodes, and the separators are separated before or during the ultrafine bubble aging treatment. with ultra-fine bubble water.
  • the hydrophilicity of the surface of the separator can be increased, and by constructing the fuel cell 10 with this separator, it is expected that the aging time of the fuel cell 10 will be shortened or the variation in cell voltage will be improved.

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Abstract

Une pile à combustible (10) selon l'invention comprend : une membrane électrolytique (22) ; et une électrode anodique (24) et une électrode cathodique (26), qui sont disposées sur les deux surfaces de la membrane électrolytique (22). Dans ce procédé de vieillissement de la pile à combustible (10), une eau à bulles ultrafines d'hydrogène (eau UFB H2), qui contient des bulles ultrafines d'hydrogène (H2) divisible en un proton (H+), est fournie à l'une des électrodes de la pile à combustible (10). Par conséquent, ce procédé de vieillissement de la pile à combustible (10) réalise un vieillissement par bulles ultrafines, des protons (H+) étant transférés de l'une des électrodes à l'autre des électrodes à travers la membrane électrolytique (22).
PCT/JP2021/012827 2021-03-26 2021-03-26 Procédé de vieillissement d'une pile à combustible WO2022201484A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH087905A (ja) * 1994-06-16 1996-01-12 British Gas Plc 燃料セルを動作する方法
JP2006331968A (ja) * 2005-05-30 2006-12-07 Equos Research Co Ltd 燃料電池装置
JP2008059960A (ja) * 2006-09-01 2008-03-13 Toyota Motor Corp 固体高分子型燃料電池及び固体高分子型燃料電池の活性化方法
WO2011125840A1 (fr) * 2010-03-31 2011-10-13 本田技研工業株式会社 Procédé d'activation de pile à combustible à polymères solides
JP2015201379A (ja) * 2014-04-09 2015-11-12 トヨタ自動車株式会社 燃料電池の検査方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH087905A (ja) * 1994-06-16 1996-01-12 British Gas Plc 燃料セルを動作する方法
JP2006331968A (ja) * 2005-05-30 2006-12-07 Equos Research Co Ltd 燃料電池装置
JP2008059960A (ja) * 2006-09-01 2008-03-13 Toyota Motor Corp 固体高分子型燃料電池及び固体高分子型燃料電池の活性化方法
WO2011125840A1 (fr) * 2010-03-31 2011-10-13 本田技研工業株式会社 Procédé d'activation de pile à combustible à polymères solides
JP2015201379A (ja) * 2014-04-09 2015-11-12 トヨタ自動車株式会社 燃料電池の検査方法

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