CN113994510B - Fuel cell system, nuclear fusion power generation system, and sealed container constituting the same - Google Patents
Fuel cell system, nuclear fusion power generation system, and sealed container constituting the same Download PDFInfo
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- CN113994510B CN113994510B CN202080041991.1A CN202080041991A CN113994510B CN 113994510 B CN113994510 B CN 113994510B CN 202080041991 A CN202080041991 A CN 202080041991A CN 113994510 B CN113994510 B CN 113994510B
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- 239000000446 fuel Substances 0.000 title claims abstract description 185
- 230000004927 fusion Effects 0.000 title claims description 19
- 238000010248 power generation Methods 0.000 title claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 77
- 239000011521 glass Substances 0.000 claims abstract description 46
- 239000002184 metal Substances 0.000 claims abstract description 32
- 229910052751 metal Inorganic materials 0.000 claims abstract description 32
- 239000002131 composite material Substances 0.000 claims abstract description 30
- 238000010304 firing Methods 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000002093 peripheral effect Effects 0.000 claims description 74
- 239000007784 solid electrolyte Substances 0.000 claims description 49
- 239000003566 sealing material Substances 0.000 claims description 36
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 239000000919 ceramic Substances 0.000 claims description 10
- -1 oxygen ions Chemical class 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 56
- 239000001257 hydrogen Substances 0.000 abstract description 56
- 238000005259 measurement Methods 0.000 description 40
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 18
- 229910052805 deuterium Inorganic materials 0.000 description 17
- 239000007789 gas Substances 0.000 description 14
- 230000004048 modification Effects 0.000 description 13
- 238000012986 modification Methods 0.000 description 13
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 229910052722 tritium Inorganic materials 0.000 description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 230000008859 change Effects 0.000 description 7
- 230000005764 inhibitory process Effects 0.000 description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 6
- 230000001012 protector Effects 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000005253 cladding Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000012466 permeate Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002737 fuel gas Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000010583 slow cooling Methods 0.000 description 3
- 230000001629 suppression Effects 0.000 description 3
- 229910000859 α-Fe Inorganic materials 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
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- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011819 refractory material Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
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- 230000000712 assembly Effects 0.000 description 1
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- 238000001354 calcination Methods 0.000 description 1
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- 230000006835 compression Effects 0.000 description 1
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- 239000000835 fiber Substances 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910000734 martensite Inorganic materials 0.000 description 1
- 229910001105 martensitic stainless steel Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
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- 239000000546 pharmaceutical excipient Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
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Classifications
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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
- H01M8/02—Details
- H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
- H01M8/0273—Sealing or supporting means around electrodes, matrices or membranes with sealing or supporting means in the form of a frame
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/10—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with metals
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/10—Oxidising
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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
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0206—Metals or alloys
-
- 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
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0206—Metals or alloys
- H01M8/0208—Alloys
-
- 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
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0215—Glass; Ceramic materials
-
- 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
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0223—Composites
- H01M8/0228—Composites in the form of layered or coated products
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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
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0232—Metals or alloys
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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
- H01M8/02—Details
- H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
-
- 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
- H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
- H01M8/028—Sealing means characterised by their material
- H01M8/0282—Inorganic material
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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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04007—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids related to heat exchange
- H01M8/04037—Electrical heating
-
- 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
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
- H01M8/065—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants by dissolution of metals or alloys; by dehydriding metallic substances
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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
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
- H01M8/0656—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants by electrochemical means
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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
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
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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
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/1213—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E30/00—Energy generation of nuclear origin
- Y02E30/10—Nuclear fusion reactors
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Fuel Cell (AREA)
- Composite Materials (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
Abstract
The invention provides a fuel cell system capable of stably supplying electric power for a long period of time. The fuel cell system 10 includes a flat plate-like electrode composite 20, a negative electrode fuel object 30, and a closed vessel 40. The flat plate-like electrode assembly 20 includes a fuel electrode 22 that oxidizes hydrogen to water vapor during discharge. The anode fuel object 30 reacts with water vapor to produce hydrogen gas and itself becomes oxide. The closed vessel 40 includes an inner space 42 for hermetically receiving the anode fuel object 30. The electrode assembly 20 and the anode fuel object 30 are insulated at respective predetermined temperatures. The closed vessel 40 is made of metal and includes a glass film 50 in addition to an oxide layer 48. The oxide layer 48 is formed on the surface of the wall of the closed casing 40 by air firing. Among the oxide layers 48, the glass film 50 covers the oxide layer 48 formed on at least one of the outer surface and the inner surface of the wall of the closed vessel 40.
Description
Technical Field
The present invention relates to a fuel cell system used as a power source for stationary vehicles, automobiles, and the like, and more particularly, to a solid oxide fuel cell system that regenerates fuel gas in the system using iron powder.
Background
A fuel cell is a device that generates electric power in a generator by supplying fuel gas. Among fuel cells, a solid oxide fuel cell (SOFC, solid Oxide Fuel Cell) using an inorganic solid electrolyte having oxygen ion conductivity is known to be a clean and excellent power generation device having high power generation efficiency. In addition, a fuel cell system having a mechanism for recovering the consumed fuel gas by the discharge of the fuel cell and serving as a secondary battery has been developed.
Patent document 1 describes a solid oxide fuel cell system having a simple and compact structure with a sufficiently large cell capacity and energy density. However, this fuel cell system has a problem of energy loss due to permeation of hydrogen into the closed container, and a problem of damage to the solid oxide fuel cell due to a decrease in the internal pressure of the closed container. As one of techniques for solving this problem, patent document 2 describes a technique for solving the problem that hydrogen released from the reformer and the cell stack permeates through the wall of the vacuum insulation structure and permeates into the inside, and the internal pressure increases, so that the insulation performance decreases.
[ related literature ]
Patent document 1: WO2017/135451
Patent document 2: japanese invention No. 4359079
Disclosure of Invention
Technical problem of the invention
Patent document 2 describes that glass generally has a lower hydrogen permeability than metal, and therefore, when a confirmation experiment is performed, hydrogen permeation inhibition performance in a predetermined target range cannot be achieved, and there is a problem that stable power supply cannot be performed for a long period of time.
The present invention has been made in view of the above problems, and an object of the present invention is to provide a fuel cell system capable of stably supplying electric power for a long period of time.
Further, in addition to the above object, another object of the present invention is to provide a fuel cell system capable of continuously supplying electric power for a period of time above conventional and flexibly constructing an aggregate of fuel cell systems.
Further, in addition to the above object, it is still another object of the present invention to provide a closed container capable of suppressing leakage of hydrogen isotopes due to permeation.
The technical proposal of the invention
The present inventors have made intensive studies to achieve the above object, and as a result, first, in a fuel cell system including a flat plate-like electrode composite, a negative electrode fuel object, and a sealed container made of metal, hydrogen permeation inhibition performance is improved by covering a glass film on an oxide layer formed on at least one of an outer surface and an inner surface of the sealed container.
Further, the present inventors have completed the present invention by providing an oxide layer formed by air calcination between the surface of a closed container and a glass film, and thereby stably supplying electric power for a long period of time.
That is, in the 1 st aspect of the present invention, the fuel cell system includes a flat plate-like electrode composite including a fuel electrode for oxidizing hydrogen gas into water vapor at the time of discharge, a negative electrode fuel object for reacting with water vapor to generate hydrogen gas and itself becoming oxide, and an internal space for hermetically housing the negative electrode fuel object, a portion of a wall constituting the internal space includes an opening portion for bringing hydrogen gas in the internal space into contact with a surface of the fuel electrode, and a closed container for hermetically fixing the electrode composite to block an outer peripheral portion of the opening portion, the electrode composite and the negative electrode fuel object are insulated at respective predetermined temperatures, the closed container is made of metal, and a glass film covers an oxide layer formed on at least one surface of an outer surface and an inner surface of a wall of the closed container in the oxide layer while a surface of the wall of the closed container includes an oxide layer formed by air firing.
Here, in the above-described aspect, the electrode assembly further includes a plate-shaped airtight solid electrolyte body which is provided on one surface of the fuel electrode and which conducts oxygen ions during charge and discharge, the solid electrolyte body being made of ceramic, and the closed vessel being preferably made of a metal having a thermal expansion coefficient of 0.8 to 2.0 times that of the solid electrolyte body.
The outer peripheral portion includes an outer peripheral base portion for supporting an outer peripheral portion of the solid electrolyte body surface provided with the fuel electrode, and an outer peripheral wall portion covering an end face of the solid electrolyte body, and is preferably fixed to the end face of the solid electrolyte body using a sealing material.
The outer peripheral portion includes an outer peripheral base portion for supporting the outer peripheral portion of the surface of the fuel electrode on the opposite side of the solid electrolyte, and an outer peripheral wall portion covering the end face of the fuel electrode, and is preferably fixed to the end face of the fuel electrode using a sealing material.
The electrode assembly further includes an air electrode provided on a surface of the solid electrolyte body on the opposite side of the fuel electrode and reducing oxygen in the air to oxygen ions upon discharge, and the outer peripheral portion includes an outer peripheral base portion supporting the outer peripheral portion of the surface of the solid electrolyte body on which the fuel electrode is provided, and an outer peripheral wall portion covering an end face of the solid electrolyte body and an end face of the air electrode, and the outer peripheral wall portion is preferably fixed to the end face of the solid electrolyte body and the end face of the air electrode using a sealing material.
The electrode composite further includes a porous metal plate provided on the surface of the fuel electrode on the opposite side of the solid electrolyte body and permeated with hydrogen gas during charge and discharge, and the outer peripheral portion includes an outer peripheral base portion for supporting the outer peripheral portion of the surface of the fuel electrode on the porous metal plate and an outer peripheral wall portion covering the end face of the porous metal plate, the outer peripheral wall portion being preferably fixed to the end face of the porous metal plate using a sealing material.
The closed container is preferably made of SUS430, and the oxide layer is preferably formed by air firing the closed container at 680-1020 ℃ for 58-86 hours and then slowly cooling.
The closed vessel is preferably made of SUS430, and the oxide layer preferably includes an outer layer rich in Fe and an inner layer rich in Cr.
The thickness of the oxide layer is preferably 10nm to 10. Mu.m.
The glass film is preferably a crystallized glass film.
The predetermined temperature of the electrode composite is preferably 450 to 1000 c, and the predetermined temperature of the anode fuel body is preferably 300 to 1000 c.
Further, it is preferable to include a heater provided on at least one of the outside and the inside of the case formed of the closed container and the electrode composite and for insulating the electrode composite and the anode fuel object.
Further, in the 2 nd aspect of the present invention, a closed container includes an outer wall provided with an inner space for hermetically receiving hydrogen gas, the outer wall being a metal product insulated at a predetermined temperature, the surface of the outer wall including an oxide layer formed by air firing, and in the oxide layer, a glass film covers an oxide layer formed on at least one of the outer surface and the inner surface of the outer wall.
In the above-mentioned embodiments, the outer wall is preferably made of SUS430, and the oxide layer is preferably formed by air-firing the outer wall at 680 to 1020 ℃ for 58 to 86 hours and then slowly cooling the outer wall.
The outer wall is preferably made of SUS430, and the oxide layer preferably includes an outer layer rich in Fe and an inner layer rich in Cr.
The thickness of the oxide layer is preferably 10nm to 10. Mu.m.
The glass film is preferably a crystallized glass film.
The predetermined temperature of the outer wall is preferably 550 to 750 ℃.
Further, the 3 rd aspect of the present invention is a fuel cell system comprising the sealed container of the 2 nd aspect of the present invention.
Further, the 4 th aspect of the present invention is a nuclear fusion power generation system including the 2 nd aspect of the present invention.
Technical effects of the invention
According to aspects 1, 2 and 4 of the present invention, electric power can be stably supplied for a long period of time.
Further, according to aspects 1, 2 and 4 of the present invention, in addition to the above-described effects, electric power is continuously supplied for a specific period of time equal to or longer than a conventional time, and the aggregate of the fuel cell system can be flexibly constructed.
Further, according to the 2 nd aspect of the present invention, leakage of hydrogen isotopes due to permeation can be suppressed.
Drawings
Fig. 1 is a schematic front view of a fuel cell system according to the present invention.
Fig. 2 is a schematic cross-sectional view of a closed container of the fuel cell system of fig. 1.
Fig. 3 is a graph showing the relationship between the internal pressure of the closed vessel and the elapsed time.
Fig. 4 is a schematic front view of a modification 1 of the fuel cell system of fig. 1.
Fig. 5 is a schematic front view of a modification 2 of the fuel cell system of fig. 4.
Fig. 6 is a schematic front view of a modification 3 of the fuel cell system of fig. 4.
Fig. 7 is a schematic front view of a modification 4 of the fuel cell system of fig. 4.
Fig. 8 is a schematic front view of the hydrogen permeation quantity measuring device.
Fig. 9 is a schematic front view of a hydrogen isotope permeation quantity measurement apparatus.
Detailed Description
Hereinafter, the fuel cell system of the 1 st aspect of the invention will be described in detail based on the preferred embodiments shown in the drawings. Fig. 1 is a schematic front view of a fuel cell system according to the present invention, and fig. 2 is a schematic cross-sectional view of a closed container of the fuel cell system of fig. 1.
The fuel cell system 10 of the present invention includes a plate-like electrode composite 20, a negative electrode fuel object 30, and a closed vessel 40. The plate-like electrode assembly 20 includes a fuel electrode 22 (also referred to as a negative electrode or anode layer) that oxidizes hydrogen to water vapor during discharge. The anode fuel object 30 reacts with water vapor to produce hydrogen gas and itself becomes oxide. The closed casing 40 includes an inner space 42, an opening 44, and an outer peripheral portion 46. The internal space 42 hermetically accommodates the anode fuel object 30. The opening 44 is provided in a part of the wall constituting the internal space 42 for bringing the hydrogen gas in the internal space 42 into contact with the surface of the fuel electrode 22. The outer peripheral portion 46 is provided at a part of the wall constituting the internal space 42 and hermetically fixes the electrode assembly 20 to block the opening 44. The electrode composite 20 and the anode fuel object 30 are insulated (heated and kept at temperatures) at respective predetermined temperatures. The closed vessel 40 is made of metal and includes a glass film 50 in addition to an oxide layer 48. The oxide layer 48 is formed on the surface of the wall of the closed casing 40 by air firing. Among the oxide layers 48, the glass film 50 covers the oxide layer 48 formed on at least one of the outer surface and the inner surface of the wall of the closed vessel 40. The predetermined temperature is a predetermined temperature, and the air firing is performed in an air atmosphere without using a special gas.
With such a configuration, the fuel cell system 10 according to the present invention can achieve hydrogen permeation inhibition performance within a predetermined target range, and can stably supply electric power for a long period of time.
Next, the preset target value will be described in detail. Fig. 3 is a graph showing the relationship between the internal pressure of the closed vessel and the elapsed time.
If pressurized hydrogen gas is filled in advance in a closed container, the internal pressure may decrease due to hydrogen permeation with the lapse of time. When the rate of decrease of the internal pressure is slow (straight line LS), the hydrogen fuel is supplied to the fuel electrode for a long period of time, so that the electric power can be stably supplied for a long period of time. In contrast, when the falling speed of the internal pressure is rapid (straight line HS), the hydrogen fuel becomes insufficient in a short time, thereby shortening the period in which electric power can be supplied. Therefore, the target range in which the electric power is supplied for a sufficiently long period is set so that the internal pressure falls at a rate of 10Pa/H or less.
On the other hand, it has been found that the above-described evaluation of the internal pressure drop rate has the following problems. That is, first, the time required from the start to the end of the evaluation, and second, the temperature and the internal pressure in the closed container often fluctuate due to the change in the room temperature, so that the falling speed of the internal pressure is positively affected by the fluctuation. To solve these problems, we decided to use another measurement apparatus to compare the permeation coefficients of deuterium gas and set the target range to 1.00E-13 or less.
The predetermined temperature of the electrode assembly 20 constituting the fuel cell system 10 of the present invention may be 450 to 1000 c and the predetermined temperature of the anode fuel object 30 may be 300 to 1000 c. That is, if the temperature of the electrode composite 20 is lower than 450 ℃ or the temperature of the anode fuel object 30 is lower than 300 ℃, the fuel cell system 10 may not be operated. When the temperature of the electrode composite 20 exceeds 1000 ℃ or the temperature of the anode fuel object 30 exceeds 1000 ℃, the output may be reduced with the aggregation of the anode fuel object 30. The predetermined temperature of the wall of the closed vessel 40 is preferably 550 to 750 ℃. When the temperature of the wall of the closed vessel 40 is lower than 550 c or higher than 750 c, the hydrogen permeation suppression performance may be deteriorated.
With such a configuration, the fuel cell system 10 of the present invention satisfies the temperature conditions required for stable operation, and can continuously supply electric power for a certain period of time.
The shape of the electrode assembly 20 constituting the fuel cell system 10 of the present invention is not particularly limited, and may be a cylinder or a rectangular parallelepiped, and a rectangular parallelepiped is preferable in view of space efficiency. In addition, the size and color of the electrode assembly 20 are not particularly limited.
The anode fuel object 30 constituting the fuel cell system 10 of the present invention is not particularly limited as long as it reacts with water vapor to generate hydrogen gas and forms itself into an oxide, and is preferably an object in which iron particles or iron powder and a excipient form pellet shapes. The shaping material is composed of a refractory material or a mixture thereof. The refractory material is, for example, alumina, silica, magnesia, zirconia. At least a part of the surface of the anode fuel object 30 is covered with a molding material, and the mass ratio of the molding material to the anode fuel object 30 is 0.1% or more and 5% or less. If the mass ratio is less than 0.1%, the surface of the anode fuel object 30 may be sintered without undergoing a redox reaction, and if it exceeds 5%, it may result in excessive suppression of the redox rate. The diameter of the pellets is, for example, 2 to 10mm.
The shape of the closed vessel 40 constituting the fuel cell system 10 of the present invention is not particularly limited, and may be a cylinder or a hollow rectangular parallelepiped, and a rectangular parallelepiped is preferable in view of space efficiency. In addition, the size and color of the closed vessel 40 are not particularly limited.
The fuel cell system 10 of the present invention may also include a heater 60. In this case, the heater 60 is provided on at least one of the outside and the inside of the case formed by the closed casing 40 and the electrode composite body 20 for insulating the electrode composite body 20 and the anode fuel object 30. That is, as long as the electrode composite 20 and the anode fuel object 30 can be insulated, one heater that is compatible with other devices may be provided in combination, and even in the case where a dedicated heater is provided for the fuel cell system 10 of the present invention, one heater may be provided in combination in a plurality of fuel cell systems 10, preferably, as in the heater 60, a heater is provided separately in each fuel cell system 10. When the electric heater is disposed inside the case constituted by the closed vessel 40 and the electrode complex 20, in order to prevent the wiring of the electric heater from being short-circuited, to maintain the air tightness of the case, the wiring penetrates through a portion of the wall of the case, for example, conax seal land (Conax sealing grands) manufactured by IBP Technology co., ltd.
With such a configuration, modularization can be achieved, so that the fuel cell system 10 of the present invention can flexibly construct an aggregate of the fuel cell systems.
The electrode assembly 20 constituting the fuel cell system 10 of the present invention may further include a plate-like airtight solid electrolyte body 24. In this case, the solid electrolyte body 24 is provided on one surface of the fuel electrode 22, and conducts oxygen ions at the time of charge and discharge. Also, the solid electrolyte body 24 may be made of ceramic. The electrode assembly 20 comprising the fuel cell system 10 of the present invention may also include air electrodes 26 (also referred to as positive and cathode layers). In this case, the air electrode 26 is provided on the surface of the solid electrolyte body 24 on the opposite side of the fuel electrode 22, and reduces oxygen in the air to oxygen ions during discharge.
Next, the material of the sealed container will be specifically described.
The sealed container 40 may be made of a metal having a thermal expansion coefficient of 0.8 to 2.0 times that of the solid electrolyte body 24. That is, the ceramic used as the material of the solid electrolyte body 24 has a thermal expansion coefficient of about 100×10 -7 The coefficient of thermal expansion of the material of the sealed vessel 40 may be about (80-200). Times.10 -7 and/C. As a material corresponding to this case, for example, martensite (SUS) 403 and SUS410, ferrite-based SUS405 and SUS430. However, martensitic stainless steel is not suitable as a material for the closed vessel 40 because of its poor weldability. Therefore, ferrite-based SUS405 and SUS430 are preferable, and a thermal expansion coefficient close to 100X 10 is more preferable -7 SUS430 at/DEG C. In addition, the sealed container 40 may be formed by a plurality of different metal joints having very close coefficients of thermal expansion.
With this configuration, the fuel cell system 10 of the invention can prevent breakage of the sealing material described later due to temperature change and accompanying hydrogen leakage, so that electric power can be continuously supplied for a certain period.
Next, a surface treatment method of the sealed container will be specifically described.
The closed vessel 40 constituting the fuel cell system 10 of the present invention is not particularly limited as long as it is made of metal, and is preferably made of stainless steel, more preferably made of ferrite-based stainless steel, and still more preferably made of SUS430. In this case, the oxide layer 48 may be formed by being slowly cooled after air firing at 680 to 1020 ℃ for 58 to 86 hours, or may include an outer layer rich in Fe and an inner layer rich in Cr. The glass film 50 may be a crystallized glass film, preferably having a coefficient of thermal expansion of about (80-200) x 10 -7 Preferably, the crystallized glass film at a temperature of/. Degree.C is La as the main component 2 O 3 ，B 2 O 3 And/or a crystalline glass film of MgO. That is, in the case where the air firing condition of the hermetic container 40 is at a temperature lower than 680 ℃ or for a time lower than 58 hours, the thickness of the oxide layer 48 may be insufficient and the hydrogen permeation inhibition performance may be degraded. In addition, in the case where the air firing condition of the sealed vessel 40 is at a temperature higher than 1020 ℃ or for a time longer than 86 hours, energy loss may occur with excessive heat treatment. In addition, slow cooling is slow cooling taking time while managing the cooling rate. The crystallized glass is produced by heating glass to precipitate crystals.
The thickness of oxide layer 48 may be 10nm to 10 μm. That is, when the thickness of the oxide layer 48 of the closed vessel 40 is less than 10nm, the thickness of the oxide layer 48 is insufficient, and the hydrogen permeation suppression performance may be degraded. Further, when the thickness of the oxide layer 48 of the closed vessel 40 is more than 10 μm, energy loss may occur with excessive heat treatment.
With such a configuration, the fuel cell system 10 according to the present invention can achieve hydrogen permeation inhibition performance within a predetermined target range, and can stably supply electric power for a long period of time.
Next, a modification 1 of the fuel cell system of the present invention will be described. Fig. 4 is a schematic front view of a modification 1 of the fuel cell system of fig. 1.
The fuel cell system 70 of the present invention has the same configuration as the fuel cell system 10 except that the outer peripheral portion 74 is substituted for the outer peripheral portion 46, and therefore, the same reference numerals are added to the same components, and the description thereof is omitted.
The outer peripheral portion 74 of the closed container 72 constituting the fuel cell system 70 of the present invention may include an outer peripheral base portion 76 and an outer peripheral wall portion 78. In this way, the outer peripheral base 76 supports the outer peripheral portion of the surface of the solid electrolyte body 24 provided with the fuel electrode 22. Further, the outer peripheral wall portion 78 covers the end face of the solid electrolyte body 24 and is fixed to the end face of the solid electrolyte body 24 using a sealing material. That is, when the flat outer peripheral base 76 and the outer peripheral portion of the solid electrolyte body 24 are fixed with the sealing material, the sealing material is liable to break when the force generated to the sealing material at the time of a temperature change is a shearing direction force due to a difference in thermal expansion coefficient between the solid electrolyte body 24 and the closed vessel 40, and on the other hand, when the outer peripheral wall portion 78 and the end face of the solid electrolyte body 24 opposed to each other are fixed with the sealing material at substantially equal intervals over the entire circumference, the force is generated in the stretching direction or the compression direction, and the sealing material is not liable to break.
With such a configuration, the fuel cell system 70 of the present invention can prevent the damage of the sealing material due to the temperature change and the accompanying leakage of hydrogen, so that the electric power can be continuously supplied for a certain period of time.
Next, modification 2 of the fuel cell system of the present invention will be described. Fig. 5 is a schematic front view of a modification 2 of the fuel cell system of fig. 4.
The fuel cell system 80 of the present invention has the same configuration as that of the fuel cell system 70 except that the electrode composite 90 is substituted for the electrode composite 20, and therefore, the same reference numerals are added to the same components, and the description thereof is omitted.
The electrode composite 90 constituting the fuel cell system 80 of the present invention may include a fuel electrode 92, a solid electrolyte body 94, and an air electrode 96. In this case, the outer peripheral base 76 supports the outer peripheral portion of the surface of the fuel electrode 92 on the opposite side of the solid electrolyte body 94. Further, the outer peripheral wall portion 78 covers the end face of the fuel electrode 92 and is fixed to the end face of the fuel electrode 92 by using a sealing material. That is, as in the fuel cell system 70 of the present invention, when the flat outer peripheral base 76 and the outer peripheral portion of the fuel electrode 92 are fixed with the sealing material, the sealing material is liable to break, while when the outer peripheral wall 78 and the end face of the fuel electrode 92 facing each other are fixed with the sealing material at substantially equal intervals over the entire circumference, the sealing material is not liable to break.
With such a configuration, the fuel cell system 80 of the present invention can prevent the damage of the sealing material due to the temperature change and the accompanying leakage of hydrogen, so that the electric power can be continuously supplied for a certain period of time.
Next, modification 3 of the fuel cell system of the present invention will be described. Fig. 6 is a schematic front view of a modification 3 of the fuel cell system of fig. 4.
The fuel cell system 100 of the present invention has the same configuration as that of the fuel cell system 70 except that the electrode complex 110 is substituted for the electrode complex 20, and therefore, the same reference numerals are added to the same components, and the description thereof is omitted.
The electrode composite 110 constituting the fuel cell system 100 of the present invention may include a fuel electrode 112, a solid electrolyte body 114, and an air electrode 116. In this case, the air electrode 116 is disposed on the surface of the solid electrolyte body 114 on the opposite side of the fuel electrode 112, and reduces oxygen in the air to oxygen ions at the time of discharge. Further, the outer peripheral base 76 supports an outer peripheral portion of the surface of the solid electrolyte body 114 provided with the fuel electrode 112. The outer peripheral wall 78 covers the end face of the solid electrolyte body 114 and the end face of the air electrode 116, and is fixed to the end face of the solid electrolyte body 114 and the end face of the air electrode 116 by using a sealing material. That is, as in the fuel cell system 70 of the present invention, when the flat outer peripheral base 76 and the outer peripheral portion of the solid electrolyte body 114 are fixed with the sealing material, the sealing material is liable to break, whereas when the end faces of the outer peripheral wall 78 and the solid electrolyte body 114, which are opposed to each other, and the end faces of the air electrode 116 are fixed with the sealing material at substantially equal intervals over the entire circumference, the sealing material is not liable to break.
With such a configuration, the fuel cell system 100 of the present invention can prevent the damage of the sealing material due to the temperature change and the accompanying leakage of hydrogen, so that the electric power can be continuously supplied for a certain period of time.
Next, modification 4 of the fuel cell system of the present invention will be described. Fig. 7 is a schematic front view of a modification 4 of the fuel cell system of fig. 4.
The fuel cell system 120 of the present invention has the same configuration as compared to the fuel cell system 70 except that the electrode composite 130 is substituted for the electrode composite 20, and therefore, the same reference numerals are added to the same components, and the description thereof is omitted.
The electrode assembly 130 constituting the fuel cell system 120 of the present invention may include a fuel electrode 132, a solid electrolyte body 134, an air electrode 136, and a porous metal plate 138. In this case, the porous metal plate 138 is provided on the surface of the opposite side of the solid electrolyte 134 of the fuel electrode 132, and can permeate hydrogen gas at the time of charge and discharge. Further, the outer peripheral base 76 supports the outer peripheral portion of the surface of the porous metal plate 138 on the opposite side of the fuel electrode 132. Further, the outer peripheral wall portion 78 covers the end face of the porous metal plate 138 and is fixed to the end face of the porous metal plate 138 by using a sealing material. That is, as in the fuel cell system 70 of the present invention, when the flat outer peripheral base 76 and the outer peripheral portion of the porous metal plate 138 are fixed with the sealing material, the sealing material is liable to break, while when the outer peripheral wall 78 and the end face of the porous metal plate 138 facing each other are fixed with the sealing material at substantially equal intervals over the entire circumference, the sealing material is not liable to break. The porous metal plate 138 is not particularly limited as long as it can permeate hydrogen gas, and is preferably a porous plate made of SUS 430. Further, the end face of the fuel electrode 132 and the externally exposed surface of the porous metal plate 138 need to be covered with a sealing material.
With such a configuration, the fuel cell system 120 of the present invention can prevent the damage of the sealing material due to the temperature change and the accompanying leakage of hydrogen, so that the electric power can be continuously supplied for a certain period of time.
The configuration of the 1 st fuel cell system of the invention is basically as described above.
Next, a fuel cell system of the 2 nd kind of the present invention is specifically described.
In the fuel cell system of the 2 nd aspect of the present invention, as compared with the closed casing 40 constituting the fuel cell system of the 1 st aspect, since the same constitution is provided except for the parts excluding the closed casing 40 of the battery system, the description of the features unrelated to the other parts will be omitted.
The closed container includes an outer wall with an interior space. The inner space accommodates a hydrogen isotope gas hermetically. The outer wall is a metal product which is insulated at a preset temperature and is provided with an oxide layer and a glass film. The surface of the oxide layer, which is the outer wall, is formed by air firing. Among the oxide layers, the glass film covers the oxide layer formed on at least one of the outer surface and the inner surface of the outer wall. The closed container may be provided with an inlet (supply port) for a hydrogen isotope or an inlet (supply port) for a substance generating a hydrogen isotope.
The predetermined temperature of the outer wall is preferably 550 to 750 ℃. If the outer wall temperature is lower than 550 ℃ or higher than 750 ℃, the hydrogen isotope permeation inhibition performance may be degraded. The hydrogen isotopes are hydrogen, deuterium and tritium. Deuterium is also known as deutella, an isotope of hydrogen with a mass number of 2, i.e. a stable isotope in the nucleus consisting of one proton and one neutron. Tritium, also known as tritium, is an isotope of hydrogen with a mass number of 3, i.e., a radioisotope whose nucleus consists of one proton and two neutrons, and whose half-life is 12.32 years, decays to He via beta.
With such a configuration, the sealed container according to item 2 of the present invention can suppress leakage due to permeation of hydrogen isotopes.
The construction of the closed vessel in the invention 2 is basically as described above.
Next, a fuel cell system of the 3 rd aspect of the invention will be described in detail.
The fuel cell system according to claim 3 includes the sealed container according to claim 2, and has the same structure as the fuel cell system according to claim 1 except that the flat plate-shaped electrode assembly 20 and the negative electrode fuel body 30 of the fuel cell system are not necessarily required, and therefore, the description thereof is omitted.
With this configuration, the fuel cell system according to the 3 rd aspect of the present invention can realize hydrogen permeation inhibition performance within a predetermined target range, and can stably supply electric power for a long period of time.
The construction of the fuel cell system of item 3 of the present invention is basically as described above.
Next, a nuclear fusion power generation system of the 4 th aspect of the present invention will be described in detail.
The nuclear fusion power generation system according to the invention No. 4 has the sealed container according to the invention No. 2.
The nuclear fusion power generation system includes a nuclear fusion reactor that receives neutrons from a plasma source and generates heat energy, a steam generator that generates steam using cooling water heated by the nuclear fusion reactor, a circulation pump that circulates cooling water between the nuclear fusion reactor and the steam generator, a turbine generator that rotates a turbine using steam from the steam generator to generate power, a water re-heater that cools and returns the steam to water, and a water supply pump that supplies water from the water re-heater to the steam generator.
Further, the nuclear fusion power generation system includes a cladding installed in the nuclear fusion reactor and generating tritium from neutrons using neutron multiplication material and tritium multiplication material, a device separating deuterium and tritium from exhaust gas of the nuclear fusion reactor, a storage device for storing deuterium and tritium, and a supply device for supplying deuterium and tritium as nuclear fusion reaction fuel into a space surrounded by the cladding.
In order to cause a nuclear fusion reaction, the fuel must be heated to become a plasma. The cladding heats up due to the heat of the plasma and the heat of reaction between neutrons and tritium breeder material. The closed vessel constituting the nuclear fusion power generation system of the present invention corresponds to a vessel accommodating the cladding.
By such a configuration, the nuclear fusion power generation system of the 4 th aspect of the present invention can achieve the performance of suppressing permeation of deuterium and tritium within a preset target range, so that power supply can be stably maintained for a long period of time.
The construction of the nuclear fusion power generation system of item 4 of the present invention is substantially as described above.
Examples
Specific examples of the present invention are given below, and the present invention will be described in more detail.
< A. Evaluation of internal pressure drop Rate >
First, as example 1, a cylindrical container 140 was manufactured by the following procedure.
1. (step A1) SUS tube 142 made of SUS 430 having an outer diameter of 19mm and an inner diameter of 16mm was placed in an electric furnace, fired at 850℃in air for 72 hours, and then cooled slowly, forming oxide layers on the outer and inner surfaces of SUS tube 142.
2. (step A2) the outer surface of the SUS tube 142 after firing in air was coated with a glass paste previously adjusted to an easy-to-coat viscosity with a spatula. The glass paste used was a material having a thermal expansion coefficient of 97X 10 -7 At a temperature of/DEG C and with a main component of La 2 O 3 、B 2 O 3 And/or MgO crystalline glass.
3. (step A3) the SUS tube 142 coated with the glass paste was placed in an electric furnace, heated at 100℃for 1 hour, dried, heated at 400℃for 30 minutes, subjected to a binder removal treatment, heated at 850℃for 6 hours, solidified, and then cooled slowly, whereby a glass film was formed on the outer surface of the SUS tube 142 after air firing.
4. (step A4) in order to reduce the volume of the SUS tube 142 formed with the glass film, the ceramic protector 144 is inserted from one end of the SUS tube 142. The ceramic protector 144 is a structure in which zirconia balls having a diameter of 1mm are placed in an alumina tube having an outer diameter of 1mm smaller than the inner diameter of the SUS tube 142, and the lower end of the alumina tube is made of polyimide with a fixed nickel mesh, and the upper end of the alumina tube is filled with cotton-like refractory fibers.
5. (process A5) the SUS tube 142 inserted into the ceramic protector 144 was placed in an electric furnace, the other end of the SUS tube 142 was coated with the glass paste as an adhesive, and then the YSZ plate 146 was placed thereon and heated at 850 ℃ for 6 hours to be cured to form the glass seal 148, and then maintained at 700 ℃.
In the cylindrical container 140 manufactured through the above steps, the SUS tube 142 inserted with the ceramic protector 144 is used as a substitute for the closed container 40 constituting the fuel cell system 10 of the present invention, the YSZ plate 146 is used as a substitute for the electrode composite 20 constituting the fuel cell system 10 of the present invention, and the glass seal 148 is used as a substitute for a sealing material for fixing the closed container 40 and the electrode composite 20. YSZ, yttria stabilized zirconia, which is a zirconia-based oxide, is added to stabilize the crystal structure of zirconia at room temperature.
Next, as comparative example 1, a cylindrical container 140a was manufactured by the following steps.
1. The steps A1 to 3 are omitted, and the step A4 is performed using the SUS tube 142 having neither an oxide layer nor a glass film formed, instead of the SUS tube 142 having a glass film formed.
2. The above step A5 is performed.
Next, as comparative example 2, a cylindrical container 140b was produced by the following procedure.
1. The step A1 is omitted, and the step A2 is performed using the SUS tube 142 having no oxide layer formed thereon instead of the SUS tube 142 fired in air.
2. The steps A3 to 5 are executed.
< measurement of Hydrogen permeation amount >
Next, a process of measuring the hydrogen permeation quantity will be described in detail. FIG. 8 is a schematic front view of the hydrogen permeation quantity measuring device.
1. (step A1) the cylindrical vessel 140 was set in the electric furnace 152 of the hydrogen permeation quantity measuring apparatus 150, the pipe member 154 was connected to the end portion of the cylindrical vessel 140 on the side where the ceramic protector 144 was inserted, the supply valve 156a and the discharge valve 156b were opened while maintaining the temperature at 700℃and the hydrogen gas was continuously flowed in for 24 hours or more, and the gas in the cylindrical vessel 140 was replaced with hydrogen gas.
2. (step A2) after 24 hours or more from the start of hydrogen gas supply, the discharge valve 156b was closed so that the pressure in the cylindrical vessel 140 was 0.01MPa higher than the atmospheric pressure, and the supply valve 156a was closed.
3. (step A3) the elapsed time from the closing of the supply valve 156a (measurement start time) is recorded, and the internal pressure and the external temperature of the cylindrical container 140 are recorded simultaneously using the pressure sensor 158p and the temperature sensor 158 t.
4. (step A4) determining a specific temperature by the outside temperature of the cylindrical vessel 140 rising and falling with the daily temperature fluctuation, and measuring the inside pressure of the cylindrical vessel 140 when the temperature reaches the temperature for an elapsed time exceeding 250 hours.
5. (step A5) the internal pressures of the cylindrical containers 140a and 140b are measured by the same steps as those of the above steps A1 to A4.
Table 1 shows the above measurement results and the internal pressure when the supply valve 156a is closed.
TABLE 1
In the cylindrical container 140 of example 1, the internal pressure drop rate obtained by dividing the difference between the internal pressure P0 at the start of measurement and the internal pressure P2 at the time of elapsed time exceeding 500 hours by 500 hours is 6.0Pa/H, and therefore is included in a predetermined target range of 10Pa/H or less, whereas the internal pressure drop rate obtained by dividing the difference between the internal pressure P0 and the internal pressure P1 of the cylindrical container 140a of comparative example 1 by 250 hours is 164.0Pa/H, and therefore outside the predetermined target range, the internal pressure drop rate obtained by dividing the difference between the internal pressure P0 and the internal pressure P2 by 500 hours is 14.0Pa/H in the cylindrical container 140b of comparative example 2. From this result, it is clear that the fuel cell system is configured in the same manner as the cylindrical container 140 of example 1, and thus the electric power can be stably supplied for a long period of time.
< B. Evaluation of deuterium permeation coefficient >
Next, as example 2, a measurement sample 160 was prepared by the following procedure.
1. (step B1) a palladium film was formed on one side surface of a SUS plate made of SUS 430 having a square of 25mm (25 square millimeters) and a thickness of 0.5 mm.
2. (step B2) the SUS plate with the palladium film formed thereon was placed in an electric furnace, air-fired at 850℃for 72 hours, and then cooled slowly, whereby an oxide layer was formed on the other side of SUS.
3. (step B3) coating a glass paste previously adjusted to an easy-to-coat viscosity on the oxide layer surface of the SUS plate after air firing with a spatula. The glass paste used was the same as the crystallized glass in example 1.
4. (step B4) the SUS plate coated with the glass paste was placed in an electric furnace, heated at 100℃for 1 hour, dried, heated at 400℃for 30 minutes, subjected to a binder removal treatment, heated at 850℃for 6 hours, and solidified, and then a glass film was formed on the surface of the oxidized layer of the SUS plate after firing in air by slow cooling, whereby a measurement sample 160 was obtained.
The measurement sample 160 produced in the above-described step is a substitute for the closed casing 40 constituting the fuel cell system 10 of the present invention.
Next, as comparative example 3, the above steps B2 to 4 were omitted, and a palladium film was formed on the other side surface of the SUS plate, thereby producing a measurement sample 160a.
Next, as comparative example 4, the measurement sample 160B was prepared by omitting the above-mentioned steps B3 and B4.
Next, as comparative example 5, the above-mentioned step B2 was omitted, and instead of the SUS plate after air firing, the above-mentioned steps B3 and B4 were performed to prepare a measurement sample 160c.
< measurement of Hydrogen permeation amount >
Next, the hydrogen permeation quantity measuring device will be described in detail. Fig. 8 is a schematic front view of a hydrogen isotope permeation quantity measuring apparatus.
The hydrogen isotope permeation quantity measuring apparatus 170 includes a primary container 180, a secondary container 190, and an electric furnace 200. The primary container 180 includes a primary connection pipe portion 180a having one end connected to the primary container 180 and a primary flange portion 180b (primary flange portion 180 b) provided at the other end of the primary connection pipe portion 180 a. Further, the primary tank 180 includes a primary rotary pump 182a that exhausts the inside of the primary tank 180 in a high pressure range, a primary turbo molecular pump 182b that exhausts the inside of the primary tank 180 in a low pressure range, a primary exhaust valve 182c that switches between exhausting and not exhausting the inside of the primary tank 180, a primary high pressure range gauge 184 that measures the internal pressure of the primary tank 180 in the high pressure range, a primary low pressure range gauge 186 that measures the internal pressure of the primary tank 180 in the low pressure range, a hydrogen gas supply pipe 188 that supplies hydrogen gas to the inside of the primary tank 180, and a hydrogen gas supply valve 188a for switching between supplying and non-supplying hydrogen gas. The primary high pressure range pressure gauge 184 has a measurement range of 1.3E0 to 1.3E5 Pa, and the primary low pressure range pressure gauge 186 has a measurement range of 1.0E-7 to 1.0E5 Pa.
The sub-tank 190 includes a sub-connection pipe portion 190a having one end connected to the sub-tank 190 and a sub-flange portion 190b (sub-flange portion 190 b) provided at the other end of the sub-connection pipe portion 190 a. The sub-tank 190 includes a sub-rotary pump 192a for exhausting the inside of the sub-tank 190 in a high pressure range, a sub-turbo molecular pump 192b for exhausting the inside of the sub-tank 190 in a low pressure range, a sub-exhaust valve 192c for switching between exhausting and not exhausting the inside of the sub-tank 190, a sub-pressure gauge 194 for measuring the internal pressure of the sub-tank 190 in the low pressure range, a mass spectrometer 196 for accurately measuring the amount of hydrogen in the inside of the sub-tank 190, a volume measuring tank 198 for measuring the volume of the sub-tank 190, and a volume measuring valve 198a for switching between measuring and not measuring the volume of the sub-tank 190. And the secondary pressure gauge 194 has a measurement range of 1.0E-7 to 1.0E5 Pa.
The mass spectrometer 196 is a device that electromagnetically separates ion masses and measures ion masses by mass. In addition to the quadrupole mass spectrometer of evaluation example 2, there are a time-of-flight mass spectrometer, a high frequency mass spectrometer, an Ion Cyclotron Resonance (ICR) mass spectrometer, and the like. If the ions do not fly in high vacuum they are subject to scattering by other gas molecules and therefore the ion flow path must be maintained at high vacuum. The mass spectrometer 196 is unable to separate hydrogen gas having a measured molecular weight of 2 from helium gas having a monoatomic molecule having a molecular weight of 2, resulting in helium gas in air being mixed in the measured value of molecular weight 2. Therefore, in the hydrogen permeation quantity measurement using the hydrogen isotope permeation quantity measurement device 170, it is decided to use deuterium gas having a molecular weight of 4 instead of hydrogen gas having a molecular weight of 2. It is a well known common practice to use deuterium instead of hydrogen and tritium for permeation measurements to study the permeation behaviour of hydrogen isotopes in materials.
The electric furnace 200 heats the measurement sample 160 to a predetermined temperature. The measurement sample 160 fixed between the primary flange portion 180b and the secondary flange portion 190b, a part of the other end of the primary connection pipe portion 180a, the primary flange portion 180b, a part of the other end of the secondary connection pipe portion 190a, and the secondary flange portion 190b are installed inside the electric furnace 200. On the other hand, the remaining part of one end of the primary connection pipe portion 180a and the remaining part of one end of the secondary connection pipe portion 190a are installed outside the electric furnace 200.
Next, a measurement process describing the hydrogen permeation quantity will be specifically described.
1. (step B1) as preparation, the liquid is filled into the volume measurement container 198 of which the mass is measured in advance, and the volume Vc in the volume measurement container 198 is calculated from the increase in the mass of the liquid in the volume measurement container 198 and the density of the liquid.
2. (step B2) the secondary flange portion 190B of the secondary tank 190 is attached to close the other end of the secondary connection pipe portion 190a, and the volume measurement valve 198a and the secondary exhaust valve 192c are opened, whereby the secondary rotary pump 192a and the secondary turbo molecular pump 192B start to exhaust the secondary tank 190 and the volume measurement tank 198 until the internal pressure reaches a level that can be measured by the secondary pressure gauge 194. The filling pressure P3 of the gas in the volume measuring vessel 198 is measured by the secondary pressure gauge 194.
3. (step B3) the valve 198a for measuring the volume is closed, the secondary rotary pump 192a and the secondary turbo molecular pump 192B are started, and the secondary tank 190 is exhausted until the internal pressure reaches a level of 1.0E-6 Pa. Then, the secondary exhaust valve 192c is closed, and the internal pressure P4 of the secondary tank 190 is measured by the secondary pressure gauge 194.
4. (step B4) after the valve 198a for measuring the volume is opened and the air in the valve 198a for measuring the volume flows into the secondary container 190, the internal pressure P5 of the secondary container 190 is measured by the secondary pressure gauge 194.
5. (step B5) the volume Vc of the volume measurement container 198 calculated in step B1, the filling pressure P3 measured in step B2, the internal pressure P4 measured in step B3, and the internal pressure P5 measured in step B4 are used to calculate the volume V of the sub-container 190 using the following formula. This is a preparation.
(1)
V＝Vc×(P3-P5)/(P5-P4)
6. (step B6) the measurement sample 160 is sandwiched between the primary flange portion 180B and the secondary flange portion 190B, and the measurement sample 160 (not shown) is fixed by bolts (not shown) through holes (not shown) of both flanges and nuts fitted to the bolts. At this time, the surface on the measurement sample 160 on which the palladium film is formed is always arranged on the secondary flange portion 190b side, and the other surface of the measurement sample 160, that is, at least one of the oxide layer and the glass film, or the surface on which the palladium film is formed is arranged on the primary flange portion 180b side.
7. (step B7) the measurement sample 160 fixed in the step B5 is mounted in the electric furnace 200, and the electric furnace 200 is powered on to heat the measurement sample 160 to a predetermined temperature T. The predetermined temperatures were 500 ℃, 600 ℃ and 700 ℃.
8. (step B8) opening the primary exhaust valve 182c and the secondary exhaust valve 192c, starting the primary rotary pump 182a, the primary turbo-molecular pump 182B, the secondary rotary pump 192a and the secondary turbo-molecular pump 192B, simultaneously exhausting the primary container 180 and the secondary container 190 until the internal pressure reaches the level of 1.0E-6Pa, closing the primary exhaust valve 182c and the secondary exhaust valve 192c, and measuring the internal pressure P6 of the primary container 180 as a background value by using the primary low pressure range pressure gauge 186.
9. (step B9) the output value X0 corresponding to the deuterium amount in the secondary container 190 is measured as a background value using the mass spectrometer 196.
10. (step B10) the hydrogen supply valve 188a is opened, deuterium gas is injected from the hydrogen supply pipe 188 into the primary container 180 to a predetermined internal pressure P7, and the internal pressure of the primary container 180 at this time is measured by the primary low pressure range manometer 186. The predetermined pressure is 10 to 80kPa.
11. (step B11) while the internal pressure P7 in step B10 is kept constant, the output value X corresponding to the amount of deuterium in the secondary container 190 is measured by the mass spectrometer 196.
12. (step B12) the volume V calculated in step B5, the temperature T of the sample 160 obtained in step B7, the internal pressure P6 measured in step B8, the output value X0 corresponding to the deuterium amount measured in step B9, the internal pressure P7 measured in step B10, the output value X corresponding to the deuterium amount measured in step B11, the thickness d of the sample 160, the area A of the permeated portion and the molar gas constant R (8.31 JK) -1 mol -1 ) The permeation coefficient K of heavy hydrogen is calculated from the following formula.
(2)
K＝{(X-X0)×V×d}/{A×R×T×√(P7-P6)}
The calculation results are shown in table 2.
In the measurement sample 160 of example 2, the permeation coefficient of deuterium gas was 2.19E-15 at 700℃and 2.16E-14 at 600℃and was 1.00E-13 or less in the preset target range and was 1.30E-13 or more at 500℃and was outside the preset target range. On the other hand, in the measurement sample 160a of comparative example 3, the permeation coefficient of deuterium gas was 1.78E-10 at 700 ℃, 8.92E-11 at 600 ℃, 5.07E-11 at 500 ℃, and outside the preset target range. In the measurement sample 160b of comparative example 4, the temperature was 6.75E-12 at 700 ℃, 2.59E-12 at 600 ℃ and 2.86E-13 at 500 ℃, which were outside the predetermined target range. In the measurement sample 160c of comparative example 5, the values at 700℃and 600℃were 1.58E-13, 6.41E-12 and 500℃were 2.03E-13, respectively, and were outside the predetermined target range. From the results, it was found that by configuring the closed vessel in the same manner as the measurement sample 160 of example 2, leakage of hydrogen isotopes due to permeation can be suppressed.
In summary, the present invention is specifically described by taking examples 1 and 2 as examples, but the present invention is not limited to the above description, and various modifications and changes can be made without departing from the gist of the present invention.
The fuel cell systems 1 and 3 and the nuclear fusion power generation system 4 of the present invention have an effect of being able to stably supply power for a long period of time, and can continuously supply power for a predetermined period of time or longer in a conventional manner and flexibly construct an assembly of fuel cell systems, and the sealed container 2 of the present invention is able to suppress leakage of hydrogen isotopes due to permeation, and is industrially useful.
Symbol description:
fuel cell system 10, 70, 80, 100, 120
Electrode assemblies 20, 90, 110, 130
Fuel electrodes 22, 92, 112, 132
Solid electrolyte bodies 24, 94, 114, 134
Air electrode 26, 96, 116, 136
Anode fuel object 30
Sealed container 40, 72
Interior space 42
Opening 44
Peripheral portion 46, 74
Oxide layer 48
Glass film 50
Heater 60
Peripheral base 76
Peripheral wall portion 78
Porous metal plate 138
Cylindrical containers 140, 140a, 140b
SUS tube 142
Ceramic protector 144
YSZ plate 146
Glass seal 148
Hydrogen permeation quantity measuring device 150
Electric furnace 152
Conduit member 154
Supply valve 156a
Discharge valve 156b
Pressure sensor 158p
Temperature sensor 158t
Measurement samples 160, 160a, 160b, 160c
Hydrogen isotope permeation quantity measuring apparatus 170
Primary container 180
Primary connecting tube portion 180a
Primary flange portion 180b
Primary rotary pump 182a
Primary turbomolecular pump 182b
Primary exhaust valve 182c
Primary high-pressure range pressure gauge 184
Primary low pressure range manometer 186
Hydrogen supply pipe 188
Hydrogen supply valve 188a
Secondary container 190
Secondary connection pipe portion 190a
Secondary flange portion 190b
Secondary rotary pump 192a
Secondary turbomolecular pump 192b
Secondary exhaust valve 192c
Secondary pressure gauge 194
Mass spectrometer 196
Container 198 for measuring volume
Valve 198a for measuring volume
Electric stove 200
Claims (20)
1. A fuel cell system, comprising:
a plate-like electrode composite including a fuel electrode for oxidizing hydrogen gas into water vapor at the time of discharge,
a negative electrode fuel object for reacting with the water vapor to generate the hydrogen gas and itself becoming an oxide,
and a closed container including an opening portion for bringing the hydrogen gas in the internal space into contact with the fuel electrode surface and an outer peripheral portion for hermetically fixing the electrode composite to block the opening portion while including an internal space for hermetically housing the anode fuel object,
The electrode composite and the anode fuel object are insulated at respective predetermined temperatures,
the closed container is made of metal, and a glass film covers an oxide layer formed on at least one of an outer surface and an inner surface of a wall of the closed container in the oxide layer while the surface of the wall of the closed container includes the oxide layer formed by air firing.
2. The fuel cell system according to claim 1, wherein: the electrode assembly further includes a plate-shaped airtight solid electrolyte body provided on one surface of the fuel electrode and conducting oxygen ions during charge and discharge,
the solid electrolyte body is made of ceramic, and the closed container is formed by metal with the thermal expansion coefficient of 0.8-2.0 times that of the solid electrolyte body.
3. The fuel cell system according to claim 2, characterized in that: the outer peripheral portion includes an outer peripheral base portion for supporting an outer peripheral portion of a surface of the solid electrolyte body provided with a fuel electrode and an outer peripheral wall portion covering an end face of the solid electrolyte body,
the outer peripheral wall portion is fixed to an end face of the solid electrolyte body with a sealing material.
4. The fuel cell system according to claim 2, characterized in that: the outer peripheral portion includes an outer peripheral base portion for supporting an outer peripheral portion of a surface of the fuel electrode on the opposite side of the solid electrolyte and an outer peripheral wall portion covering an end face of the fuel electrode,
the outer peripheral wall portion is fixed to an end face of the fuel electrode with a sealing material.
5. The fuel cell system according to claim 2, characterized in that: the electrode assembly further includes an air electrode provided on a surface of the solid electrolyte body on an opposite side of the fuel electrode and reducing oxygen in air to oxygen ions upon discharge,
the outer peripheral portion includes an outer peripheral base portion supporting an outer peripheral portion of the solid electrolyte body surface provided with the fuel electrode and an outer peripheral wall portion covering an end face of the solid electrolyte body and an end face of the air electrode,
the outer peripheral wall portion is fixed to an end face of the solid electrolyte and an end face of the air electrode using a sealing material.
6. The fuel cell system according to claim 2, characterized in that: the electrode assembly further includes a porous metal plate disposed on a surface of the fuel electrode on the opposite side of the solid electrolyte body and permeated with hydrogen gas during charge and discharge,
The outer peripheral portion includes an outer peripheral base portion for supporting an outer peripheral portion of a surface on the opposite side of the fuel electrode on the porous metal plate and an outer peripheral wall portion covering an end face of the porous metal plate,
the outer peripheral wall portion is fixed to an end face of the porous metal plate using a sealing material.
7. The fuel cell system according to any one of claims 1 to 6, characterized in that: the closed container is made of SUS430, and the oxide layer is formed by air firing the closed container at 680-1020 ℃ for 58-86 hours and then slowly cooling.
8. The fuel cell system according to any one of claims 1 to 6, characterized in that: the closed vessel SUS430 is made, and the oxide layer comprises an outer layer rich in Fe and an inner layer rich in Cr.
9. The fuel cell system according to any one of claims 1 to 6, characterized in that: the thickness of the oxide layer is 10 nm-10 mu m.
10. The fuel cell system according to any one of claims 1 to 6, characterized in that: the glass film is a crystallized glass film.
11. The fuel cell system according to any one of claims 1 to 6, characterized in that: the predetermined temperature of the electrode composite is 450-1000 ℃, and the predetermined temperature of the anode fuel object is 300-1000 ℃.
12. The fuel cell system according to any one of claims 1 to 6, characterized in that: and a heater provided on at least one of an outer side and an inner side of a case formed by the closed container and the electrode composite body and for insulating the electrode composite body and the anode fuel object.
13. A closed container, characterized in that: comprising an outer wall provided with an inner space,
the inner space is for hermetically receiving hydrogen gas,
the outer wall is a metal product insulated at a preset temperature, the surface of the outer wall comprises an oxide layer formed by air firing, and meanwhile, a glass film in the oxide layer covers the oxide layer formed on at least one surface of the outer surface and the inner surface of the outer wall.
14. The closed container according to claim 13, wherein: the outer wall is made of SUS430, and the oxide layer is formed by air firing the outer wall at 680-1020 ℃ for 58-86 hours and then slowly cooling.
15. The closed container according to claim 13, wherein: the outer wall is made of SUS430, and the oxide layer comprises an outer layer rich in Fe and an inner layer rich in Cr.
16. The closed container according to any one of claims 13 to 15, wherein: the thickness of the oxide layer is 10 nm-10 mu m.
17. The closed container according to any one of claims 13 to 15, wherein: the glass film is a crystallized glass film.
18. The closed container according to any one of claims 13 to 15, wherein: the predetermined temperature of the outer wall is 550-750 ℃.
19. A fuel cell system comprising the sealed container according to any one of claims 13 to 18.
20. A nuclear fusion power generation system comprising the closed vessel of any one of claims 13 to 18.
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| JP2019149501 | 2019-07-30 | ||
| JP2019-149501 | 2019-07-30 | ||
| PCT/JP2020/029131 WO2021020467A1 (en) | 2019-07-30 | 2020-07-29 | Fuel cell system, nuclear fusion power generation system, and sealed container constituting same |
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| JP2005009553A (en) * | 2003-06-18 | 2005-01-13 | Zojirushi Corp | Heat insulating structure of gas filling body |
| JP2011021220A (en) * | 2009-07-14 | 2011-02-03 | Toyama Univ | Method of generating film on metal surface |
| JP2014139894A (en) * | 2013-01-21 | 2014-07-31 | Ｃｏｎｎｅｘｘ Ｓｙｓｔｅｍｓ株式会社 | Fuel battery |
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| US8652589B2 (en) * | 2008-01-25 | 2014-02-18 | Oerlikon Trading Ag, Truebbach | Permeation barrier layer |
| JP2011116596A (en) * | 2009-12-04 | 2011-06-16 | Nippon Electric Glass Co Ltd | Fired film for glass production vessel, glass production vessel, glass production device, method for producing glass and method for producing glass production device |
| KR101273936B1 (en) * | 2011-08-12 | 2013-06-11 | 한국과학기술연구원 | Ferritic stainless steel with excellent oxidation resistance, manufacturing method thereof and fuel cell interconnector using the same |
| JP6137259B2 (en) * | 2014-09-24 | 2017-05-31 | Ｊｆｅスチール株式会社 | Steel structure for hydrogen |
| WO2017135451A1 (en) * | 2016-02-04 | 2017-08-10 | Ｃｏｎｎｅｘｘ Ｓｙｓｔｅｍｓ株式会社 | Fuel cell |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2005009553A (en) * | 2003-06-18 | 2005-01-13 | Zojirushi Corp | Heat insulating structure of gas filling body |
| JP2011021220A (en) * | 2009-07-14 | 2011-02-03 | Toyama Univ | Method of generating film on metal surface |
| JP2014139894A (en) * | 2013-01-21 | 2014-07-31 | Ｃｏｎｎｅｘｘ Ｓｙｓｔｅｍｓ株式会社 | Fuel battery |
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| CN113994510A (en) | 2022-01-28 |
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