WO2022244805A1 - アニオン交換膜型水電解槽 - Google Patents

アニオン交換膜型水電解槽 Download PDF

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Publication number
WO2022244805A1
WO2022244805A1 PCT/JP2022/020669 JP2022020669W WO2022244805A1 WO 2022244805 A1 WO2022244805 A1 WO 2022244805A1 JP 2022020669 W JP2022020669 W JP 2022020669W WO 2022244805 A1 WO2022244805 A1 WO 2022244805A1
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Prior art keywords
anolyte
conductive porous
porous member
exchange membrane
anion exchange
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Ceased
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English (en)
French (fr)
Japanese (ja)
Inventor
克典 ▲高▼本
康行 田中
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Tokuyama Corp
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Tokuyama Corp
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Priority to JP2023522696A priority Critical patent/JPWO2022244805A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/04—Diaphragms; Spacing elements characterised by the material
    • C25B13/08—Diaphragms; Spacing elements characterised by the material based on organic materials
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/70—Assemblies comprising two or more cells
    • C25B9/73—Assemblies comprising two or more cells of the filter-press type
    • C25B9/75—Assemblies comprising two or more cells of the filter-press type having bipolar electrodes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/70—Assemblies comprising two or more cells
    • C25B9/73—Assemblies comprising two or more cells of the filter-press type
    • C25B9/77—Assemblies comprising two or more cells of the filter-press type having diaphragms
    • 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

Definitions

  • the present invention relates to an electrolytic cell for water electrolysis, and more particularly to a water electrolytic cell equipped with an anion exchange membrane.
  • a cation exchange membrane (hereinafter sometimes referred to as "PEMWE method")
  • PEM cation exchange membrane
  • pure water is supplied to the anode chamber.
  • Hydrogen ions generated together with oxygen gas by an anode reaction in the anode chamber are transported to the cathode chamber via the cation exchange membrane, and generate hydrogen gas by a cathode reaction.
  • PEMWE method since the inside of the electrolytic cell becomes a strongly acidic environment, precious metal catalysts having high acid resistance such as Pt for hydrogen generation and Ir for oxygen generation are used as electrode catalysts, and each electrode chamber is defined.
  • a metal material having high acid resistance such as Ti is also used for members of the electrolytic cell. The use of these materials makes the adoption of the PEMWE process in large-scale water electrolysis plants difficult from a resource and economic point of view.
  • alkaline water electrolysis method In the alkaline water electrolysis method (hereinafter sometimes referred to as "AWE method"), a basic aqueous solution (alkaline water) in which an alkali metal hydroxide (eg, NaOH, KOH, etc.) is dissolved is used as an electrolyte in the anode chamber and Hydrogen gas is generated from the cathode and oxygen gas is generated from the anode by being supplied to the cathode chamber and energized.
  • alkali metal hydroxide eg, NaOH, KOH, etc.
  • an electrolytic cell for alkaline water electrolysis, an electrolytic cell is known which is provided with an anode chamber and a cathode chamber separated by an ion-permeable diaphragm, in which the anode is arranged in the anode chamber and the cathode is arranged in the cathode chamber.
  • hydroxide ions generated together with hydrogen gas by the cathode reaction permeate the ion-permeable diaphragm and move to the anode chamber.
  • an ion exchange membrane as the ion-permeable diaphragm
  • a porous membrane is usually used from the viewpoint of membrane resistance and cost.
  • Each of the electrode liquids in the anode chamber and the cathode chamber of the alkaline water electrolytic cell is generally alkaline with a pH (25° C.) of 12 or higher.
  • an inexpensive porous membrane can be used as a diaphragm, and a non-noble metal catalyst such as Ni for hydrogen generation and Fe, Co, Ni for oxygen generation can be used as an electrode catalyst.
  • a non-noble metal catalyst such as Ni for hydrogen generation and Fe, Co, Ni for oxygen generation
  • relatively inexpensive metal materials such as stainless steel, Ni, and Fe for the members of the electrolytic cell that define each electrode chamber.
  • the AWE method has high price competitiveness in large-scale water electrolysis plants, it is disadvantageous in that a large amount of concentrated alkaline aqueous solution is used as the electrolyte.
  • an anion exchange membrane type water electrolysis method (hereinafter sometimes referred to as "AEMWE method") has been proposed.
  • AEMWE method an anion exchange membrane (hereinafter sometimes referred to as "AEM") is used as a membrane separating an anode chamber and a cathode chamber, and pure water or a basic aqueous solution is supplied to the anode chamber as an anolyte. be done.
  • pure water or a basic aqueous solution may be supplied to the cathode chamber as the polar liquid, it is also possible to use a dry cathode type electrolytic cell in which the polar liquid is not supplied to the cathode chamber.
  • an aqueous solution of carbonate and/or bicarbonate such as alkali metal carbonate and alkali metal bicarbonate is used. It is also possible to use In the AEMWE method, it is possible to use non-noble metal catalysts such as Ni for hydrogen generation and Fe, Co, Ni, etc. for oxygen generation as electrode catalysts. , Ni and the like can be used, which is advantageous over the PEMWE method.
  • the AEMWE process is also characterized by the ability to use aqueous solutions of relatively less corrosive alkali metal carbonates and/or alkali metal bicarbonates as the anolyte, and by the dry cathode type electrolyzer configuration, which is relatively dry. This is advantageous over the AWE process in that the hydrogen gas can be taken directly from the electrolytic cell.
  • the AEMWE method is particularly expected to be applied to small- and medium-sized water electrolysis plants.
  • FIG. 1 is a cross-sectional view schematically illustrating the structure of a conventional anion-exchange membrane-type water electrolytic cell 900 (hereinafter sometimes referred to as "electrolytic cell 900") according to one embodiment.
  • electrolytic cell 900 is an AEM type water electrolytic cell having a dry cathode type configuration.
  • the electrolytic cell 900 includes a conductive first partition wall 910, a conductive first gas diffusion layer 920, an anion exchange membrane 930, a conductive second gas diffusion layer 940, and a conductive second gas diffusion layer 940.
  • a partition wall 950 is provided in the above order, an anode chamber is defined between the first partition wall 910 and the anion exchange membrane 930, and a cathode chamber is defined between the second partition wall 950 and the anion exchange membrane 930. ing.
  • the first partition 910 and the first gas diffusion layer 920 are in physical and electrical contact.
  • the second partition 950 and the second gas diffusion layer 940 are in physical and electrical contact.
  • the first partition 910 includes an anolyte inflow path 912 for inflowing the anolyte into the anode chamber, an anolyte/gas outflow path 913 for outflowing the anolyte and gas from the anode chamber, the anolyte inflow path 912 and the anode.
  • the second partition wall 950 has a cathode chamber gas outflow path 953 for causing gas to flow out from the cathode chamber, and a second flow path provided on the surface of the second partition wall 950 in fluid communication with the cathode chamber gas outflow path 953. and a groove 951 .
  • an anode catalyst for generating oxygen gas is carried, and in the vicinity of the interface between the anion exchange membrane 930 and the second gas diffusion layer 940, a cathodic catalyst for hydrogen gas generation is supported.
  • the anolyte permeates the first gas diffusion layer 920 from the flow in the first channel groove 911 .
  • the first gas diffusion layer 920 and the second gas diffusion layer 940 are in physical contact with the anion exchange membrane 930, and water permeates the anion exchange membrane 930 from the first gas diffusion layer 920 into the cathode chamber. supplied.
  • hydroxide ions are consumed by an anode reaction to generate oxygen gas and water
  • water is consumed by a cathode reaction to generate hydrogen gas and hydroxide ions.
  • Oxygen gas generated by the anode reaction in the anode chamber joins the flow in the first flow channel 911 from the first gas diffusion layer 920, passes through the first flow channel 911 together with the anolyte, and enters the anode chamber. flows out of the anolyte/gas outlet 913 .
  • the hydrogen gas generated by the cathode reaction in the cathode chamber moves from the second gas diffusion layer 940 to the second flow channel groove 951, flows through the second flow channel groove 951, flows into the cathode chamber, and the cathode chamber gas flows out. Outflow from path 953 . Hydroxide ions generated by the cathodic reaction in the cathode chamber are transported to the anode chamber by the anion exchange ability of the anion exchange membrane 930 .
  • the AEMWE method is a developing technology, and the application of the AEMWE method is still limited to laboratory scale.
  • the performance of the AEM water electrolyzer deteriorates rapidly with the passage of operating time, and it is difficult to maintain the initial performance over a long period of time. ing.
  • An object of the present invention is to provide an anion-exchange membrane-type water electrolyzer capable of reducing deterioration in performance over time.
  • the heat resistance of currently known anion exchange membranes is generally lower than that of porous diaphragms used in alkaline water electrolysis cells and proton exchange membranes used in PEM type water electrolysis cells. Electrolytic heat locally increases the temperature at locations where the current density is high, so in the AEM water electrolyzer, the uneven current density distribution tends to cause serious deterioration of the membrane and the catalyst present in the vicinity of the membrane.
  • an anolyte inlet channel 912 and an anolyte/gas outlet channel 913 are provided on the surface of the first partition wall 910 in order to supply fresh anolyte to the entire current-carrying surface. and the anolyte permeates into the first gas diffusion layer 920 from the flow in the first channel groove 911 provided on the surface of the first partition wall 910 . do.
  • the liquid content of the first gas diffusion layer 920 that is, the proportion of the pores of the first gas diffusion layer 920 occupied by the anolyte is high at the location facing the flow channel 911 . It tends to be low in places that do not face the
  • the uneven liquid content of the first gas diffusion layer 920 acts to increase the current density at locations with high liquid content and to decrease the current density at locations with low liquid content. It is thought that it causes non-uniformity.
  • the present invention includes the following forms [1] to [15].
  • An anion exchange membrane type water electrolytic cell comprising an anode chamber is defined between the first partition and the anion exchange membrane; a cathode chamber is defined between the second partition and the anion exchange membrane;
  • the first conductive porous member and the first partition are in at least electrical contact,
  • the second conductive porous member and the second partition are in at least electrical contact,
  • the electrolytic cell is an anolyte inflow passage for flowing the anolyte into the anode chamber; an anolyte/gas outflow path for causing the anolyte and gas to flow out from the anode chamber;
  • the opening of the anolyte inflow path facing the anode chamber is disposed above the opening of the anolyte/gas outflow path facing the anode chamber.
  • Anion exchange membrane type water electrolyzer is disposed above the opening of the anolyte/gas outflow path facing the anode chamber.
  • the anode chamber is a region not occupied by the first conductive porous member, provided in fluid communication with the anolyte inlet channel, and further comprising a distributed region extending in the outer peripheral direction of the first conductive porous member along a portion of the outer peripheral edge; Anion-exchange membrane-type water electrolysis according to [1] or [2], wherein at least part of the anolyte flowing into the anode chamber enters the first conductive porous member via the dispersion region. tank.
  • a frame member that holds the outer peripheral portions of the first conductive porous member and the second conductive porous member and defines the outer peripheral portion of the anode chamber and the outer peripheral portion of the cathode chamber. further prepared, the anolyte inflow path and the anolyte/gas outflow path are provided through the frame member;
  • a first frame member that holds the outer peripheral portion of the first conductive porous member and defines the outer peripheral portion of the anode chamber; a second frame member that holds the outer periphery of the second conductive porous member and defines the outer periphery of the cathode chamber; further comprising the anolyte inflow path and the anolyte/gas outflow path are provided through the first frame member; Anion-exchange membrane-type water electrolysis according to [3], wherein the dispersion region is defined between the inner peripheral portion of the first frame member and the outer peripheral portion of the first conductive porous member. tank.
  • the first frame member is a member integral with the first partition;
  • the overlap between the region where the anion exchange membrane is in contact with the first conductive porous member and the region where the anion exchange membrane is in contact with the second conductive porous member is The anion exchange membrane water electrolytic cell according to any one of [1] to [11], which is circular, elliptical, oval, polygonal, or fan-shaped.
  • An anion exchange membrane water electrolyzer having a laminated structure in which two or more anion exchange membrane water electrolyzers according to [14] are laminated and electrically connected in series.
  • the flow field in which the anolyte permeates the first conductive porous member is such that the anolyte flows into the anode chamber from the anolyte inflow channel and the anolyte/gas flows out.
  • the flow out of the channel it is possible to reduce the current density distribution on the current-carrying surface of the electrolyser, thus reducing the deterioration of performance over time.
  • FIG. 1 is a cross-sectional view schematically illustrating a conventional anion-exchange membrane-type water electrolytic cell 900 according to one embodiment;
  • FIG. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross-sectional view schematically illustrating an anion-exchange membrane-type water electrolytic cell 100 according to one embodiment of the present invention;
  • FIG. 3 is a cross-sectional view taken along the line AA of FIG. 2;
  • Figure 3 is an exploded view of Figure 2;
  • 4 is a plan view of the first partition wall 10.
  • FIG. FIG. 5 is a plan view of the second partition wall 50 (view along arrows HH in FIG.
  • FIG. 4 (A) is a plan view of a first conductive porous member 20; (B) is a plan view of an anion exchange membrane 30.
  • FIG. (A) is a plan view of a second conductive porous member 40; (B) is a plan view of the gasket 70;
  • 5 is a plan view of the frame member 60 (a view of the frame member 60 taken along line AA in FIG. 4);
  • FIG. 5 is a bottom view of the frame member 60 (a view of the frame member 60 taken along line GG in FIG. 4);
  • FIG. FIG. 5 is a BB cross-sectional view of the frame member 60 in FIG. 4;
  • FIG. 5 is a CC cross-sectional view of the frame member 60 in FIG. 4;
  • FIG. 5 is a cross-sectional view of the frame member 60 taken along line DD in FIG. 4;
  • FIG. 5 is a cross-sectional view of the frame member 60 in FIG. 4 taken along line EE.
  • FIG. 5 is a cross-sectional view of the frame member 60 in FIG. 4 taken along line FF.
  • FIG. 3 is a cross-sectional view (a cross-sectional view of an anode chamber) taken along the line BB in FIG. 2;
  • FIG. 3 is a diagram for explaining the shape of the current-carrying portion in the electrolytic cell 100, and is a view showing the current-carrying portion superimposed on the CC cross-sectional view of FIG. BRIEF DESCRIPTION OF THE DRAWINGS Fig.
  • FIG. 1 is a cross-sectional view schematically illustrating an anion exchange membrane water electrolytic cell 200 according to one embodiment of the present invention
  • FIG. 19 is a cross-sectional view taken along the line AA of FIG. 18
  • Figure 3 is an exploded view of Figure 2
  • 3 is a plan view of a first partition wall 210
  • FIG. FIG. 21 is a plan view of the second partition wall 250 (view along arrows HH in FIG. 20)
  • (A) is a plan view of a first conductive porous member 220
  • (B) is a plan view of an anion exchange membrane 30.
  • FIG. (A) is a plan view of a second conductive porous member 240
  • (B) is a plan view of the gasket 270;
  • FIG. 21 is a plan view of the frame member 260 (a view of the frame member 260 taken along line AA in FIG. 20);
  • FIG. 21 is a bottom view of the frame member 260 (a view of the frame member 260 taken along line GG in FIG. 20);
  • FIG. 21 is a BB cross-sectional view of the frame member 260 in FIG. 20;
  • FIG. 21 is a CC cross-sectional view of the frame member 260 in FIG. 20;
  • FIG. 21 is a DD cross-sectional view of the frame member 260 in FIG. 20;
  • FIG. 21 is a DD cross-sectional view of the frame member 260 in FIG. 20;
  • FIG. 21 is a cross-sectional view of the frame member 260 in FIG. 20 taken along line FF.
  • FIG. 21 is a plan view of the frame member 260 (a view of the frame member 260 taken along line AA in FIG. 20);
  • FIG. 21 is a bottom view of the frame member 260 (a
  • FIG. 19 is a cross-sectional view (a cross-sectional view of the anode chamber) taken along the line BB in FIG. 18;
  • FIG. 19 is a diagram for explaining the shape of the current-carrying portion in the electrolytic cell 200, and is a view showing the current-carrying portion superimposed on the CC cross-sectional view of FIG. 18.
  • FIG. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view schematically illustrating an anion exchange membrane water electrolytic bath 300 according to one embodiment of the present invention;
  • FIG. 35 is a cross-sectional view taken along the line AA of FIG.
  • FIG. 34 Figure 35 is an exploded view of Figure 34;
  • (A) is a plan view of a first conductive porous member 320;
  • (B) is a plan view of an anion exchange membrane 330.
  • FIG. (A) is a plan view of a second conductive porous member 340;
  • (B) is a plan view of the gasket 370;
  • FIG. 37 is a plan view of the frame member 360 (a view of the frame member 360 taken along line AA in FIG. 36);
  • FIG. 37 is a bottom view of the frame member 360 (a view of the frame member 360 taken along line GG in FIG. 36);
  • FIG. 37 is a BB cross-sectional view of the frame member 360 in FIG. 36;
  • FIG. 37 is a CC cross-sectional view of the frame member 360 in FIG. 36;
  • FIG. 37 is a DD sectional view of the frame member 360 in FIG. 36;
  • 37 is a cross-sectional view along EE of the frame member 360 in FIG. 36;
  • 37 is a cross-sectional view of the frame member 360 in FIG. 36 taken along line FF.
  • FIG. 35 is a cross-sectional view (a cross-sectional view of the anode chamber) taken along the line BB in FIG. 34;
  • FIG. 35 is a diagram for explaining the shape of the current-carrying portion in the electrolytic cell 300, and is a diagram showing the current-carrying portion superimposed on the CC cross-sectional view of FIG.
  • FIG. 1 is a cross-sectional view schematically illustrating an anion exchange membrane water electrolytic bath 400 according to one embodiment of the present invention
  • FIG. 49 is a cross-sectional view taken along the line AA of FIG. 48
  • Figure 49 is an exploded view of Figure 48
  • FIG. 50 is a plan view of the first electrolytic element 410 (a view taken along line AA in FIG. 50);
  • FIG. 50 is a bottom view of the first electrolytic element 410 (view along arrows EE in FIG. 50).
  • 51 is a BB cross-sectional view of the first electrolytic element 410 in FIG. 50.
  • FIG. 51 is a CC cross-sectional view of the first electrolytic element 410 in FIG. 50.
  • FIG. 49 is a cross-sectional view schematically illustrating an anion exchange membrane water electrolytic bath 400 according to one embodiment of the present invention
  • FIG. 49 is a cross-sectional view taken along the line AA of FIG. 48
  • Figure 49 is an exploded view of Figure 48
  • FIG. 51 is a DD cross-sectional view of the first electrolytic element 410 in FIG. 50;
  • FIG. 51 is a plan view of the second electrolytic element 450 (view taken along arrows FF in FIG. 50);
  • FIG. 51 is a bottom view of the second electrolytic element 450 (a view taken along line II in FIG. 50);
  • FIG. 51 is a GG cross-sectional view of the second electrolytic element 450 in FIG. 50;
  • FIG. 51 is an HH cross-sectional view of the second electrolytic element 450 in FIG. 50;
  • (A) is a plan view of a first conductive porous member 420 and a second conductive porous member 440;
  • (B) is a plan view of a conductive carbon mesh 490;
  • FIG. 50 is a plan view of the anion exchange membrane element 430 (view along JJ in FIG. 50).
  • FIG. 51 is a plan view of the gasket 470 (view along arrows KK in FIG. 50);
  • FIG. 49 is a cross-sectional view (a cross-sectional view of the anode chamber) taken along the line BB in FIG. 48;
  • BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view schematically illustrating an anion exchange membrane type water electrolytic cell 1000 according to one embodiment of the present invention;
  • FIG. 65 is a cross-sectional view taken along the line AA of FIG. 64; BRIEF DESCRIPTION OF THE DRAWINGS Fig.
  • FIG. 1 is a cross-sectional view schematically illustrating an anion exchange membrane water electrolytic cell 2000 according to one embodiment of the present invention
  • FIG. 67 is a cross-sectional view taken along the line AA of FIG. 66
  • 67 is an exploded view of FIG. 66
  • FIG. FIG. 4 is a cross-sectional view schematically explaining an electrolytic element 2460
  • FIG. 70 is a cross-sectional view taken along the line AA of FIG. 69
  • FIG. 69 is a plan view of the electrolytic element 2460 (a view taken along line BB in FIG. 69);
  • FIG. 69 is a bottom view of the electrolytic element 2460 (view along arrows HH in FIG. 69).
  • FIG. 67 is a cross-sectional view schematically illustrating an anion exchange membrane water electrolytic cell 2000 according to one embodiment of the present invention
  • FIG. 67 is a cross-sectional view taken along the line AA of FIG. 66
  • 67 is an exploded view
  • FIG. 70 is a CC cross-sectional view of the electrolytic element 2460 in FIG. 69;
  • FIG. 70 is a DD cross-sectional view of the electrolytic element 2460 in FIG. 69;
  • FIG. 70 is an EE cross-sectional view of the electrolytic element 2460 in FIG. 69;
  • FIG. 70 is a cross-sectional view of electrolytic element 2460 in FIG. 69 taken along line FF.
  • FIG. 70 is a GG cross-sectional view of electrolytic element 2460 in FIG. 69;
  • E1 and / or E2 for the elements E1 and E2 means “ E1 or E2, or a combination thereof", and the elements E1, ..., EN ( N is 3 above integers), the notation "E 1 , ..., E N-1 , and/or E N " shall mean “E 1 , ..., E N-1 , or E N , or combinations thereof.” do.
  • N is an integer of 3 or more
  • elements that have already appeared in FIGS. may be omitted.
  • FIG. 2 is a cross-sectional view schematically illustrating an anion exchange membrane type water electrolytic cell 100 (hereinafter sometimes referred to as "electrolytic cell 100") according to one embodiment of the present invention.
  • the up-down direction on the paper surface is the vertical up-down direction
  • the upper side on the paper surface is the vertical upper side.
  • FIG. 3 is a cross-sectional view taken along line AA of FIG.
  • FIG. 4 is an exploded view of FIG.
  • the electrolytic cell 100 includes a conductive first partition 10, a first conductive porous member 20, an anion exchange membrane 30, a second conductive porous member 40, and a conductive second partition. 50 and , in the above order.
  • An anode compartment is defined between the first partition 10 and the anion exchange membrane 30
  • a cathode compartment is defined between the second partition 50 and the anion exchange membrane 30 .
  • the first conductive porous member 20 and the first partition wall 10 are in at least electrical contact.
  • the second conductive porous member 40 and the second partition wall 50 are in at least electrical contact.
  • the first conductive porous member 20 and the first partition wall 10 are in direct contact, and the second conductive porous member 40 and the second partition wall 50 are in direct contact.
  • the electrolytic cell 100 further includes an anolyte inflow passage 81 for inflowing the anolyte into the anode chamber, an anolyte/gas outflow passage 82 for outflowing the anolyte and gas from the anode chamber, and a cathode chamber gas for outflowing gas from the cathode chamber. and an outflow channel 83 .
  • the electrolytic cell 100 includes a frame member 60 that holds the outer peripheries of the first conductive porous member 20 and the second conductive porous member 40 and defines the outer periphery of the anode chamber and the outer periphery of the cathode chamber. is further provided.
  • the anode liquid inflow path 81 , the anode liquid/gas outflow path 82 , and the cathode chamber gas outflow path 83 are provided through the frame member 60 .
  • the electrolytic cell 100 further includes a gasket 70 arranged in contact with the anion exchange membrane 30 and the frame member 60 to keep the anode chamber and the cathode chamber watertight and airtight.
  • FIG. 5 is a plan view of the first partition wall 10
  • FIG. 6 is a plan view of the second partition wall 50 (view from arrow HH in FIG. 4).
  • the second partition wall 50 includes an anode liquid supply through hole 50h1, an anode liquid/gas recovery through hole 50h2, and a cathode chamber gas recovery through hole 50h3.
  • the anolyte supply through-hole 50h1 forms part of the anolyte inflow passage 81
  • the anolyte/gas recovery through-hole 50h2 forms part of the anolyte/gas outflow passage 82
  • the cathode chamber gas recovery through-hole 50h2 forms part of the anolyte/gas outflow passage 82.
  • the hole 50h3 constitutes a part of the cathode chamber gas outlet passage 83.
  • the first partition 10 is not provided with these through holes.
  • a rigid conductive material having alkali resistance can be used as a material for the first partition 10 and the second partition 50.
  • a metal material such as stainless steel can be preferably employed. These metal materials may be used after being plated with nickel in order to improve corrosion resistance and conductivity.
  • FIG. 7(A) is a plan view of the first conductive porous member 20.
  • the first conductive porous member 20 is a plate-like conductive porous member, and can be received from the first surface 60a side of the frame member 60 in a main through hole 60h0 of the frame member 60, which will be described later. and is sandwiched between the first partition wall 10 and the anion exchange membrane 30 .
  • the first conductive porous member 20 allows the anolyte and the gas to flow at least in the in-plane direction (that is, the up-down direction and the depth direction in FIGS. 2 to 4).
  • the first conductive porous member 20 allows the anolyte and the gas to flow also in the thickness direction (that is, the lateral direction of the paper of FIGS. 2 to 4). It is preferable that the first conductive porous member 20 allows the anolyte and the gas to flow in both the in-plane direction and the thickness direction.
  • a rigid conductive material having alkali resistance can be used as the material of the first conductive porous member 20 .
  • Metal materials such as stainless steel, nickel steel, carbon steel, plated carbon steel, etc. can be preferably employed.
  • a metal for plating carbon steel a metal having alkali resistance such as nickel and platinum can be preferably used.
  • a plate-like member made of porous metal can be preferably employed as the first conductive porous member 20.
  • a porous metal having air bubbles in fluid communication can be preferably used.
  • Such a porous metal is known as an open-cell porous metal. There is no particular limitation on the method of manufacturing the open-cell type porous metal.
  • Examples of open-cell type porous metal manufacturing methods include hollow metal sintering (MHS method), in which pre-manufactured metal spheres are sintered; Degreasing and sintering, powder space holder MIM (Metal Injection Molding) method (PSH-MIM method); fiber space holder (FSH) method; plating method; metal fiber compression bonding method; slurry of metal powder as template (mold) A slurry coating method in which the material is coated and then dried and sintered, or the template is removed by heating after coating the surface of the material to be the template with a metal; Examples include a slurry foaming method in which foaming is performed by injecting a gas or the like, and the foamed state is maintained (for example, by using a surfactant) and then dried and sintered.
  • MHS method hollow metal sintering
  • PSH-MIM method Metal Injection Molding method
  • FSH fiber space holder
  • plating method metal fiber compression bonding method
  • an open-cell type porous metal can be manufactured by a precision casting method or a powder metallurgy method (spacer method) using a spacer material for forming cells.
  • an open-cell porous metal can be obtained by sintering a mixture of metal powder and spacer resin powder after press molding.
  • an open-cell type porous metal can be obtained by impregnating a foamed resin template (mold) with a slurry obtained by dispersing metal powder in a solvent, followed by drying and firing.
  • a foamed resin template for example, a template made of a known foamed resin such as foamed polyurethane or foamed polystyrene can be used.
  • the average porosity of the first conductive porous member 20 is not particularly limited, it may preferably be, for example, 5-98% by volume, or 70-90% by volume. Note that the average porosity of the first conductive porous member 20 is the actual volume (unit: cm 3 ) of the first conductive porous member 20 and the member volume of the first conductive porous member 20 (that is, , (the mass of the first conductive porous member 20)/(the original specific gravity of the constituent material of the first conductive porous member 20)) (unit: cm 3 ).
  • Average porosity (unit: volume %) 100 ⁇ ((actual volume of first conductive porous member 20) - (member volume of first conductive porous member 20)) / (first conductivity Actual volume of porous member 20)
  • the average pore diameter D of the first conductive porous member 20 is not particularly limited, it is preferably 0.001 to 4.0 mm, or 0.002 to 0.05 mm, for example.
  • the average pore diameter of the porous metal can be measured by measuring the pore diameters at three points extracted from a 1 cm square area of the surface with an optical microscope and calculating the average value.
  • the thickness t of the first conductive porous member 20 is not particularly limited, but can be preferably 0.1 to 50 mm, or 0.3 to 5.0 mm, for example.
  • the ratio t/D between the thickness t of the first conductive porous member 20 and the average pore diameter D is not particularly limited, it is preferably 0.025 to 50000, or 6 to 5000, for example.
  • FIG. 7(B) is a plan view of the anion exchange membrane 30.
  • the anion exchange membrane 30 has a dimension that allows it to be received from the first surface 60a side of the frame member 60 in a main through hole 60h0 of the frame member 60, which will be described later. It is sandwiched between the portion 62 and the first conductive porous member 20 .
  • an anion exchange membrane having a hydroxide ion exchange capacity, an alkali resistance, and permeation of water can be employed without particular limitation.
  • anion exchange membranes that can be used as the anion exchange membrane 30 include membranes containing polymers having quaternary ammonium groups in side chains.
  • anion exchange membranes examples include A201, A901 (both manufactured by Tokuyama Corporation); -50, FAA-3-PK-130, FAA-3-PP-75), FAB (both manufactured by Fumatech); Sustainion (trademark) 37-50 (manufactured by Dioxide Materials); NEOSEPTA (registered trademark) ACM, AM-1, ACS, ACLE-5P, AHA, AMH, (all manufactured by Astom Co., Ltd.); SELEMION (registered trademark) AMT, DSV, AAV, ASV, AHT, APS (all manufactured by Asahi Glass Co., Ltd.); Aciplex ( Registered trademark) A-501, A-231, A-101 (all manufactured by Asahi Kasei Corporation), and the like.
  • the thickness of the anion exchange membrane 30 is not particularly limited, it can be, for example, 5 to 100 ⁇ m.
  • FIG. 8(A) is a plan view of the second conductive porous member 40.
  • the second conductive porous member 40 is a plate-like second conductive porous member, and can be received in a main through hole 60h0 of the frame member 60, which will be described later, from the second surface 60b side. and is sandwiched between the anion exchange membrane 30 and the second partition 50 . Also, the second conductive porous member 40 has dimensions that allow it to be received in the gasket 70 .
  • the second conductive porous member 40 is a conductive porous member through which at least gas can flow. In the electrolytic cell 100, the second conductive porous member 40 is arranged in the in-plane direction (that is, the vertical direction and the depth direction in FIGS.
  • the second conductive porous member 40 allows gas to flow in both the in-plane direction and the thickness direction.
  • a rigid conductive material can be used as the material of the second conductive porous member 40.
  • single metals such as nickel, copper, and titanium; Metal materials such as nickel steel, carbon steel, plated carbon steel, etc. can be preferably employed. Metals such as nickel and platinum can be preferably used as metals for plating carbon steel.
  • the second conductive porous member 40 a plate-like member made of porous metal (metallic porous body) can be preferably employed.
  • the porous metal the porous metal (open-cell type porous metal) having fluid-communicating cells described above in relation to the first conductive porous member 20 can be preferably employed. Same as above.
  • the electrolytic cell 100 further includes an oxygen-generating anode catalyst (not shown) placed in the anode chamber and a hydrogen-generating cathode catalyst (not shown) placed in the cathode chamber.
  • an anode catalyst for generating oxygen for example, an anode catalyst containing nickel as an element can be preferably used.
  • the anode catalyst preferably comprises nickel oxide, nickel metal, or nickel hydroxide, or combinations thereof, and may comprise alloys of nickel with one or more other metals. It is particularly preferred that the anode catalyst consists of metallic nickel.
  • the anode catalyst may further contain chromium, molybdenum, cobalt, tantalum, zirconium, aluminum, iron, zinc, platinum group elements, rare earth elements, or combinations thereof.
  • Rhodium, palladium, iridium, or ruthenium, or a combination thereof may be further supported on the surface of the anode catalyst as an additional catalyst.
  • the anode catalyst include iridium dioxide; complex oxides of cobalt and copper (eg, CuCoO 3 , CuCoO x (x is a real number corresponding to the average oxidation number of the metal element), Cu x Co 3-x O 4 (x is a real number of 0 ⁇ x ⁇ 3), Cu 0.7 Co 2.3 O 4 etc.); a composite oxide of nickel and cobalt (eg NiCo 2 O 4 etc.); iron in a composite oxide of nickel and cobalt doped catalyst (NiCoO x : Fe (x is a real number corresponding to the average oxidation number of the metal element)); a composite oxide of nickel and iron (e.g.
  • NiFe 2 O 4 etc. a composite oxide of ruthenium and lead ( composite oxides of manganese, iron and cerium ( eg Ce 0.2 MnFe 1.8 O 4 etc.); Ni — Fe alloys; Ni—Al alloys, etc. be able to.
  • cathode catalyst for hydrogen generation for example, noble metal oxides, nickel, cobalt, molybdenum, ruthenium or manganese, oxides thereof, or cathode catalysts containing noble metal oxides can be preferably employed.
  • cathodic catalysts include platinum (such as platinum on activated carbon (Pt/C) and Pt black), cerium dioxide on activated carbon, and nickel on lanthanum (III) oxide ( Ni/CeO 2 -La 2 O 3 /C), Ni--Mo alloys, Ni--Fe--Co alloys, Ni--Al--Mo alloys, and the like.
  • the anode catalyst is preferably carried on the surface of the first conductive porous member 20 or the anion exchange membrane 30 facing the anode chamber, and the cathode catalyst is preferably carried on the second conductive porous member 40. Alternatively, it is supported on the cathode chamber side surface of the anion exchange membrane 30 . In one preferred embodiment, the anode catalyst is carried on the first electrically conductive porous member 20 .
  • the cathode catalyst may be carried on the second conductive porous member 40, or may be carried on the surface of the anion exchange membrane 30 facing the cathode chamber. preferably.
  • FIG. 8(B) is a plan view of the gasket 70.
  • the gasket 70 has a dimension that allows it to be inserted from the first surface 60a side into the main through hole 60h0 of the frame member 60 described later, and the gasket positioning portion 63 of the frame member 60 described later. and the anion exchange membrane 30 to keep the anode chamber and the cathode chamber watertight and airtight.
  • Gasket 70 is preferably made of an elastomer having alkali resistance.
  • Examples of materials constituting the gasket 70 include natural rubber (NR), styrene-butadiene rubber (SBR), chloroprene rubber (CR), butadiene rubber (BR), acrylonitrile-butadiene rubber (NBR), and silicone rubber (SR). , ethylene-propylene rubber (EPT), ethylene-propylene-diene rubber (EPDM), fluororubber (FR), isobutylene-isoprene rubber (IIR), urethane rubber (UR), chlorosulfonated polyethylene rubber (CSM), etc. can be mentioned.
  • a layer of a material having alkali resistance may be provided by coating or the like on the surface of the gasket material.
  • the frame member 60 includes a frame-shaped base body 61 (hereinafter sometimes simply referred to as "base body 61") having a main through hole 60h0, and has a first surface 60a and a second surface 60b (FIG. 4).
  • FIG. 9 is a plan view of the frame member 60 (a view of the frame member 60 taken along line AA in FIG. 4).
  • the first surface 60a of the frame member 60 is shown in FIG.
  • FIG. 10 is a bottom view of the frame member 60 (a view of the frame member 60 taken along line GG in FIG. 4).
  • the second surface 60b of the frame member 60 is shown in FIG.
  • the frame-shaped base body 61 further has an anode liquid supply through hole 60h1, an anode liquid/gas recovery through hole 60h1, and an anode liquid supply through hole 60h1 provided through the first surface 60a and the second surface 60b on the outer peripheral side of the main through hole 60h0. It has a through hole 60h2 and a cathode chamber gas recovery through hole 60h3.
  • the anode liquid supply through-hole 60h1, the anode liquid/gas recovery through-hole 60h2, and the cathode chamber gas recovery through-hole 60h3 of the frame member 60 correspond to the anode liquid supply through-hole 50h1 of the second partition wall 50, It is provided at a position corresponding to the anode liquid/gas recovery through hole 50h2 and the cathode chamber gas recovery through hole 50h3.
  • the anode liquid supply through-hole 60h1 constitutes a part of the anode liquid inflow passage 81
  • the anode liquid/gas recovery through-hole 60h2 constitutes a part of the anode liquid/gas outflow passage 82
  • the cathode chamber gas recovery through-hole 60h2 constitutes a part of the anode liquid/gas outflow passage 82.
  • the hole 60h3 constitutes a part of the cathode chamber gas outflow path 83. As shown in FIG.
  • the frame member 60 further includes an AEM positioning portion 62 that protrudes inwardly along the inner peripheral portion of the frame-shaped base 61 , and an AEM positioning portion 62 that protrudes along the inner peripheral portion of the frame-shaped base 61 .
  • a gasket positioning portion 63 is provided so as to protrude further toward the inner peripheral side.
  • the inner peripheral portion of the frame member 60 the inner peripheral portion of the base 61, the inner peripheral portion of the AEM positioning portion 62, and the inner peripheral portion of the gasket positioning portion 63 are arranged in the thickness direction of the frame member 60 (that is, the horizontal direction of the paper surface of FIG. 4). ) are arranged in this order.
  • the first surface 60a, the AEM positioning portion 62, and the gasket positioning portion 63 form a stepped shape (see FIG. 4).
  • FIG. 10 which is a bottom view of the frame member, the second surface 60b of the frame member 60 and the inner peripheral portion of the gasket positioning portion 63 are shown.
  • the frame-shaped base 61, the AEM positioning portion 62, and the gasket positioning portion 63 of the frame member 60 may be integrally formed, and the separately formed members may be integrally fixed in a specific arrangement.
  • the frame member 60 may be formed by
  • FIG. 11 is a BB cross-sectional view of the frame member 60 in FIG. FIG. 11 also shows the main through hole 60h0, the anode liquid supply through hole 60h1, the anode liquid/gas recovery through hole 60h2, and the cathode chamber gas recovery through hole 60h3.
  • FIG. 11 also shows the inner peripheral portion of the frame-shaped base 61 facing the main through hole 60h0.
  • the frame member 60 is provided in the vicinity of the first surface 60a so as to extend along part of the inner peripheral portion of the frame-shaped base 61. It further comprises an anolyte distribution groove 65 that opens toward the surface 60a and the main through hole 60h0.
  • the anolyte distribution groove 65 and the anolyte supply through hole 60 h 1 are in fluid communication with each other through the anolyte supply groove 64 .
  • the anolyte supply groove 64 and the anolyte distribution groove 65 open toward the top of the circular main through-hole 60h0.
  • the frame member 60 is provided in the vicinity of the first surface 60a so as to provide fluid communication between the anolyte and gas recovery through holes 60h2 and the main through holes 60h0.
  • An anolyte/gas recovery groove 66 opening toward 60h0 is further provided.
  • the anolyte/gas recovery groove 66 opens toward the lower portion of the circular main through-hole 60h0.
  • FIG. 12 is a CC cross-sectional view of the frame member 60 in FIG. FIG. 12 also shows the main through hole 60h0, the anode liquid supply through hole 60h1, the anode liquid/gas recovery through hole 60h2, and the cathode chamber gas recovery through hole 60h3.
  • FIG. 12 also shows the inner peripheral portion of the frame-shaped base 61 facing the main through hole 60h0.
  • FIG. 13 is a DD cross-sectional view of the frame member 60 in FIG.
  • FIG. 13 also shows the main through hole 60h0, the anode liquid supply through hole 60h1, the anode liquid/gas recovery through hole 60h2, and the cathode chamber gas recovery through hole 60h3.
  • FIG. 13 also shows the inner peripheral portion of the AEM positioning portion 62 facing the main through hole 60h0.
  • FIG. 14 is an EE cross-sectional view of the frame member 60 in FIG.
  • FIG. 14 also shows the main through hole 60h0, the anode liquid supply through hole 60h1, the anode liquid/gas recovery through hole 60h2, and the cathode chamber gas recovery through hole 60h3.
  • FIG. 14 also shows the inner peripheral portion of the gasket positioning portion 63 facing the main through hole 60h0.
  • FIG. 15 is a cross-sectional view of the frame member 60 taken along line FF in FIG.
  • FIG. 15 also shows the main through hole 60h0, the anode liquid supply through hole 60h1, the anode liquid/gas recovery through hole 60h2, and the cathode chamber gas recovery through hole 60h3.
  • FIG. 15 also shows the inner peripheral portion of the gasket positioning portion 63 facing the main through hole 60h0.
  • the frame member 60 is provided in the vicinity of the second surface 60b so as to provide fluid communication between the cathode chamber gas recovery through hole 60h3 and the main through hole 60h0, It further includes a cathode chamber gas recovery groove 67 that opens toward the second surface 60b and the main through hole 60h0.
  • the frame member 60 is electrically insulating against voltage application from the outside.
  • frame member 60 is formed from an electrically insulating material.
  • a resin material having alkali resistance and strength to withstand the pressing force applied in the stacking direction can be preferably used.
  • rigid vinyl chloride resin, polypropylene resin, polyethylene resin, polyetherimide resin, polyphenylene sulfide resin, polybenzimidazole resin, polytetrafluoroethylene resin, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin, tetrafluoroethylene-ethylene A copolymer resin etc. can be mentioned.
  • the frame member 60 comprises a core made of a metal material and a coating layer of an electrically insulating material covering the surface of the core.
  • the metal material forming the core material of the frame member 60 include a rigid metal material such as single metal such as iron and stainless steel such as SUS304.
  • Preferred examples of the electrically insulating material forming the coating layer of the frame member 60 include the electrically insulating resin material described above and an elastomer having electrical insulating properties and alkali resistance.
  • elastomers include natural rubber (NR), styrene-butadiene rubber (SBR), chloroprene rubber (CR), butadiene rubber (BR), acrylonitrile-butadiene rubber (NBR), ethylene-propylene rubber (EPT). , ethylene-propylene-diene rubber (EPDM), isobutylene-isoprene rubber (IIR), chlorosulfonated polyethylene rubber (CSM), and the like.
  • NR natural rubber
  • SBR styrene-butadiene rubber
  • CR chloroprene rubber
  • BR butadiene rubber
  • NBR acrylonitrile-butadiene rubber
  • EPT ethylene-propylene rubber
  • EPDM ethylene-propylene-diene rubber
  • IIR isobutylene-isoprene rubber
  • CSM chlorosulfonated polyethylene rubber
  • the gasket 70, the anion exchange membrane 30, and the first conductive porous member 20 are inserted into the main through hole 60h0 of the frame member 60 in this order from the first surface 60a side, and the second conductive porous member 40 is inserted into the main through hole 60h0 of the frame member 60 from the second surface 60b side.
  • the first partition 10 is fixed to the first surface 60a of the frame member 60
  • the second partition 50 is fixed to the second surface 60b of the frame member 60, whereby the first partition 10 and the anion exchange membrane 30 and a cathode chamber is defined between the second partition 50 and the anion exchange membrane 30 .
  • the second partition wall 50 communicates with the anode liquid supply through hole 50h1 of the second partition wall 50 with the anode liquid supply through hole 60h1 of the frame member 60, and the second partition wall 50 recovers the anode liquid and gas.
  • through-hole 50h2 communicates with anode liquid/gas recovery through-hole 60h2 of frame member 60
  • cathode chamber gas recovery through-hole 50h3 of second partition wall 50 communicates with cathode chamber gas recovery through-hole 60h3 of frame member 60. It is fixed to the second surface 60b of the frame member 60 so as to communicate therewith.
  • the anolyte distribution groove 65 and the anolyte supply groove 64 (FIGS.
  • a cathode chamber gas recovery groove 67 (FIGS. 10 and 15) opened in the second surface 60b of the frame member 60 is covered by the second partition wall 50 and constitutes a part of the cathode chamber gas outflow path 83. .
  • an anolyte supply through hole 50h1 of the second partition wall 50, an anolyte supply through hole 60h1 of the frame member 60, and an opening facing the first surface 60a of the frame member 60 are
  • the anolyte distribution groove 65 and the anolyte supply groove 64 closed by the first partition wall 10 communicate with each other to form an integrated anolyte inlet channel 81 .
  • the anode liquid/gas recovery through-hole 50h2 of the second partition wall 50, the anode liquid/gas recovery through-hole 60h2 of the frame member 60, and the opening toward the first surface 60a of the frame member 60 are the first.
  • the anode liquid/gas recovery groove 66 closed by the partition wall 10 communicates with the anode liquid/gas recovery groove 66 to form an integral anode liquid/gas outflow path 82 .
  • the cathode chamber gas recovery through-hole 50h3 of the second partition wall 50, the cathode chamber gas recovery through-hole 60h3 of the frame member 60, and the opening toward the second surface 60b of the frame member 60 are the second An integral cathode chamber gas outlet passage 83 is formed by communicating with the cathode chamber gas recovery groove 67 closed by the partition wall 50 .
  • the gasket 70 is sandwiched between the gasket positioning portion 63 of the frame member 60 and the anion exchange membrane 30, and the anion exchange membrane 30 is sandwiched between the AEM positioning portion 62 of the frame member 60 and the first
  • the first conductive porous member 20 is sandwiched between the anion exchange membrane 30 and the first partition wall 10 .
  • the second conductive porous member 40 is sandwiched between the anion exchange membrane 30 and the second partition wall 50 .
  • the first partition wall 10 presses the first conductive porous member 20 , the anion exchange membrane 30 and the gasket 70 toward the frame member 60 .
  • the second partition wall 50 also presses the second conductive porous member 40 toward the anion exchange membrane 30 and the first conductive porous member 20 behind it.
  • first partition 10 and the second partition 50 As means for fixing the first partition 10 and the second partition 50 to the frame member 60, known fixing means such as bolt fixing, brazing, welding, and pressing can be used. Additional sealing members are arranged between the first partition 10 and the first surface 60a of the frame member 60 and between the second partition 50 and the second surface 60b of the frame member 60, respectively. You may
  • the operation of electrolytic cell 100 will be described.
  • the electrolytic cell 100 is a dry cathode type electrolytic cell.
  • the first partition 10 is connected to the positive pole of the DC power supply, and the second partition 50 is connected to the negative pole of the DC power supply.
  • the anolyte that has flowed into the anode chamber from the anolyte inlet channel 81 flows through the first conductive porous member 20 at least in the in-plane direction, and flows out from the anolyte/gas outlet channel 82 .
  • the first conductive porous member 20 is in physical contact with the anion exchange membrane 30, and water permeates the anion exchange membrane 30 from the first conductive porous member 20 and is supplied to the cathode chamber.
  • hydroxide ions are consumed by an anode reaction to generate oxygen gas and water
  • water is consumed by a cathode reaction to generate hydrogen gas and hydroxide ions.
  • Oxygen gas generated by the anode reaction in the anode chamber flows through the first conductive porous member 20 together with the anode liquid and flows out from the anode liquid/gas outflow path 83 .
  • Hydrogen gas generated by the cathode reaction in the cathode chamber flows through the second conductive porous member 40 and flows out from the cathode chamber gas outflow path 83 .
  • FIG. 16 is a cross-sectional view taken along line BB of FIG. 2, that is, a cross-sectional view of the anode chamber.
  • the frame member 60 and the first conductive porous member 20 are shown in FIG. FIG. 16 also shows openings (64, 65: see also FIG. 11) facing the anode chamber of the anolyte inflow passage 81, and openings (66: See also FIG. 11).
  • the anode chamber is a region not occupied by the first electrically conductive porous member 20, which is provided in fluid communication with the anolyte inlet channel 81 and which is the first It further includes a distributed region 81 a extending in the outer peripheral direction of the first conductive porous member 20 along a portion of the outer peripheral edge of the conductive porous member 20 . At least part of the anolyte flowing into the anode chamber enters the first conductive porous member 20 via the dispersion region 81a (arrows B, C).
  • the dispersion region 81a includes the inner peripheral portion of the frame member 60 (that is, the anolyte distribution groove 65 provided in the inner peripheral portion of the frame member 60: see also FIG. 11) and the first conductive It is defined between the outer periphery of the porous member 20 .
  • the conventional AEM type water electrolyzer 900 FIG. 1
  • the anolyte that has flowed into the anode chamber from the anolyte inlet channel 912 flows through the first channel groove 911 provided on the surface of the first partition wall 910 and the first flow channel 911 . and the gas diffusion layer 920 , and out of the anolyte/gas outflow path 913 .
  • the first gas diffusion layer 920 is arranged parallel to this anolyte flow. That is, in the anode chamber of the conventional AEM-type water electrolyzer 900, the anode liquid introduced from the anode liquid inflow passage 912 into the first flow groove 911 passes only through the first flow groove 911 to the anode chamber. and the anolyte seeps into the first gas diffusion layer 920 from the first flow channel 911 and flows through the inside of the first gas diffusion layer 920 . There are two streams in parallel, one flowing back to and out of the anode chamber.
  • the flow field in which the anolyte permeates the first conductive porous member 20 is such that the anolyte flows from the anolyte inflow channel 81 into the anode chamber and the anolyte/gas outflow channel. It is arranged in series with the flow exiting from 82 . That is, in order for the anolyte that has flowed in from the anolyte inflow channel 81 to flow out from the anolyte/gas outflow channel 82, the anolyte must pass through the first conductive porous member 20 at least in the in-plane direction (the plane of FIG. 2). up-down direction).
  • the anolyte that has flowed into the anode chamber flows substantially only through the first conductive porous member 20, excluding the dispersion region 81a, and flows out of the anode chamber.
  • the expression that the anolyte "substantially flows only through the first conductive porous member 20" means that the anolyte inevitably flows through the outer surface of the first conductive porous member 20 and other members. It means that the anolyte other than the part that can flow through the contact portions with (for example, the anion exchange membrane 30 , the first partition wall 10 , the frame member 60 ) flows only through the first conductive porous member 20 .
  • the anolyte may flow from the first conductive porous member 20.
  • a flow that seeps into the contact portion between the first conductive porous member 20 and another member and returns to the first conductive porous member 20 may inevitably occur.
  • "A part of the anolyte that can inevitably flow through the contact part” means a part of the anolyte that makes this flow.
  • Non-uniform bubble distribution on current-carrying surface In the conventional AEM-type water electrolyzer 900 (FIG. 1), oxygen gas generated by the anodic reaction joins the flow of the anolyte from the first gas diffusion layer 920. come. Therefore, while the anolyte flows through the first channel groove 911, the number of oxygen gas bubbles in the anolyte increases. , non-uniform bubble distribution occurs. Since the bubbles in the anolyte act as a resistance to the electrolysis current, the non-uniform distribution of the bubbles acts to make the current density non-uniform between the upstream side and the downstream side inside the anode chamber.
  • Non-uniform temperature distribution on current-carrying surfaces In the conventional AEM water electrolyzer 900 (Fig. 1), the anolyte adjusted to a temperature suitable for the electrolytic reaction is allowed to flow from the anolyte inlet channel 912 into the anode chamber. Even so, the temperature of the anolyte differs between the upstream side and the downstream side in the anode chamber due to heat radiation from the main body of the electrolytic cell 900 and generation of electrolysis heat, resulting in non-uniform temperature distribution. Since the solution resistance changes depending on the temperature of the anolyte, this non-uniform temperature distribution acts to cause non-uniform current density between the upstream side and the downstream side within the anode chamber.
  • the openings (64, 65: see also FIG. 11) of the anolyte inflow passage 81 facing the anode chamber (64, 65: see also FIG. 11) correspond to the openings (66: 11).
  • the anolyte that has flowed into the anode chamber from the anolyte inlet channel 81 flows into the first conductive porous member 20 from the upper side of the outer peripheral portion of the first conductive porous member 20 (arrows A, B, and C), together with the gas generated in the anode chamber, flows out from the lower outer peripheral portion of the first conductive porous member 20 and enters the anolyte/gas outflow path 82 (arrows D and E).
  • the anolyte flows downward from above, at least from a macroscopic point of view.
  • This flow direction is in contrast to the conventional AEM-type water electrolyzer 900 (FIG. 1).
  • the conventional AEM type water electrolysis cell 900 the anolyte flows into the anode chamber from the lower side of the anode chamber and flows out from the upper side of the anode chamber. That is, the flow of the anolyte in the anode chamber of the conventional AEM-type water electrolyzer 900 is substantially in the same direction as the buoyancy of gas bubbles generated in the anode chamber.
  • the flow of the anolyte in the anode chamber of the electrolytic cell 100 is substantially opposite to the direction of buoyancy (arrow F) of gas bubbles generated in the anode chamber. Therefore, in the electrolytic cell 100, the anolyte flowing inside the first conductive porous member 20 is agitated (arrow G) by the buoyancy (arrow F) of gas bubbles generated in the anode chamber. Uneven concentration distribution of the anolyte inside the anode chamber (factor (i) above), uneven bubble distribution inside the anode chamber (factor (ii) above), and uneven temperature distribution inside the anode chamber (Factor (iii) above) can also be reduced. According to such an electrolytic cell 100, non-uniformity in the current density distribution can be further reduced, so it is possible to further reduce deterioration in performance with the lapse of operating time.
  • the anode chamber is the area not occupied by the first electrically conductive porous member 20, which is provided in fluid communication with the anolyte inlet channel 81 and which is of the first electrically conductive type. It includes a dispersed region 81a extending in the outer peripheral direction of the first conductive porous member 20 along a portion of the outer peripheral edge of the porous member 20 (FIG. 16). At least part of the anolyte flowing into the anode chamber enters the first conductive porous member 20 via the dispersion region 81a (arrows B, C).
  • the dispersion region 81a includes the inner peripheral portion of the frame member 60 (that is, the anolyte distribution groove 65 provided in the inner peripheral portion of the frame member 60: see also FIG. 11) and the first conductive It is defined between the outer periphery of the porous member 20 . According to the electrolytic cell 100 having such a dispersion region 81a, the position where the anolyte flows into the first conductive porous member 20 can be widened in the width direction (horizontal direction in FIG. 16).
  • the uniformity of the flow rate distribution of the anolyte in the first conductive porous member 20 can be improved, and therefore the non-uniformity of the concentration distribution of the anolyte in the anode chamber (factor (i) above), the anode chamber It is possible to further reduce the nonuniformity of bubble distribution inside (factor (ii) above) and the nonuniformity of temperature distribution inside the anode chamber (factor (iii) above). According to such an electrolytic cell 100, non-uniformity in the current density distribution can be further reduced, so it is possible to further reduce deterioration in performance with the lapse of operating time.
  • FIG. 17 is a diagram for explaining the shape of the current-carrying portion in the electrolytic cell 100, and is a view showing the current-carrying portion superimposed on the CC cross-sectional view of FIG. 2, in which the anion exchange membrane 30 appears.
  • the region 30a occupied by the conducting portion in the anion exchange membrane 30 is indicated by cross hatching.
  • the conducting portion 30a an area where the anion exchange membrane 30 is in contact with the first conductive porous member 20 and an area where the anion exchange membrane 30 is in contact with the second conductive porous member 40 overlap each other. defined as As shown in FIG. 17, the electrolytic cell 100 has a circular conducting portion 30a.
  • the phenomenon that the anolyte stays locally is less likely to occur. Therefore, uneven concentration distribution of the anolyte inside the anode chamber (factor (i) above), uneven bubble distribution inside the anode chamber (factor (ii) above), and It is possible to further reduce the uneven temperature distribution (factor (iii) above).
  • non-uniformity of the current density distribution can be further reduced, so it is possible to further reduce deterioration in performance with the lapse of operating time. Similar benefits can be obtained with electrolytic cells having elliptical or oblong current-carrying parts in addition to circular ones.
  • FIG. 18 is a cross-sectional view schematically illustrating an anion exchange membrane type water electrolytic cell 200 (hereinafter sometimes referred to as "electrolytic cell 200") according to such another embodiment. 2 corresponds to FIG. In FIG. 18, the up-down direction on the paper surface is the vertical up-down direction, and the upper side on the paper surface is the vertical upper side.
  • the electrolytic cell 200 includes a conductive first partition 210, a first conductive porous member 220, an anion exchange membrane 230, a second conductive porous member 240, and a conductive second partition. 250 and , in the above order.
  • An anode compartment is defined between the first partition 210 and the anion exchange membrane 230
  • a cathode compartment is defined between the second partition 250 and the anion exchange membrane 230 .
  • the first conductive porous member 220 and the first partition 210 are in at least electrical contact.
  • Electrolytic cell 200 further includes anolyte inlet channels 281-1, 281-2 (not visible in FIGS. 18-20), and 281-3 (not visible in FIGS. 18-20) that allow anolyte to flow into the anode chamber. , an anolyte/gas outflow path 282 for outflowing anolyte and gas from the anode chamber, and a cathode chamber gas outflow path 283 for outflowing gas from the cathode chamber.
  • the electrolytic cell 200 includes a frame member 260 that holds the outer peripheries of the first conductive porous member 220 and the second conductive porous member 240 and defines the outer periphery of the anode chamber and the outer periphery of the cathode chamber. is further provided.
  • the anolyte inflow channels 281 - 1 , 281 - 2 , 281 - 3 , the anolyte/gas outflow channel 282 , and the cathode chamber gas outflow channel 283 are provided through the frame member 260 .
  • the electrolytic cell 200 further includes a gasket 270 arranged in contact with the anion exchange membrane 230 and the frame member 260 to keep the anode chamber and the cathode chamber watertight and airtight.
  • FIG. 21 is a plan view of the first partition wall 210 and corresponds to FIG.
  • FIG. 22 is a plan view of the second partition wall 250 (view taken along line HH in FIG. 20) and corresponds to FIG.
  • the second partition wall 250 includes anolyte supply through holes 250h1-1, 250h1-2, and 250h1-3, an anolyte/gas recovery through hole 250h2, and a cathode chamber gas recovery through hole 250h2. It has a hole 250h3.
  • the anolyte supply through hole 250h1-1 constitutes a part of the anolyte inflow channel 281-1
  • the anolyte supply through hole 250h1-2 constitutes a part of the anolyte inflow channel 281-2.
  • the supply through-hole 250h1-3 constitutes a part of the anolyte inflow passage 281-3
  • the anolyte/gas recovery through-hole 250h2 constitutes a part of the anolyte/gas outflow passage 282, and recovers the cathode chamber gas.
  • the through-hole 250h3 constitutes a part of the cathode chamber gas outlet passage 283. As shown in FIG. As shown in FIG. 21, the first partition 210 is not provided with these through holes.
  • the rigid conductive material having alkali resistance described above in relation to the first partition 10 and the second partition 50 can be used, The preferred aspects are also the same as above.
  • FIG. 23(A) is a plan view of the first conductive porous member 220 and corresponds to FIG. 7(A).
  • the first conductive porous member 220 is a plate-like conductive porous member, and can be received from the first surface 260a side of the frame member 260 in a main through hole 260h0 of the frame member 260, which will be described later. and is sandwiched between the first partition wall 210 and the anion exchange membrane 230 .
  • the first conductive porous member 220 allows the anolyte and the gas to flow at least in the in-plane direction (that is, the up-down direction and the depth direction in FIGS. 18 to 20).
  • the first conductive porous member 220 allows the anolyte and the gas to flow also in the thickness direction (that is, the lateral direction of the paper of FIGS. 18 to 20).
  • the material of the first conductive porous member 220 the rigid conductive material having alkali resistance described above in relation to the first conductive porous member 20 can be used. is the same as above.
  • the plate-shaped member made of the open-cell porous metal (metallic porous body) described above in relation to the first conductive porous member 20 is used. It can be preferably employed, and its preferred embodiment is also the same as described above.
  • FIG. 23(B) is a plan view of the anion exchange membrane 30 and corresponds to FIG. 7(B).
  • the anion exchange membrane 230 has dimensions that allow it to be received from the first surface 260a side of the frame member 260 in a main through hole 260h0 of the frame member 260, which will be described later. It is sandwiched between the portion 262 and the first conductive porous member 220 .
  • the anion-exchange membrane 230 the anion-exchange membrane having the ability to exchange hydroxide ions and having alkali resistance, which is described above in relation to the anion-exchange membrane 30, and which is permeable to water, is particularly used. It can be adopted without limitation, and its preferred mode is also the same as above.
  • FIG. 24(A) is a plan view of the second conductive porous member 240 and corresponds to FIG. 8(A).
  • the second conductive porous member 240 is a plate-like second conductive porous member, and can be received in a main through hole 260h0 of the frame member 260, which will be described later, from the second surface 260b side. and is sandwiched between the anion exchange membrane 230 and the second partition 250 .
  • Second electrically conductive porous member 240 also has dimensions that allow it to be received in gasket 270 .
  • the second conductive porous member 240 is a conductive porous member through which at least gas can flow.
  • the second conductive porous member 240 is arranged in the in-plane direction (ie, the vertical direction and the depth direction in FIGS. 18 to 20) and the thickness direction (ie, in FIGS. 18 to 20).
  • the gas can flow in the left and right direction of the paper surface.
  • the material of the second conductive porous member 240 the rigid conductive material described above in relation to the second conductive porous member 40 can be used, and its preferred embodiment is also the same as described above.
  • the second conductive porous member 240 the plate-shaped member made of the open-cell porous metal (metallic porous body) described above in relation to the second conductive porous member 40 is used. It can be preferably employed, and its details and preferred embodiments are also the same as above.
  • the electrolytic cell 200 further includes an oxygen-generating anode catalyst (not shown) arranged in the anode chamber and a hydrogen-generating cathode catalyst (not shown) arranged in the cathode chamber.
  • anode catalyst and the cathode catalyst the anode catalyst and the cathode catalyst described above in relation to the electrolytic cell 100 can be used, respectively, and the preferred embodiments thereof are also the same as above.
  • the anode catalyst is preferably supported on the surface of the first conductive porous member 220 or the anion exchange membrane 230 facing the anode chamber, and the cathode catalyst is preferably supported on the second conductive porous member 240. Alternatively, it is supported on the cathode chamber side surface of the anion exchange membrane 230 . In one preferred embodiment, the anode catalyst is carried on the first electrically conductive porous member 220 .
  • the cathode catalyst may be supported on the second conductive porous member 240, or may be supported on the surface of the anion exchange membrane 230 facing the cathode chamber. preferably.
  • FIG. 24(B) is a plan view of the gasket 270 and corresponds to FIG. 8(B).
  • the gasket 270 has a dimension that allows it to be inserted from the first surface 260a side into the main through hole 260h0 of the frame member 260, which will be described later. and the anion exchange membrane 230 to keep the anode and cathode chambers watertight and airtight.
  • Gasket 270 is preferably made of an elastomer having alkali resistance.
  • the materials described above in relation to the gasket 70 can be used, and the preferred aspects thereof are also the same as described above.
  • the frame member 260 includes a frame-shaped base 261 (hereinafter sometimes simply referred to as "base 261") having a main through hole 260h0, and has a first surface 260a and a second surface 260b (FIG. 20).
  • . 25 is a plan view of the frame member 260 (a view of the frame member 260 taken along line AA in FIG. 20) and corresponds to FIG.
  • a first surface 260a of the frame member 260 is shown in FIG.
  • FIG. 26 is a bottom view of the frame member 260 (a view of the frame member 260 taken along line GG in FIG. 20), and corresponds to FIG.
  • a second surface 260b of the frame member 260 is shown in FIG.
  • the frame-shaped base body 261 further includes anolyte supply through holes 260h1-1, 260h1-2, 260h1-2, 260h1-1, 260h1-2, 260h1-2, 260h1-2, 260h1-2, 260h1-2, 260h1-2, 260h1-2, 260h1-1, 260h1-2, 260h1-1, 260h1-2, 260h1-2, 260h1-2, 260h1-2, 260h1-2, 260h1-2, 260h1-2, 260h1-2, 260h1-2, 260h1-1, 260h1-2, and 260h1-2. and 260h1-3, an anolyte/gas recovery through hole 260h2, and a cathode chamber gas recovery through hole 260h3.
  • the anolyte supply through holes 260h1-1, 260h-2, and 260h-3 of the frame member 260 correspond to the anolyte supply through holes 250h1-1, 250h1-2, and 250h1- of the second partition wall 250, respectively.
  • the anode liquid/gas recovery through-hole 260h2 and the cathode chamber gas recovery through-hole 260h3 of the frame member 260 are provided in the second partition wall 250 for anode liquid/gas recovery through-holes 260h2 and 260h3, respectively. It is provided at a position corresponding to the hole 250h2 and the cathode chamber gas recovery through hole 250h3.
  • the anolyte supply through hole 260h1-1 constitutes a part of the anolyte inflow channel 281-1
  • the anolyte supply through hole 260h1-2 constitutes a part of the anolyte inflow channel 281-2.
  • the supply through-hole 260h1-3 constitutes part of the anode liquid inflow path 281-3
  • the anode liquid/gas recovery through-hole 260h2 constitutes part of the anode liquid/gas outflow path 282, and cathode chamber gas recovery.
  • the through-hole 260h3 constitutes a part of the cathode chamber gas outlet passage 283. As shown in FIG.
  • the frame member 260 further includes an AEM positioning portion 262 protruding inwardly along the inner peripheral portion of the frame-shaped base 261 and an AEM positioning portion 262 extending along the inner peripheral portion of the frame-shaped base 261 .
  • a gasket positioning portion 263 is provided so as to protrude further toward the inner peripheral side.
  • the inner peripheral portion of the frame member 260 the inner peripheral portion of the base 261, the inner peripheral portion of the AEM positioning portion 262, and the inner peripheral portion of the gasket positioning portion 263 are arranged in the thickness direction of the frame member 260 (that is, the horizontal direction of the paper surface of FIG. 20). ) are arranged in this order.
  • the first surface 260a, the AEM positioning portion 262, and the gasket positioning portion 263 form a stepped shape (see FIG. 20).
  • 25 which is a plan view of the frame member 260
  • the AEM positioning portion 262 and the gasket positioning portion 263 are shown together with the first surface 260a of the frame member 260.
  • FIG. 26 which is a bottom view of the frame member, the second surface 260b of the frame member 260 and the inner peripheral portion of the gasket positioning portion 263 are shown.
  • the frame-shaped base 261, the AEM positioning portion 262, and the gasket positioning portion 263 of the frame member 260 may be integrally formed, and separately formed members may be integrally fixed in a specific arrangement.
  • the frame member 260 may be formed by
  • FIG. 27 is a BB cross-sectional view of the frame member 260 in FIG. 20, corresponding to FIG. FIG. 27 also shows the main through-hole 260h0, the anode liquid supply through-holes 260h1-1, 260h1-2, and 260h1-3, the anode liquid/gas recovery through-hole 260h2, and the cathode chamber gas recovery through-hole 260h3. ing.
  • FIG. 27 also shows the inner peripheral portion of the frame-shaped base 261 facing the main through hole 260h0.
  • the frame member 260 is provided in the vicinity of the first surface 260a so as to extend along part of the inner peripheral portion of the frame-shaped base body 261.
  • the frame member 260 is provided in the vicinity of the first surface 260a so as to provide fluid communication between the anolyte supply through holes 260h1-2 and the main through holes 260h0. It further comprises an anolyte supply groove 264-2 that opens toward 260h0 and provides fluid communication between the anolyte supply through holes 260h1-3 and the main through hole 260h0 in the vicinity of the first surface 260a.
  • the anolyte supply groove 264-1 and the anolyte distribution groove 265 open toward the uppermost vertex of the regular hexagonal main through-hole 260h0, and the anolyte supply grooves 264-2 and 264-2 are hexagonal. are open toward the other two upper vertices of the main through-hole 260h0.
  • the frame member 260 is also provided to provide fluid communication between the anolyte and gas recovery through holes 260h2 and the main through holes 260h0 in the vicinity of the first surface 260a.
  • An anolyte/gas recovery groove 266 that opens toward the hole 260h0 is further provided. The anolyte/gas recovery groove 266 opens toward the lowermost vertex of the regular hexagonal main through-hole 260h0.
  • FIG. 28 is a CC cross-sectional view of the frame member 260 in FIG. 20, corresponding to FIG. FIG. 28 also shows the main through-hole 260h0, the anode liquid supply through-holes 260h1-1, 260h1-2, and 260h1-3, the anode liquid/gas recovery through-hole 260h2, and the cathode chamber gas recovery through-hole 260h3. ing.
  • FIG. 28 also shows the inner peripheral portion of the frame-shaped base 261 facing the main through hole 260h0.
  • FIG. 29 is a DD cross-sectional view of the frame member 260 in FIG. 20, and corresponds to FIG. FIG. 29 also shows the main through hole 260h0, the anode liquid supply through holes 260h1-1, 260h1-2, and 260h1-3, the anode liquid/gas recovery through hole 260h2, and the cathode chamber gas recovery through hole 260h3. ing.
  • FIG. 29 also shows the inner peripheral portion of the AEM positioning portion 262 facing the main through hole 260h0.
  • FIG. 30 is a DD cross-sectional view of the frame member 260 in FIG. 20, and corresponds to FIG. FIG. 30 also shows the main through-hole 260h0, the anode liquid supply through-holes 260h1-1, 260h1-2, and 260h1-3, the anode liquid/gas recovery through-hole 260h2, and the cathode chamber gas recovery through-hole 260h3. ing.
  • FIG. 30 also shows the inner peripheral portion of the gasket positioning portion 263 facing the main through hole 260h0.
  • FIG. 31 is a cross-sectional view of the frame member 260 taken along line FF of FIG. 20, and corresponds to FIG.
  • FIG. 31 also shows the main through hole 260h0, the anode liquid supply through holes 260h1-1, 260h1-2, and 260h1-3, the anode liquid/gas recovery through hole 260h2, and the cathode chamber gas recovery through hole 260h3.
  • FIG. 31 also shows the inner peripheral portion of the gasket positioning portion 263 facing the main through hole 260h0. As shown in FIGS.
  • the frame member 260 is provided in the vicinity of the second surface 260b so as to provide fluid communication between the cathode chamber gas recovery through hole 260h3 and the main through hole 260h0, It further includes a cathode chamber gas recovery groove 267 that opens toward the second surface 260b and the main through hole 260h0.
  • the frame member 260 is electrically insulating against voltage application from the outside.
  • the materials described above for the frame member 60 can be used, and the preferred aspects thereof are also the same as described above.
  • the gasket 270, the anion exchange membrane 230, and the first conductive porous member 220 are inserted into the main through hole 260h0 of the frame member 260 in this order from the first surface 260a side, and the second conductive porous member 240 is inserted into the main through hole 260h0 of the frame member 260 from the second surface 260b side.
  • the first partition 210 is fixed to the first surface 260a of the frame member 260
  • the second partition 250 is fixed to the second surface 260b of the frame member 260, whereby the first partition 210 and the anion exchange membrane 230 , and a cathode chamber is defined between the second partition 250 and the anion exchange membrane 230 .
  • the second partition wall 250 communicates with the anode liquid supply through hole 250h1-1 of the second partition wall 250 with the anode liquid supply through hole 260h1-1 of the frame member 260, and the anode of the second partition wall 250 is connected.
  • the liquid supply through-hole 250h1-2 communicates with the anode liquid supply through-hole 260h1-2 of the frame member 260, and the anode liquid supply through-hole 250h1-3 of the second partition wall 250 communicates with the frame member 260 for anode liquid supply.
  • the anode liquid/gas recovery through-hole 250h2 of the second partition 250 communicates with the anode liquid/gas recovery through-hole 260h2 of the frame member 260, and the cathode chamber of the second partition 250 communicates with the through-hole 260h1-3. It is fixed to the second surface 260b of the frame member 260 so that the gas recovery through-hole 250h3 communicates with the cathode chamber gas recovery through-hole 260h3 of the frame member 260. As shown in FIG.
  • the anolyte distribution groove 265 and the anolyte supply groove 264-1 (FIGS. 25 and 27) opened in the first surface 260a of the frame member 260 are covered by the first partition wall 210 to form the anolyte inlet channel 281.
  • the anolyte/gas recovery groove 266 (FIGS. 25 and 27) opened in the first surface 260a of the frame member 260 is covered by the first partition wall 210 and partially serves as the anolyte/gas outlet channel 282.
  • a cathode chamber gas recovery groove 267 (FIGS. 26 and 31) opened in the second surface 260b of the frame member 260 is covered by the second partition wall 250 and constitutes a part of the cathode chamber gas outflow path 283. .
  • the anode liquid supply through hole 250h1-1 of the second partition wall 250, the anode liquid supply through hole 260h1-1 of the frame member 260, and the opening facing the first surface 260a of the frame member 260 The anolyte distribution groove 265 and the anolyte supply groove 264-1, whose parts are closed by the first partition wall 210, communicate with each other to form an integrated anolyte inflow path 281-1.
  • the anode liquid supply through-hole 250h1-2 of the second partition wall 250, the anode liquid supply through-hole 260h1-2 of the frame member 260, and the opening toward the first surface 260a of the frame member 260 are the first
  • the anode fluid supply groove 264-2 closed by the partition wall 210 communicates with the anode fluid supply groove 264-2 to form an integral anode fluid inlet channel 281-2.
  • the anode liquid supply through hole 250h1-3 of the second partition wall 250, the anode liquid supply through hole 260h1-3 of the frame member 260, and the opening facing the first surface 260a of the frame member 260 are the first
  • the anode fluid supply groove 264-3 closed by the partition wall 210 communicates with the anode fluid supply groove 264-3 to form an integral anode fluid inlet channel 281-3.
  • the anode liquid/gas recovery through-hole 250h2 of the second partition wall 250, the anode liquid/gas recovery through-hole 260h2 of the frame member 260, and the opening toward the first surface 620a of the frame member 260 are the first.
  • the anode liquid/gas recovery groove 266 closed by the partition wall 210 communicates with the anode liquid/gas recovery groove 266 to form an integral anode liquid/gas outflow path 282 .
  • the cathode chamber gas recovery through-hole 250h3 of the second partition wall 250, the cathode chamber gas recovery through-hole 260h3 of the frame member 260, and the opening toward the second surface 260b of the frame member 260 are the second
  • An integral cathode chamber gas outlet passage 283 is formed by communicating with the cathode chamber gas recovery groove 267 closed by the partition wall 250 .
  • the gasket 270 is sandwiched between the gasket positioning portion 263 of the frame member 260 and the anion exchange membrane 230, and the anion exchange membrane 230 is sandwiched between the AEM positioning portion 262 of the frame member 260 and the first
  • the first conductive porous member 220 is sandwiched between the anion exchange membrane 230 and the first partition wall 210 .
  • the second conductive porous member 240 is sandwiched between the anion exchange membrane 230 and the second partition wall 250 .
  • the first partition wall 210 presses the first conductive porous member 220 , the anion exchange membrane 230 and the gasket 270 toward the frame member 260 .
  • the second partition 250 also presses the second conductive porous member 240 toward the anion exchange membrane 230 and the first conductive porous member 220 behind it.
  • the fixing means described above in relation to the electrolytic cell 100 can be used, and the preferred mode thereof is also the same as described above. .
  • the operation of electrolytic cell 200 will be described.
  • the electrolytic cell 200 is a dry cathode type electrolytic cell.
  • the first partition 210 is connected to the positive pole of the DC power supply, and the second partition wall 250 is connected to the negative pole of the DC power supply.
  • the anolyte that has flowed into the anode chamber from the anolyte inflow channels 281-1, 281-2, and 281-3 flows through the first conductive porous member 220 at least in the in-plane direction to produce the anolyte/gas. It flows out of the outflow path 282 .
  • the first conductive porous member 220 is in physical contact with the anion exchange membrane 230, and water permeates the anion exchange membrane 230 from the first conductive porous member 220 and is supplied to the cathode chamber.
  • hydroxide ions are consumed by an anode reaction to generate oxygen gas and water
  • water is consumed by a cathode reaction to generate hydrogen gas and hydroxide ions.
  • Oxygen gas generated by the anode reaction in the anode chamber flows through the first conductive porous member 220 together with the anode liquid and flows out from the anode liquid/gas outflow path 283 .
  • FIG. 32 is a cross-sectional view taken along the line BB of FIG. 18, that is, a cross-sectional view of the anode chamber, and corresponds to FIG.
  • the frame member 260 and the first conductive porous member 220 are shown in FIG.
  • Also shown in FIG. 32 are openings (264-1, 264-2, 264-3, 265; see also FIG.
  • the anode chamber is a region not occupied by the first conductive porous member 220, which is provided in fluid communication with the anolyte inlet channel 281-1, and It further includes a distributed region 281 a extending in the outer peripheral direction of the first conductive porous member 220 along a portion of the outer peripheral edge of the first conductive porous member 220 .
  • the dispersion region 281a includes the inner peripheral portion of the frame member 260 (that is, the anolyte distribution groove 265 provided in the inner peripheral portion of the frame member 260: see also FIG. 27) and the first conductive It is defined between the outer periphery of the porous member 220 .
  • the flow field in which the anolyte permeates the first conductive porous member 220 is such that the anolyte flows into the anode chamber from the anolyte inflow channels 281-1, 281-2, and 281-3. It is arranged in series with the flow exiting the anolyte/gas outlet 282 . That is, in order for the anolyte that has flowed in from the anolyte inflow channels 281-1, 281-2, and 281-3 to flow out from the anolyte/gas outflow channel 282, the anolyte must flow through the first conductive porous member 220. must flow at least in the in-plane direction (vertical direction on the paper surface of FIG. 18).
  • the anolyte that has flowed into the anode chamber flows substantially only through the first conductive porous member 220, except for the dispersion region 281a, and flows out of the anode chamber. That is, here, the expression that the anolyte "flows substantially only through the first conductive porous member 220" means that the anolyte inevitably flows through the outer surface of the first conductive porous member 220 and other surfaces. (for example, the anion exchange membrane 230, the first partition wall 210, and the frame member 260). do.
  • the anolyte may flow from the first conductive porous member 220.
  • a flow that seeps into the contact portion between the first conductive porous member 220 and another member and returns to the first conductive porous member 220 may inevitably occur.
  • "A part of the anolyte that can inevitably flow through the contact part” means a part of the anolyte that makes this flow.
  • the electrolytic cell 200 also uses the conductive porous member (220) itself as a flow path for the anolyte. Therefore, non-uniformity of current density distribution can be reduced. Therefore, like the electrolytic cell 100, the electrolytic cell 200 can also reduce deterioration in performance over time.
  • openings facing the anode chamber of the anolyte inflow channels 281-1, 281-2, and 281-3 is arranged above the opening (266: see also FIG. 27) of the anode liquid/gas outflow path 282 facing the anode chamber.
  • the anolyte that has flowed into the anode chamber from the anolyte inflow channels 281-1, 281-2, and 281-3 flows from the upper peripheral portion of the first conductive porous member 220 to the first conductive porous member 220.
  • the member 220 It flows into the member 220 (arrows A1 to A3, B, and C1 to C3), flows out from the lower outer peripheral portion of the first conductive porous member 220 together with the gas generated in the anode chamber, and flows out through the anode liquid/gas outflow path 282. (arrows D and E). That is, in the anode chamber of electrolytic cell 200, as in electrolytic cell 100, the anolyte flows downward from above, at least from a macroscopic point of view. As in the electrolytic cell 100, the flow of the anolyte in the anode chamber of the electrolytic cell 200 is substantially opposite to the direction of buoyancy (arrow F) of gas bubbles generated in the anode chamber.
  • the anolyte flowing inside the first conductive porous member 220 is agitated (arrow G) by the buoyancy (arrow F) of gas bubbles generated in the anode chamber.
  • Uneven concentration distribution of the anolyte inside the anode chamber (factor (i) above), uneven bubble distribution inside the anode chamber (factor (ii) above), and uneven temperature distribution inside the anode chamber (Factor (iii) above) can also be reduced. Even with such an electrolytic cell 200, it is possible to further reduce the non-uniformity of the current density distribution, so that it is possible to further reduce the deterioration in performance with the lapse of operating time.
  • the anode chamber is the area not occupied by the first conductive porous member 220 and provided in fluid communication with the anolyte inlet channel 281-1. It includes a dispersed region 281a extending in the outer peripheral direction of the first electrically conductive porous member 220 along a portion of the outer peripheral edge of the electrically conductive porous member 220 (Fig. 32). At least part of the anolyte flowing into the anode chamber enters the first conductive porous member 220 via the dispersion region 281a (arrows B, C1).
  • the dispersion region 281a includes the inner peripheral portion of the frame member 260 (that is, the anolyte distribution groove 265 provided in the inner peripheral portion of the frame member 260: see also FIG. 27) and the first conductive It is defined between the outer periphery of the porous member 220 . Even with the electrolytic cell 200 having such a dispersed region 281a, the position where the anolyte flows into the first conductive porous member 220 can be widened in the width direction (horizontal direction of the paper surface of FIG. 32).
  • the uniformity of the flow rate distribution of the anolyte in the first conductive porous member 220 can be improved, so that the non-uniformity of the concentration distribution of the anolyte inside the anode chamber (factor (i) above), the inside of the anode chamber It is possible to further reduce the non-uniformity of bubble distribution in the anode chamber (factor (ii) above) and the non-uniformity of temperature distribution in the anode chamber (factor (iii) above). Even with such an electrolytic cell 200, it is possible to further reduce the non-uniformity of the current density distribution, so that it is possible to further reduce the deterioration in performance with the lapse of operating time.
  • FIG. 33 is a diagram for explaining the shape of the current-carrying portion in the electrolytic cell 200, and corresponds to FIG. In FIG. 33, in which the anion exchange membrane 230 appears, the region 230a occupied by the conducting portion in the anion exchange membrane 230 is indicated by cross hatching. Conducting portion 230 a overlaps a region where anion exchange membrane 230 is in contact with first conductive porous member 220 and a region where anion exchange membrane 230 is in contact with second conductive porous member 240 . defined as As shown in FIG. 33, the electrolytic cell 200 has a hexagonal (regular hexagonal) conducting portion 230a.
  • the electrolytic cell 200 having such a polygonal current-carrying part, the anolyte is less likely to stay locally, so the uniformity of the flow rate distribution of the anolyte in the first conductive porous member 220 is improved. Therefore, uneven concentration distribution of the anolyte inside the anode chamber (factor (i) above), uneven bubble distribution inside the anode chamber (factor (ii) above), and It is possible to further reduce the non-uniformity of the temperature distribution (factor (iii) above). Even with such an electrolytic cell 200, it is possible to further reduce the non-uniformity of the current density distribution, so that it is possible to further reduce the deterioration in performance with the lapse of operating time.
  • the conducting portion has a polygonal shape
  • the number of vertices is preferably four or more, more preferably five or more, and the polygon may have rounded vertices.
  • the opening of the anolyte inflow passage facing the anode chamber is generally the most vertical of the current-carrying portions. It is preferable to include an opening facing the upper portion, and the opening facing the anode chamber of the anolyte/gas outflow passage is provided facing the most vertically lower portion of the current-carrying portion.
  • one vertex of the polygonal current-carrying portion may be arranged at the uppermost or lowermost position in the vertical direction of the current-carrying portion.
  • the number of vertices of the polygonal current-carrying portion is an even number.
  • an electrolytic cell having a fan-shaped current-carrying portion can provide similar benefits.
  • the arc part of the fan-shaped current-carrying part is arranged on the uppermost side of the current-carrying part in the vertical direction. It is preferable that the apex of the portion is arranged on the most vertically lower side of the current-carrying portion.
  • the opening of the anolyte inflow path facing the anode chamber preferably includes an opening facing the arc portion of the fan-shaped current-carrying part, and the opening of the anolyte/gas outflow path facing the anode chamber preferably includes a fan-shaped opening.
  • the current-carrying part may have a shape having a larger area than the original triangle, in which one side of the triangle is replaced by an arc having a different radius than the other two sides.
  • the opening facing the anode chamber of the anolyte inflow passage is the convex curved portion of the current-carrying portion, from the viewpoint of further improving the uniformity of the flow rate distribution of the anolyte.
  • the opening facing the anode chamber of the outflow passage is an opening facing the most vertically lower vertex of the vertices of the current-carrying portion and/or the most vertical of the convex curved portions of the current-carrying portion. It preferably includes an opening facing the lower curve.
  • one vertex of the expanding polygonal current-carrying portion is arranged at the most vertically upper side or the most vertically lower side of the current-carrying portion.
  • one of the convex curved portions of the expanded polygonal current-carrying portion is arranged at the uppermost position in the vertical direction of the current-carrying portion, and the opening facing the anode chamber of the anolyte inflow passage is It preferably includes an opening facing the convex curve.
  • one of the convex curved portions of the expanded polygonal current-carrying portion is arranged at the lowermost position in the vertical direction of the current-carrying portion, and is an opening facing the anode chamber of the anolyte/gas outflow passage.
  • the section includes an opening facing the convex curved section.
  • one of the convex curved portions (the first curved portion) of the expanding polygonal current-carrying portion is arranged on the uppermost side of the current-carrying portion in the vertical direction.
  • the other curved portion (the second curved portion) is arranged at the lowest vertically lower side of the current-carrying portion, and the opening facing the anode chamber of the anolyte inflow passage is the first curved portion. and the opening facing the anode chamber of the anolyte/gas outlet channel may include an opening facing the second curved portion. preferable.
  • one convex curved portion of the expanded triangle is arranged at the uppermost position in the vertical direction of the current-carrying portion, and a vertex facing the convex curved portion.
  • the current-carrying part is arranged at the lowermost position in the vertical direction.
  • the opening facing the anode chamber of the anolyte/gas outlet channel is at the lowermost vertical vertex of the expansion triangle (i.e., at the uppermost vertically convex curve). It preferably includes openings provided facing the opposite apex portions.
  • the first conductive porous member is preferably a plate-like conductive porous member having a circular, oval, elliptical, polygonal, fan-shaped, or expanded polygonal planar shape.
  • the first conductive porous member 20 described above in relation to the electrolytic cell 100 is a plate-like conductive porous member having a circular planar shape, and is the same as the first conductive porous member described in relation to the electrolytic cell 200 .
  • the conductive porous member 220 of is a plate-like conductive porous member having a regular hexagonal planar shape.
  • the number of vertices is preferably 4 or more, more preferably 5 or more, and the polygon has rounded vertices. may have.
  • the opening facing the anode chamber of the anolyte inflow passage is generally provided so as to face the most vertically upper portion of the first conductive porous member.
  • the opening facing the anode chamber of the anolyte/gas outflow path is the opening provided facing the most vertically lower portion of the first conductive porous member. It is preferable to include a part.
  • the planar shape of the first conductive porous member is a polygon
  • the polygon has an even number of vertices.
  • one vertex of the polygon is the most vertically upper side or the most vertically It is preferably arranged in the downward direction.
  • the apex of the fan-shaped member is arranged at the lowermost position in the vertical direction of the first conductive porous member.
  • the opening facing the anode chamber of the channel preferably comprises an opening facing the arc portion of the sector-shaped first electrically conductive porous member
  • the opening facing the anode chamber of the anolyte/gas outflow channel preferably comprises: , preferably includes openings facing apex portions facing arcuate portions of the sector-shaped first electrically conductive porous member.
  • the opening facing the anode chamber of the anolyte/gas outflow path is an opening facing the most vertically lower vertex of the vertices of the expansion polygon; and
  • one vertex of the first conductive porous member of the expanded polygon may be arranged at the most vertically upper side or the most vertically lower side of the first conductive porous member. preferable.
  • one of the convex curved portions of the expanded polygonal first conductive porous member is arranged on the uppermost side in the vertical direction of the first conductive porous member, and the anolyte is
  • the opening facing the anode chamber of the inflow passage includes an opening facing the convex curved portion.
  • one of the convex curved portions of the first conductive porous member having an expanded polygonal shape is arranged at the most vertically lower side of the first conductive porous member, and the anode It is preferable that the opening of the liquid/gas outlet channel facing the anode chamber includes an opening facing the convex curved portion.
  • one of the convex curved portions (first curved portion) of the expanded polygonal first conductive porous member is the most vertically upper side of the first conductive porous member. and the other one (second curved portion) of the convex curved portions of the expanded polygonal first conductive porous member is the most vertically downward of the first conductive porous member and the opening facing the anode chamber of the anolyte inflow passage comprises an opening facing the first curved portion, and the anolyte/gas outflow passage faces the anode chamber.
  • the opening includes an opening facing the second curved portion.
  • one convex curved portion of the expansion triangle is arranged on the uppermost side in the vertical direction of the first conductive porous member. It is preferable that the apex facing the convex curved portion is arranged on the most vertically lower side of the first conductive porous member, and the opening facing the anode chamber of the anolyte inflow passage. preferably includes an opening facing the uppermost convex curved portion of the expansion triangle, and the opening facing the anode chamber of the anolyte/gas outflow passage is located at the most vertical position of the expansion triangle. It preferably includes an opening facing the vertically lower vertex (ie, the vertex facing the most vertically upper convex curved portion).
  • FIG. 34 is a cross-sectional view schematically illustrating an anion exchange membrane type water electrolytic cell 300 (hereinafter sometimes referred to as "electrolytic cell 300") according to such another embodiment, and FIG.
  • FIG. 34 the up-down direction on the paper surface is the vertical up-down direction, and the upper side on the paper surface is the vertical upper side.
  • FIG. 35 is a cross-sectional view taken along line AA of FIG. 34, corresponding to FIG.
  • FIG. 36 is an exploded view of FIG. 34 and a view corresponding to FIG.
  • the electrolytic cell 300 includes a conductive first partition wall 10, a first conductive porous member 320, an anion exchange membrane 330, a conductive carbon mesh 390, and a second conductive porous member 340. , and a conductive second partition wall 50 in the above order.
  • An anode compartment is defined between the first partition 10 and the anion exchange membrane 330
  • a cathode compartment is defined between the second partition 50 and the anion exchange membrane 330 .
  • the first conductive porous member 320 and the first partition wall 10 are in at least electrical contact.
  • the second conductive porous member 340 and the second partition wall 50 are in at least electrical contact.
  • the first conductive porous member 320 and the first partition wall 10 are in direct contact
  • the second conductive porous member 340 and the second partition wall 50 are in direct contact.
  • the electrolytic cell 300 further includes an anolyte inflow passage 381 for inflowing the anolyte into the anode chamber, an anolyte/gas outflow passage 382 for outflowing the anolyte and gas from the anode chamber, and a cathode chamber gas for outflowing gas from the cathode chamber. and an outflow channel 383 .
  • the electrolytic cell 300 includes a frame member 360 that holds the outer peripheries of the first conductive porous member 320 and the second conductive porous member 340 and defines the outer periphery of the anode chamber and the outer periphery of the cathode chamber. is further provided.
  • the anolyte inflow path 381 , the anolyte/gas outflow path 382 , and the cathode chamber gas outflow path 383 are provided through the frame member 360 .
  • the electrolytic cell 300 further comprises a gasket 370 arranged in contact with the anion exchange membrane 330 and the frame member 360 to keep the anode chamber and the cathode chamber watertight and airtight.
  • FIG. 5 for the plan view of the first partition 10
  • FIG. 6 for the plan view of the second partition 50 (view from arrow GG in FIG. 36).
  • the anode liquid supply through hole 50h1 of the second partition wall 50 constitutes a part of the anode liquid inflow path 381
  • the anode liquid/gas recovery through hole 50h2 constitutes a part of the anode liquid/gas outflow path 382
  • the cathode chamber gas recovery through-hole 50 h 3 constitutes a part of the cathode chamber gas outflow path 383 .
  • FIG. 37(A) is a plan view of the first conductive porous member 320 and corresponds to FIG. 7(A).
  • the first conductive porous member 320 is a plate-like conductive porous member, and can be received from the first surface 360a side of the frame member 360 in a main through hole 360h0 of the frame member 360, which will be described later. and is sandwiched between the first partition wall 10 and the anion exchange membrane 330 .
  • the first conductive porous member 320 allows the anolyte and the gas to flow at least in the in-plane direction (that is, the up-down direction and the depth direction in FIGS. 34 to 36).
  • the first conductive porous member 320 allows the anolyte and the gas to flow also in the thickness direction (that is, the lateral direction of the paper of FIGS. 34 to 36).
  • the material of the first conductive porous member 320 the rigid conductive material having alkali resistance described above in relation to the first conductive porous member 20 can be used. is the same as above.
  • the plate-shaped member made of the open-cell porous metal (metal porous body) described above in relation to the first conductive porous member 20 is used. It can be preferably employed, and its preferred embodiment is also the same as described above.
  • FIG. 37(B) is a plan view of the anion exchange membrane 330 and corresponds to FIG. 7(B).
  • the anion exchange membrane 330 has dimensions that allow it to be received from the first surface 360a side of the frame member 360 in a main through hole 360h0 of the frame member 360, which will be described later. It is sandwiched between the portion 362 and the first conductive porous member 320 .
  • the anion-exchange membrane 330 the anion-exchange membrane having the ability to exchange hydroxide ions and having alkali resistance, which is described above in relation to the anion-exchange membrane 30, and which is permeable to water, is particularly used. It can be adopted without limitation, and its preferred mode is also the same as above.
  • FIG. 38(A) is a plan view of the second conductive porous member 340 and corresponds to FIG. 8(A).
  • the second conductive porous member 340 is a plate-like second conductive porous member, and can be received in a main through hole 360h0 of the frame member 360, which will be described later, from the second surface 360b side. and is sandwiched between a conductive carbon mesh 390 and the second partition wall 50, which will be described later.
  • Second electrically conductive porous member 340 also has dimensions that allow it to be received in gasket 370 .
  • the second conductive porous member 340 is a conductive porous member through which at least gas can flow.
  • the second conductive porous member 340 is arranged in the in-plane direction (that is, the vertical direction and the depth direction of the paper in FIGS. 34 to 36) and the thickness direction (that is, in FIGS. The gas can flow in the left and right direction of the paper surface.
  • the material of the second conductive porous member 340 the rigid conductive material described above in relation to the second conductive porous member 40 can be used, and its preferred embodiment is also the same as described above.
  • the second conductive porous member 340 the plate-like member made of open-cell porous metal (metallic porous body) described above in relation to the second conductive porous member 40 is used. It can be preferably employed, and its details and preferred embodiments are also the same as above.
  • the electrolytic cell 300 further includes an oxygen-generating anode catalyst (not shown) placed in the anode chamber and a hydrogen-generating cathode catalyst (not shown) placed in the cathode chamber.
  • anode catalyst and the cathode catalyst the anode catalyst and the cathode catalyst described above in relation to the electrolytic cell 100 can be used, respectively, and the preferred embodiments thereof are also the same as above.
  • the anode catalyst is preferably carried on the anode chamber side surface of the first conductive porous member 320 or the anion exchange membrane 330, and the cathode catalyst is preferably carried on the second conductive porous member 340. Alternatively, it is supported on the cathode chamber side surface of the anion exchange membrane 330 . In one preferred embodiment, the anode catalyst is carried on the first electrically conductive porous member 320 .
  • the cathode catalyst may be supported on the second conductive porous member 340, may be supported on the cathode chamber side surface of the anion exchange membrane 330, or may be supported on the conductive carbon mesh 390. It is preferably carried on the surface of the anion exchange membrane 330 on the cathode chamber side.
  • FIG. 38(B) is a plan view of the gasket 370 and corresponds to FIG. 8(B).
  • the gasket 370 has a dimension that allows it to be inserted from the first surface 360a side into the main through hole 360h0 of the frame member 360 described later, and the gasket positioning portion 363 of the frame member 360 described later. and the anion exchange membrane 330 to keep the anode and cathode chambers watertight and airtight.
  • Gasket 370 is preferably made of an elastomer having alkali resistance.
  • the materials described above in relation to the gasket 70 can be used, and the preferred aspects thereof are also the same as described above.
  • FIG. 38(C) is a plan view of a conductive carbon mesh 390 (hereinafter sometimes referred to as "carbon mesh 390").
  • the carbon mesh 390 has a dimension that allows it to be received from the second surface 360b side in a main through hole 360h0 of the frame member 360, which will be described later. It is sandwiched between the conductive porous member 340 and the conductive porous member 340 . Also, the carbon mesh 390 has dimensions that allow it to be received in the gasket 370 .
  • the provision of the carbon mesh 390 between the anion exchange membrane 330 and the second conductive porous member 340 facilitates keeping the cathode catalyst wet.
  • a conductive carbon mesh capable of retaining moisture can be used without particular limitation, and such carbon mesh is commercially available.
  • the frame member 360 includes a frame-shaped base 361 (hereinafter sometimes simply referred to as "base 361") having a main through hole 360h0, and has a first surface 360a and a second surface 360b (FIG. 36).
  • base 361 a frame-shaped base 361
  • FIG. 39 is a plan view of the frame member 360 (a view of the frame member 360 taken along line AA in FIG. 36) and corresponds to FIG.
  • the first surface 360a of the frame member 360 is shown in FIG.
  • FIG. 40 is a bottom view of the frame member 360 (a view of the frame member 360 taken along line GG in FIG. 36) and corresponds to FIG.
  • the second surface 360b of the frame member 360 is shown in FIG.
  • the frame-shaped base body 361 further includes through holes 360h1 for supplying anode fluid, and for recovering anode fluid and gas, which are provided on the outer peripheral side of the main through hole 360h0 so as to penetrate the first surface 360a and the second surface 360b. It has a through hole 360h2 and a cathode chamber gas recovery through hole 360h3.
  • the anolyte supply through-hole 360h1, the anolyte/gas recovery through-hole 360h2, and the cathode chamber gas recovery through-hole 360h3 of the frame member 360 correspond to the anolyte supply through-hole 50h1 of the second partition wall 50, They are provided at positions corresponding to the anolyte/gas recovery through-hole 50h2 and the cathode chamber gas recovery through-hole 50h3.
  • the anode liquid supply through-hole 360h1 constitutes a part of the anode liquid inflow passage 381
  • the anode liquid/gas recovery through-hole 360h2 constitutes a part of the anode liquid/gas outflow passage 382
  • the cathode chamber gas recovery through-hole 360h2 constitutes a part of the anode liquid/gas outflow passage 382.
  • the hole 360h3 constitutes a part of the cathode chamber gas outlet passage 383. As shown in FIG.
  • the frame member 360 further includes an AEM positioning portion 362 protruding inwardly along the inner peripheral portion of the frame-shaped base 361 and an AEM positioning portion 362 extending along the inner peripheral portion of the frame-shaped base 361 .
  • a gasket positioning portion 363 is provided so as to protrude further toward the inner peripheral side.
  • the inner peripheral portion of the frame member 360 the inner peripheral portion of the base 361, the inner peripheral portion of the AEM positioning portion 362, and the inner peripheral portion of the gasket positioning portion 363 are arranged in the thickness direction of the frame member 360 (that is, the horizontal direction of the paper surface of FIG. 36). ) are arranged in this order.
  • the first surface 360a, the AEM positioning portion 362, and the gasket positioning portion 363 form a stepped shape (see FIG. 36).
  • 39 which is a plan view of the frame member 360
  • the AEM positioning portion 362 and the gasket positioning portion 363 are shown together with the first surface 360a of the frame member 360.
  • FIG. 40 which is a bottom view of the frame member, the second surface 360b of the frame member 360 and the inner peripheral portion of the gasket positioning portion 363 are shown.
  • the frame-shaped base 361, the AEM positioning portion 362, and the gasket positioning portion 363 of the frame member 360 may be integrally formed, and separately formed members may be integrally fixed in a specific arrangement.
  • the frame member 360 may be formed by
  • FIG. 41 is a BB cross-sectional view of the frame member 360 in FIG. 36 and corresponds to FIG. FIG. 41 also shows the main through hole 360h0, the anode liquid supply through hole 360h1, the anode liquid/gas recovery through hole 360h2, and the cathode chamber gas recovery through hole 360h3.
  • FIG. 41 also shows the inner peripheral portion of the frame-shaped base 361 facing the main through hole 360h0.
  • the frame member 360 is provided in the vicinity of the first surface 360a to provide fluid communication between the anolyte supply through hole 360h1 and the main through hole 360h0. 1 surface 360a and the main through hole 360h0.
  • the anolyte supply groove 264 opens toward the uppermost vertex of the square main through-hole 360h0.
  • the frame member 360 is also provided to provide fluid communication between the anolyte and gas recovery through holes 360h2 and the main through holes 360h0 in the vicinity of the first surface 360a.
  • An anolyte/gas recovery groove 366 that opens toward the hole 360h0 is further provided.
  • the anolyte/gas recovery groove 366 opens toward the lowermost vertex of the square main through-hole 360h0.
  • FIG. 42 is a CC sectional view of the frame member 360 in FIG. 36 and corresponds to FIG. FIG. 42 also shows the main through hole 360h0, the anode liquid supply through hole 360h1, the anode liquid/gas recovery through hole 360h2, and the cathode chamber gas recovery through hole 360h3.
  • FIG. 42 also shows the inner peripheral portion of the frame-shaped base 361 facing the main through hole 360h0.
  • FIG. 43 is a DD cross-sectional view of the frame member 360 in FIG. 36 and corresponds to FIG. FIG. 43 also shows the main through hole 360h0, the anode liquid supply through hole 360h1, the anode liquid/gas recovery through hole 360h2, and the cathode chamber gas recovery through hole 360h3.
  • FIG. 43 also shows the inner peripheral portion of the AEM positioning portion 362 facing the main through hole 360h0.
  • FIG. 44 is an EE cross-sectional view of the frame member 360 in FIG. 36 and corresponds to FIG. FIG. 44 also shows the main through hole 360h0, the anode liquid supply through hole 360h1, the anode liquid/gas recovery through hole 360h2, and the cathode chamber gas recovery through hole 360h3.
  • FIG. 44 also shows the inner peripheral portion of the gasket positioning portion 363 facing the main through hole 360h0.
  • FIG. 45 is a cross-sectional view of the frame member 360 taken along line FF of FIG. 36, and corresponds to FIG. FIG. 45 also shows the main through hole 360h0, the anode liquid supply through hole 360h1, the anode liquid/gas recovery through hole 360h2, and the cathode chamber gas recovery through hole 360h3.
  • FIG. 45 also shows the inner peripheral portion of the gasket positioning portion 363 facing the main through hole 360h0. As shown in FIGS.
  • the frame member 360 is provided in the vicinity of the second surface 360b so as to provide fluid communication between the cathode chamber gas recovery through hole 360h3 and the main through hole 360h0, It further includes a cathode chamber gas recovery groove 367 that opens toward the second surface 360b and the main through hole 360h0.
  • the frame member 360 is electrically insulating against voltage application from the outside.
  • the materials described above for the frame member 60 can be used, and the preferred aspects thereof are also the same as those described above.
  • the gasket 370, the anion exchange membrane 330, and the first conductive porous member 320 are inserted into the main through hole 360h0 of the frame member 360 in this order from the first surface 360a side, and the conductive carbon mesh 390 and the first conductive porous member 320 are inserted in this order.
  • 2 conductive porous members 340 are inserted into the main through holes 360h0 of the frame member 360 in this order from the second surface 360b side.
  • the first partition 10 and the anion exchange membrane 330 By fixing the first partition 10 to the first surface 360a of the frame member 360 and fixing the second partition 50 to the second surface 360b of the frame member 360, the first partition 10 and the anion exchange membrane 330 , and a cathode chamber is defined between the second partition 50 and the anion exchange membrane 330 .
  • the anode liquid supply through hole 50h1, the anode liquid/gas recovery through hole 50h2, and the cathode chamber gas recovery through hole 50h3 of the second partition 50 are formed in the frame member 360, respectively.
  • An anolyte supply groove 364 (FIGS. 39 and 41) opened in the first surface 360a of the frame member 360 is covered by the first partition wall 10 and constitutes a part of the anolyte inlet channel 381.
  • the anolyte/gas recovery groove 366 (FIGS. 39 and 41) opened in the first surface 360a of the frame member 360 is covered by the first partition wall 10, and part of the anolyte/gas outlet channel 382 is covered.
  • a cathode chamber gas recovery groove 367 (FIGS. 40 and 45) opened in the second surface 360b of the frame member 360 is covered by the second partition wall 50 and constitutes a part of the cathode chamber gas outflow path 383. . 34 and 35, an anode liquid supply through hole 50h1 of the second partition wall 50, an anode liquid supply through hole 360h1 of the frame member 360, and an opening facing the first surface 360a of the frame member 360 are The anode fluid supply groove 364 closed by the first partition wall 10 communicates with the anode fluid supply groove 364 to form an integral anode fluid inflow passage 381 .
  • the anode liquid/gas recovery through-hole 50h2 of the second partition wall 50, the anode liquid/gas recovery through-hole 360h2 of the frame member 360, and the opening facing the first surface 360a of the frame member 360 are the first.
  • the anode liquid/gas recovery groove 366 closed by the partition wall 10 communicates with the anode liquid/gas recovery groove 366 to form an integral anode liquid/gas outflow path 382 .
  • cathode chamber gas recovery through-hole 50h3 of the second partition wall 50 the cathode chamber gas recovery through-hole 360h3 of the frame member 360, and the opening toward the second surface 360b of the frame member 360 are the second An integral cathode chamber gas outlet passage 383 is formed by communicating with the cathode chamber gas recovery groove 367 closed by the partition wall 50 .
  • the gasket 370 is sandwiched between the gasket positioning portion 363 of the frame member 360 and the anion exchange membrane 330, and the anion exchange membrane 330 is sandwiched between the AEM positioning portion 362 of the frame member 360 and the first
  • the first conductive porous member 320 is sandwiched between the anion exchange membrane 330 and the first partition wall 10 .
  • the conductive carbon mesh 390 is sandwiched between the anion exchange membrane 330 and the second conductive porous member 340, and the second conductive porous member 340 is sandwiched between the carbon mesh 390 and the second conductive porous member 340.
  • the first partition wall 10 presses the first conductive porous member 320 , the anion exchange membrane 330 and the gasket 370 toward the frame member 360 .
  • the second partition wall 50 also presses the second conductive porous member 340 and the carbon mesh 390 toward the anion exchange membrane 330 and the first conductive porous member 320 behind it.
  • the fixing means described above in relation to the electrolytic cell 100 can be used, and the preferred mode thereof is also the same as described above. .
  • the electrolytic cell 300 is a dry cathode type electrolytic cell.
  • the first partition 10 is connected to the positive pole of the DC power supply, and the second partition 50 is connected to the negative pole of the DC power supply.
  • the anolyte that has flowed into the anode chamber from the anolyte inflow channel 381 flows through the first conductive porous member 320 at least in the in-plane direction, and flows out from the anolyte/gas outflow channel 382 .
  • the first conductive porous member 320 is in physical contact with the anion exchange membrane 330, and water permeates the anion exchange membrane 330 from the first conductive porous member 320 and is supplied to the cathode chamber.
  • hydroxide ions are consumed by an anode reaction to generate oxygen gas and water
  • water is consumed by a cathode reaction to generate hydrogen gas and hydroxide ions.
  • Oxygen gas generated by the anode reaction in the anode chamber flows through the first conductive porous member 320 together with the anode liquid and flows out from the anode liquid/gas outflow path 383 .
  • Hydrogen gas generated by the cathode reaction in the cathode chamber flows through the second conductive porous member 340 and flows out from the cathode chamber gas outlet passage 383 .
  • FIG. 46 is a cross-sectional view taken along line BB of FIG. 34, that is, a cross-sectional view of the anode chamber, and corresponds to FIG.
  • the frame member 360 and the first conductive porous member 320 are shown in FIG.
  • FIG. 46 further shows an opening (364: see also FIG. 41) facing the anode chamber of the anolyte inflow passage 381 and an opening of the anolyte/gas outflow passage 382 facing the anode chamber in the electrolytic cell 300. (366: see also FIG. 41) is displayed.
  • the flow field in which the anolyte permeates the first conductive porous member 320 is such that the anolyte flows into the anode chamber from the anolyte inflow channel 381 and flows out from the anolyte/gas outflow channel 382 .
  • the anolyte must flow through the first conductive porous member 320 at least in the in-plane direction (the plane of FIG. 34). up-down direction).
  • the anolyte that has flowed into the anode chamber substantially flows only through the first conductive porous member 320 and flows out of the anode chamber. That is, here, the expression that the anolyte "flows substantially only through the first conductive porous member 320" means that the anolyte inevitably flows through the outer surface of the first conductive porous member 320 and other surfaces. (for example, the anion exchange membrane 330, the first partition 10, the frame member 360), the anolyte other than the part that can flow through the contact portion flows only through the first conductive porous member 320. do.
  • the anolyte may flow from the first conductive porous member 320.
  • a flow that seeps into the contact portion between the first conductive porous member 320 and another member and returns to the first conductive porous member 320 may inevitably occur.
  • "A part of the anolyte that can inevitably flow through the contact part” means a part of the anolyte that makes this flow.
  • the electrolyzer 300 also uses the conductive porous member (320) itself as a flow path for the anolyte, so that the non-uniformity of the liquid content in the first conductive porous member 320 can be reduced. Therefore, non-uniformity of current density distribution can be reduced. Therefore, like the electrolytic cell 100, the electrolytic cell 300 can also reduce deterioration in performance over time.
  • the opening facing the anode chamber (364: see also FIG. 41) of the anode fluid inflow passage 381 faces the anode chamber (366: see also FIG. 41) of the anode fluid/gas outflow passage 382. See.).
  • the anolyte that has flowed into the anode chamber from the anolyte inlet channel 381 flows into the first conductive porous member 320 from the upper side of the outer peripheral portion of the first conductive porous member 320 (arrows A and C).
  • the anolyte/gas outflow path 382 (arrows D and E). That is, in the anode chamber of the electrolytic cell 300 as well as in the electrolytic cell 100, the anolyte flows downward from above, at least from a macroscopic point of view. As in the electrolytic cell 100, the flow of the anolyte in the anode chamber of the electrolytic cell 300 is substantially opposite to the direction of buoyancy (arrow F) of gas bubbles generated in the anode chamber.
  • the anolyte flowing inside the first conductive porous member 320 is agitated (arrow G) by the buoyancy (arrow F) of gas bubbles generated in the anode chamber.
  • Uneven concentration distribution of the anolyte inside the anode chamber (factor (i) above), uneven bubble distribution inside the anode chamber (factor (ii) above), and uneven temperature distribution inside the anode chamber (Factor (iii) above) can also be reduced.
  • non-uniformity in the current density distribution can be further reduced, so it is possible to further reduce deterioration in performance with the lapse of operating time.
  • FIG. 47 is a diagram for explaining the shape of the current-carrying part in the electrolytic cell 300, and corresponds to FIG.
  • FIG. 47 is a cross-sectional view taken along line CC of FIG. 34, in which the anion exchange membrane 330 is shown, and a current-carrying portion superimposed thereon.
  • the region 330a occupied by the conducting portion in the anion exchange membrane 330 is represented by cross hatching.
  • Conducting portion 330 a overlaps a region where anion exchange membrane 330 is in contact with first conductive porous member 320 and a region where anion exchange membrane 330 is in contact with second conductive porous member 340 . defined as As shown in FIG.
  • the electrolytic cell 300 has a rectangular (square) conducting portion 330a. Even with the electrolytic cell 300 having such a polygonal current-carrying part, the anolyte is less likely to stay locally, so that the uniformity of the flow rate distribution of the anolyte in the first conductive porous member 320 is improved. Therefore, uneven concentration distribution of the anolyte inside the anode chamber (factor (i) above), uneven bubble distribution inside the anode chamber (factor (ii) above), and It is possible to further reduce the non-uniformity of the temperature distribution (factor (iii) above). With such an electrolytic cell 300 as well, non-uniformity in the current density distribution can be further reduced, so it is possible to further reduce deterioration in performance with the lapse of operating time.
  • FIG. 48 is a cross-sectional view schematically illustrating an anion exchange membrane type water electrolytic cell 400 (hereinafter sometimes referred to as "electrolytic cell 400") according to still another embodiment of the present invention. 2 corresponds to FIG.
  • the up-down direction on the paper surface is the vertical up-down direction
  • the upper side on the paper surface is the vertical upper side.
  • FIG. 49 is a cross-sectional view taken along line AA of FIG. 48, which corresponds to FIG.
  • FIG. 50 is an exploded view of FIG. 48, corresponding to FIG.
  • the electrolytic cell 400 includes a first electrolytic element 410 having a conductive first partition wall 411 and a first frame member 412 provided on the outer peripheral portion of the first partition wall 411;
  • An anion exchange membrane element 430 comprising a member 420, an anion exchange membrane 431 and a protective member 432 for holding the outer periphery of the anion exchange membrane 431, a conductive carbon mesh 490, and a second conductive porous member.
  • 440 and a second electrolysis element 450 having a conductive second partition 451 and a second frame member 452 provided on the outer periphery of the second partition 451 .
  • An anode compartment is defined between the first partition 411 and the anion exchange membrane 431
  • a cathode compartment is defined between the second partition 451 and the anion exchange membrane 431 .
  • the first conductive porous member 420 and the first partition 411 are in at least electrical contact.
  • the second conductive porous member 440 and the second partition 451 are in at least electrical contact.
  • first conductive porous member 420 and first partition 411 are in direct contact
  • second conductive porous member 440 and second partition 451 are in direct contact.
  • the electrolytic cell 400 further includes anolyte inflow channels 481-1, 481-2, and 481-3 for inflowing the anolyte into the anode chamber, and an anolyte/gas outflow channel 482 for outflowing the anolyte and gas from the anode chamber. , and a cathode chamber gas outflow path 483 for discharging gas from the cathode chamber.
  • the first electrolytic element 410 includes a conductive first partition 411 and a first frame member (flange portion) 412 provided on the outer peripheral portion of the first partition 411 .
  • the first frame member 412 holds the outer peripheral portion of the first conductive porous member 420 and defines the outer peripheral portion of the anode chamber.
  • anolyte inflow channels 481 - 1 , 481 - 2 and 481 - 3 and anolyte/gas outflow channel 482 are provided through first frame member (flange portion) 412 .
  • the second electrolytic element 450 also includes a conductive second partition wall 451 and a second frame member (flange portion) 452 provided on the outer peripheral portion of the second partition wall portion 451 .
  • the second frame member 452 holds the outer peripheral portion of the second conductive porous member 440 and defines the outer peripheral portion of the cathode chamber.
  • cathode chamber gas outflow path 483 is provided through first frame member (flange portion) 412 and second frame member (flange portion) 452 .
  • the electrolytic cell 400 is divided between the protective member 432 of the anion exchange membrane element 430 and the first frame member (flange portion) 412 of the first electrolytic element 410 and between the protective member 432 of the anion exchange membrane element 430 and the first electrolytic element 410 .
  • Gaskets 470 , 470 are arranged between the second frame member (flange portion) 452 of the two electrolytic elements 450 .
  • FIG. 51 is a plan view of the first electrolytic element 410 (a view taken along line AA in FIG. 50).
  • the first frame member 412 has a first surface 412a and a second surface 412b (Fig. 50).
  • 51 shows the first surface 412a of the first frame member 412 together with the first partition wall 411.
  • FIG. 52 is a bottom view of the first electrolytic element 410 (view along EE in FIG. 50).
  • the second surface 412b of the first frame member 412 is shown in FIG.
  • the first frame member 412 further includes anolyte supply through holes 412h1-1 and 412h1- provided on the outer peripheral side of the first partition wall 411 through the first surface 412a and the second surface 412b. 2 and 412h1-3, an anolyte/gas recovery through hole 412h2, and a cathode chamber gas recovery through hole 412h3.
  • the anolyte supply through-holes 412h1-1, 412h1-2, and 412h1-3 constitute parts of the anolyte inflow channels 481-1, 481-2, and 481-3, respectively.
  • the anode liquid/gas recovery through-hole 412 h 2 constitutes a part of the anode liquid/gas outflow path 482
  • the cathode chamber gas recovery through-hole 412 h 3 constitutes a part of the cathode chamber gas out-flow path 483 .
  • FIG. 53 is a BB cross-sectional view of the first electrolytic element 410 in FIG.
  • FIG. 53 also shows the anode liquid supply through holes 412h1-1, 412h1-2, and 412h1-3, the anode liquid/gas recovery through hole 412h2, and the cathode chamber gas recovery through hole 412h3.
  • FIG. 53 also shows the inner peripheral portion of the first frame member 412 .
  • the first frame member 412 is provided to provide fluid communication between the anolyte supply through-hole 412h1-1 and the anode chamber, the first surface 412a and the anode chamber.
  • An anolyte supply groove 413-2 and an anolyte supply through-hole 412h1-3 are provided to provide fluid communication between the anode chamber and the first surface 412a and the anode chamber.
  • An open anolyte supply groove 413-3 is provided in the vicinity of the first surface 412a. The anolyte supply grooves 413-1, 413-2, and 413-3 each open toward the top of the anode chamber.
  • the first frame member 412 is provided in the vicinity of the first surface 412a so as to provide fluid communication between the anolyte/gas recovery through holes 412h2 and the anode chamber. It further comprises an anolyte and gas recovery groove 414 that opens toward. The anolyte/gas recovery groove 414 opens toward the bottom of the anode chamber.
  • FIG. 54 is a CC cross-sectional view of the first electrolytic element 410 in FIG.
  • FIG. 54 also shows the anode liquid supply through holes 412h1-1, 412h1-2, and 412h1-3, the anode liquid/gas recovery through hole 412h2, and the cathode chamber gas recovery through hole 412h3.
  • FIG. 54 also shows the inner peripheral portion of the first frame member 412 .
  • FIG. 55 is a DD cross-sectional view of the first electrolytic element 410 in FIG. FIG. 55 also shows the anode liquid supply through holes 412h1-1, 412h1-2, and 412h1-3, the anode liquid/gas recovery through hole 412h2, and the cathode chamber gas recovery through hole 412h3.
  • the conductive first partition 411 and the first frame member 412 form an integrated member, that is, the first electrolytic element 410 .
  • the first partition wall 411 and the first frame member 412 of the first electrolytic element 410 may be integrally formed of the same material, and the separately formed members are fixed in a specific arrangement.
  • a first electrolytic element 410 may be formed.
  • the rigid conductive material having alkali resistance described above in relation to the first partition wall 10 can be employed, and its preferred mode is also the same as described above.
  • the first frame member 412 may be made of metal or an electrically insulating material.
  • the metal material forming the first frame member 412 include the alkali-resistant rigid conductive material described above for the first partition wall 10, and the preferred embodiment thereof is also the same as described above.
  • the electrically insulating material forming the first frame member 412 include the same electrically insulating material as the electrically insulating material described above for the frame member 60, and the preferred mode thereof is also the same as described above. be.
  • the first frame member 412 is preferably joined to the first partition walls 411 .
  • first frame member 412 and the first partition wall 411 made of an electrically insulating material known joining means such as bonding with an adhesive can be used.
  • first frame member 412 is made of metal
  • first partition wall 411 and the first frame member 412 may be joined or integrally formed.
  • metal-to-metal joining means such as welding and brazing can be used.
  • integrally forming the metal first frame member 412 and the first partition wall 411 known means such as casting, forging, and cutting can be used.
  • FIG. 56 is a plan view of the second electrolytic element 450 (a view taken along line FF in FIG. 50).
  • the second frame member 452 has a first surface 452a and a second surface 452b (Fig. 50).
  • 56 shows the first surface 452a of the second frame member 452 together with the second partition wall 451.
  • FIG. 57 is a bottom view of the second electrolytic element 450 (a view taken along line II in FIG. 50).
  • the second surface 452b of the second frame member 452 is shown in FIG.
  • the second frame member 452 further includes a cathode chamber gas recovery groove 455 provided on the outer peripheral side of the second partition wall 451 and opening to the first surface 452a.
  • Cathode chamber gas recovery groove 455 constitutes a part of cathode chamber gas outflow path 483 .
  • FIG. 58 is a GG cross-sectional view of the second electrolytic element 450 in FIG. FIG. 58 also shows the cathode chamber gas recovery groove 455 .
  • FIG. 58 also shows the inner peripheral portion of the first frame member 452 .
  • the cathode chamber gas recovery groove 455 opens toward the first surface 512a and the cathode chamber.
  • FIG. 59 is an HH cross-sectional view of the second electrolytic element 450 in FIG. 59 shows the inner periphery of the second frame member 452.
  • FIG. 59 is an HH cross-sectional view of the second electrolytic element 450 in FIG. 59 shows the inner periphery of the second frame member 452.
  • the conductive second partition 451 and the second frame member 452 form an integrated member, that is, the second electrolytic element 450 .
  • the second partition wall 451 and the second frame member 452 of the second electrolytic element 450 may be integrally formed of the same material, and the separately formed members are fixed in a specific arrangement.
  • a second electrolytic element 450 may be formed.
  • the rigid conductive material having alkali resistance described above in relation to the second partition wall 50 can be employed, and its preferred mode is also the same as described above.
  • the second frame member 452 may be made of metal or an electrically insulating material.
  • the metal material forming the second frame member 452 the rigid conductive material described above for the second partition wall 50 can be mentioned, and the preferred mode thereof is also the same as described above.
  • the electrically insulating material forming the second frame member 452 include the same electrically insulating material as the electrically insulating material described above for the frame member 60, and the preferred mode thereof is also the same as described above. be.
  • the second frame member 452 is made of an electrically insulating material
  • the second frame member 452 is preferably joined to the second partition walls 451 .
  • a known joining means such as bonding with an adhesive can be used.
  • the second frame member 452 is made of metal
  • the second partition wall 451 and the second frame member 452 may be joined or integrally formed.
  • known metal-to-metal joining means such as welding and brazing can be used.
  • known means such as casting, forging, and cutting can be used.
  • FIG. 60(A) is a plan view of the first conductive porous member 420 and the second conductive porous member 440.
  • the first conductive porous member 420 is a plate-like conductive porous member and sandwiched between the first partition wall 411 and the anion exchange membrane 431 .
  • the first conductive porous member 420 allows the anolyte and the gas to flow at least in the in-plane direction (that is, the up-down direction and the depth direction in FIGS. 48 to 50).
  • the first conductive porous member 420 allows the anolyte and the gas to flow also in the thickness direction (that is, the lateral direction of the paper of FIGS. 48 to 50).
  • the rigid conductive material having alkali resistance described above in relation to the first conductive porous member 20 can be used. is the same as above.
  • the first conductive porous member 420 the plate-shaped member made of the open-cell porous metal (metallic porous body) described above in relation to the first conductive porous member 20 is used. It can be preferably employed, and its preferred embodiment is also the same as described above.
  • the second conductive porous member 540 is a plate-like second conductive porous member, and is sandwiched between a conductive carbon mesh 490 and a second partition wall 451, which will be described later.
  • the second conductive porous member 440 is a conductive porous member through which at least gas can flow.
  • the second conductive porous member 440 is arranged in the in-plane direction (that is, the vertical direction and the depth direction of the paper in FIGS. 48 to 50) and the thickness direction (that is, in FIGS. The gas can flow in the left and right direction of the paper surface.
  • the rigid conductive material described above in relation to the second conductive porous member 40 can be used, and its preferred embodiment is also the same as described above.
  • the second conductive porous member 440 the plate-shaped member made of the open-cell porous metal (metallic porous body) described above in relation to the second conductive porous member 40 is used. It can be preferably employed, and its details and preferred embodiments are also the same as above.
  • FIG. 60(B) is a plan view of a conductive carbon mesh 490 (hereinafter sometimes referred to as "carbon mesh 490").
  • carbon mesh 490 is sandwiched between anion exchange membrane 331 and second conductive porous member 440 .
  • the carbon mesh 490 provided between the anion exchange membrane 331 and the second conductive porous member 440 facilitates keeping the cathode catalyst wet.
  • a conductive carbon mesh capable of retaining moisture can be used without particular limitation, and such carbon mesh is commercially available.
  • FIG. 61 is a plan view of the anion exchange membrane element 430 (view along JJ in FIG. 50).
  • the anion exchange membrane element 430 includes an anion exchange membrane 431 and a protective member 432 that holds the outer periphery of the anion exchange membrane 431 .
  • the anion exchange membrane 431 the anion exchange membrane having the ability to exchange hydroxide ions and having alkali resistance, which is described above in relation to the anion exchange membrane 30, and which is permeable to water is particularly used. It can be adopted without limitation, and its preferred mode is also the same as above.
  • the planar outline of the protective member 432 is the first surface 412 a of the first frame member 412 of the first electrolytic element 410 and the first surface of the second frame member 452 of the second electrolytic element 450 . 452a.
  • the protective member 432 has, on the outer peripheral side of the anion exchange membrane 431, anolyte supply through-holes 432h1-1, 432h1-2, and 432h1-3, an anolyte/gas recovery through-hole 432h2, and a cathode chamber gas recovery through-hole 432h2. It has a through hole 432h3.
  • the anolyte supply through-holes 432h1-1, 432h1-2, and 432h1-3 constitute parts of the anolyte inflow paths 481-1, 481-2, and 481-3, respectively.
  • the anode liquid/gas recovery through hole 432 h 2 constitutes a part of the anode liquid/gas outflow path 482
  • the cathode chamber gas recovery through hole 432 h 3 constitutes a part of the cathode chamber gas outflow path 483 .
  • the anode liquid supply through holes 432h1-1, 432h1-2, and 432h1-3 are the anode liquid supply through holes 412h1-1 and 412h1- provided in the first frame member 412 of the first electrolytic element 410, respectively.
  • the anode liquid/gas recovery through-hole 432h2 and the cathode chamber gas recovery through-hole 432h3 are provided in the first frame member 412 of the first electrolytic element 410, respectively. It is provided at a position corresponding to the room gas recovery through-hole 412h3.
  • the protection member 432 may be made of metal or may be made of an electrically insulating material.
  • the metal material forming the protective member 432 the alkali-resistant rigid conductive material described above for the first partition wall 10 can be mentioned, and the preferred aspects thereof are also the same as described above.
  • Examples of the electrically insulating material forming the protective member 432 include the same electrically insulating material as the electrically insulating material described above for the frame member 60, and the preferred aspects thereof are also the same as described above.
  • the electrolytic cell 400 further includes an oxygen generating anode catalyst (not shown) arranged in the anode chamber and a hydrogen generating cathode catalyst (not shown) arranged in the cathode chamber.
  • anode catalyst and the cathode catalyst the anode catalyst and the cathode catalyst described above in relation to the electrolytic cell 400 can be used, respectively, and preferred embodiments thereof are also the same as described above.
  • the anode catalyst is preferably carried on the first conductive porous member 420 or the surface of the anion exchange membrane 431 facing the anode chamber, and the cathode catalyst is preferably carried on the second conductive porous member 440. Alternatively, it is supported on the cathode chamber side surface of the anion exchange membrane 431 . In one preferred embodiment, the anode catalyst is carried on the first electrically conductive porous member 420 .
  • the cathode catalyst may be supported on the second conductive porous member 440, may be supported on the cathode chamber side surface of the anion exchange membrane 431, or may be supported on the conductive carbon mesh 490. It is preferably carried on the surface of the anion exchange membrane 431 on the cathode chamber side.
  • FIG. 62 is a plan view of each gasket 470 (view from arrow KK in FIG. 50).
  • Each gasket 470 includes a first surface 412a of the first frame member 412 of the first electrolytic element 410, a second surface 452a of the second frame member 452 of the second electrolytic element 450, and an anion exchange membrane. It has a planar shape corresponding to the protective member 432 of the element 430 . As shown in FIG.
  • each gasket 470 includes a main through-hole 470h0, anolyte supply through-holes 470h1-1, 470h1-2, and 470h1-3 provided on the outer peripheral side of the main through-hole 470h0, an anode It has a liquid/gas recovery through hole 470h2 and a cathode chamber gas recovery through hole 470h3.
  • the main through hole 470 h 0 has dimensions that allow it to receive the first conductive porous member 420 and the second conductive porous member 440 .
  • the anolyte supply through holes 470h1-1, 470h1-2, and 470h1-3 are the anolyte supply through holes 412h1-1 and 412h1- provided in the first frame member 412 of the first electrolytic element 410, respectively. 2, and 412h1-3.
  • the anode liquid/gas recovery through-hole 470h2 and the cathode chamber gas recovery through-hole 470h3 are formed in the first frame member 412 of the first electrolytic element 410, respectively. It is provided at a position corresponding to the room gas recovery through-hole 412h3.
  • Gasket 470 is preferably made of an elastomer having alkali resistance. As the material constituting the gasket 470, the materials described above in relation to the gasket 70 can be used, and the preferred aspects thereof are also the same as described above.
  • the first conductive porous member 420 is inserted from the first surface 412a side of the first electrolytic element 410, the first conductive porous member 420 and the first partition wall 411 are in contact with each other, and the first The outer peripheral portion of the conductive porous member 420 is held by the first frame member 412 .
  • the second conductive porous member 440 is inserted from the first surface 452a side of the second electrolytic element 450, and the second conductive porous member 440 and the second partition wall 451 are in contact with each other.
  • the outer peripheral portion of the conductive porous member 440 is held by the second frame member 452 .
  • the first electrolytic element 410 holding the first conductive porous member 420 and the anion exchange membrane element 430 are stacked with one gasket 470 interposed therebetween to form the first partition wall 411 and the anion exchange membrane.
  • 431 defines an anode chamber.
  • the second electrolytic element 450 holding the second conductive porous member 440 and the anion exchange membrane element 430 are stacked with the other gasket 470 and the carbon mesh 490 interposed therebetween to form a second partition wall 451. and the anion exchange membrane 431 defines a cathode compartment.
  • the first electrolytic element 410, the gasket 470 (on the anode chamber side), and the anion exchange membrane element 430 are connected to the anolyte supply through holes 412h1-1, 412h1-2, and 412h1- of the first electrolytic element 410.
  • 3, anolyte supply through holes 470h1-1, 470h1-2, and 470h1-3 of the gasket 470, and anolyte supply through holes 432h1-1, 432h1-2, and 432h1-3 of the anion exchange membrane element 430. are stacked so as to communicate with each other, the anolyte inflow channels 481-1, 481-2 and 481-3 and the anolyte/gas outflow channel 482 are integrally formed.
  • the second electrolytic element 450, the gasket 470 (cathode chamber side), and the anion exchange membrane element 430 are connected to the cathode chamber gas recovery through hole 432h3 of the anion exchange membrane element 430 and the cathode chamber gas recovery through hole 432h3 of the gasket 470.
  • the hole 470h3 and the cathode chamber gas recovery groove 455 of the second electrolytic element 450 are stacked so as to communicate with each other, thereby forming an integrated cathode chamber gas outflow path 483. As shown in FIG.
  • the operation of electrolytic cell 400 will be described.
  • the electrolytic cell 400 is a dry cathode type electrolytic cell.
  • the first partition 411 is connected to the positive pole of the DC power supply, and the second partition 451 is connected to the negative pole of the DC power supply.
  • the anolyte that has flowed into the anode chamber from the anolyte inflow channels 481-1, 481-2, and 481-3 flows through the first conductive porous member 420 at least in the in-plane direction to produce the anolyte/gas. It flows out from the outflow path 482 .
  • the first conductive porous member 420 is in physical contact with the anion exchange membrane 431, and water permeates the anion exchange membrane 430 from the first conductive porous member 420 and is supplied to the cathode chamber.
  • hydroxide ions are consumed by an anode reaction to generate oxygen gas and water
  • water is consumed by a cathode reaction to generate hydrogen gas and hydroxide ions.
  • Oxygen gas generated by the anode reaction in the anode chamber flows through the first conductive porous member 420 together with the anode liquid and flows out from the anode liquid/gas outflow path 483 .
  • FIG. 63 is a cross-sectional view taken along line BB of FIG. 48, that is, a cross-sectional view of the anode chamber, and corresponds to FIG.
  • FIG. 63 shows the first frame member 412 and the first conductive porous member 420 of the first electrolytic element 410 .
  • FIG. 63 also shows openings (413-1, 413-2, 413-3: see also FIG.
  • anolyte that has flowed into the anode chamber from the anolyte inflow channels 481-1, 481-2, and 481-3 flows from one of the outer peripheral portions of the first conductive porous member 420 to the first conductive porous member 420. (arrows A1 to A3, C1 to C3), flows out from the other side of the outer peripheral portion of the first conductive porous member 420 together with the gas generated in the anode chamber, and enters the anode liquid/gas outflow path 482 (arrow D and E).
  • the flow field in which the anolyte permeates the first conductive porous member 420 is such that the anolyte flows into the anode chamber from the anolyte inflow channels 481-1, 481-2, and 481-3. It is arranged in series with the flow exiting the anolyte/gas outlet 482 . That is, in order for the anolyte flowing in from the anolyte inflow channels 481-1, 481-2, and 481-3 to flow out from the anolyte/gas outflow channel 482, the anolyte must flow through the first conductive porous member 420. must flow at least in the in-plane direction (vertical direction on the paper surface of FIG. 48).
  • the anolyte that has flowed into the anode chamber substantially flows only through first conductive porous member 420 and flows out of the anode chamber. That is, here, the expression that the anolyte "substantially flows only through the first conductive porous member 420" means that the anolyte inevitably flows through the outer surface of the first conductive porous member 420 and other parts of the anolyte.
  • the anolyte other than the part that can flow through the contact with the member of e.g., the anion exchange membrane element 430, the first electrolytic element 410, the gasket 470
  • the anolyte may flow from the first conductive porous member 420.
  • a flow that seeps into the contact portion between the first conductive porous member 420 and another member and returns to the first conductive porous member 420 may inevitably occur.
  • "A part of the anolyte that can inevitably flow through the contact part” means a part of the anolyte that makes this flow.
  • the electrolytic cell 400 also uses the conductive porous member (420) itself as the flow path for the anolyte, so that the liquid content in the first conductive porous member 420 is reduced. Therefore, non-uniformity of current density distribution can be reduced. Therefore, like the electrolytic cell 100, the electrolytic cell 400 can also reduce deterioration in performance over time.
  • the member 420 It flows into the member 420 (arrows A1 to A3, C1 to C3), flows out from the lower outer peripheral portion of the first conductive porous member 420 together with the gas generated in the anode chamber, and enters the anode liquid/gas outflow path 482 ( Arrows D and E). That is, in the anode chamber of the electrolytic cell 400 as well as the electrolytic cell 100, the anolyte flows downward from above at least from a macroscopic point of view. As in the electrolytic cell 100, the flow of the anolyte in the anode chamber of the electrolytic cell 400 is substantially opposite to the direction of buoyancy (arrow F) of gas bubbles generated in the anode chamber.
  • the anolyte flowing inside the first conductive porous member 420 is agitated (arrow G) by the buoyancy (arrow F) of gas bubbles generated in the anode chamber.
  • Uneven concentration distribution of the anolyte inside the anode chamber (factor (i) above), uneven bubble distribution inside the anode chamber (factor (ii) above), and uneven temperature distribution inside the anode chamber (Factor (iii) above) can also be reduced. Even with such an electrolytic cell 400, it is possible to further reduce the non-uniformity of the current density distribution, so that it is possible to further reduce the deterioration of the performance with the lapse of operation time.
  • the anolyte introduced from the anolyte inflow channels 481-1, 481-2, and 481-3 to the anolyte supply grooves 413-1, 413-2, and 413-3 directly flows into the first
  • the anion-exchange membrane-type water electrolyzer 400 in which the water flows into the conductive porous member 420 is taken as an example, the present invention is not limited to this form.
  • the present invention is not limited to this form.
  • a dispersed region extending in the outer peripheral direction of the first conductive porous member (420) along a portion of the outer peripheral edge of the first conductive porous member (420), the dispersed region is defined between the inner periphery of the first frame member (412) and the outer periphery of the first electrically conductive porous member (420), and at least a portion of the anolyte flowing into the anode chamber is It is also possible to construct an anion-exchange membrane-type water electrolytic bath in which the first conductive porous member (420) is penetrated via the dispersion region.
  • the anion exchange membrane type water electrolytic cell 400 having three anolyte inflow channels 481-1, 481-2, and 481-3 was taken as an example. Not limited. For example, an anion exchange membrane type water electrolytic cell having four or more anolyte inflow channels may be used.
  • an anion exchange membrane type water electrolytic cell 300, 400 having a configuration in which one sheet of conductive carbon mesh (390, 490) is provided in the cathode chamber was exemplified, but the present invention is The form is not limited.
  • the number of carbon meshes arranged between the anion exchange membrane and the second conductive porous member in the cathode chamber is not particularly limited, but is preferably one or more, more preferably two or more. , and may be, for example, 3 or less.
  • FIG. 64 is a cross-sectional view schematically illustrating an anion exchange membrane type water electrolytic cell 1000 (hereinafter sometimes referred to as "electrolytic cell 1000") according to such another embodiment, and FIG. It is a figure corresponding to .
  • electrolytic cell 1000 an anion exchange membrane type water electrolytic cell 1000
  • FIG. 65 is a cross-sectional view taken along line AA of FIG. 64, which corresponds to FIG.
  • the electrolytic cell 1000 includes three electrolytic cells (electrolytic cells) 100, 100'a, and 100'b which are stacked in this order and electrically connected in series.
  • electrolytic cell 100 has the same configuration as electrolytic cell 100 (FIGS. 2 to 16) described above.
  • the conductive second partition wall constituting the electrolytic cell 100 is denoted by "50a”.
  • Electrolytic cells 100'a and 100'b differ from electrolytic cell 100 (FIG. 2) in that conductive first partition 10 (FIG. 5) of electrolytic cell 100 is replaced with partition 50 (FIG. 6). different.
  • the electrolytic cell 1000 includes conductive partition walls 10, 50a, 50b, and 50c in this order.
  • An electrolytic cell (electrolyte bath) 100'a is defined between the partition walls 50b and 50c, and an electrolytic cell (electrolytic bath) 100'b is defined between the partition walls 50b and 50c.
  • the partition wall 10 and the partition wall 50a are respectively the back partition wall of the anode chamber (first conductive partition wall) and the back partition wall of the cathode chamber (second conductive partition wall) in the electrolytic cell (electrolytic bath) 100.
  • partition 50a and the partition 50b are respectively the back partition of the anode chamber (first conductive partition) and the back partition of the cathode chamber (second conductive partition) in the electrolytic cell (electrolytic bath) 100′a
  • partition walls 50b and 50c are respectively the back partition wall (first conductive partition wall) of the anode chamber and the back partition wall (second conductive partition wall) of the cathode chamber in the electrolytic cell (electrolytic bath) 100′b ).
  • the partition wall 50 a is the rear partition wall (second conductive partition wall) of the cathode chamber in the electrolytic cell (electrolytic chamber) 100 and is adjacent to the cathode chamber side of the electrolytic cell (electrolytic chamber) 100 . It is also the rear partition wall (conductive first partition wall) of the anode chamber in the electrolysis cell (electrolysis tank) 100'a.
  • the partition wall 50b is a rear partition wall (second conductive partition wall) of the cathode chamber in the electrolytic cell (electrolytic bath) 100′a, and is located on the cathode chamber side of the electrolytic cell (electrolytic bath) 100′a.
  • partitions 50a and 50b are bipolar plates.
  • the cathode chamber rear partition wall 50a conductive second partition wall
  • the anode chamber rear partition wall 50b conductive In the electrolysis cell (electrolytic bath) 100'a, the anode chamber back partition 50a (conductive first partition) and the cathode chamber back partition 50b (conductive first partition) are bipolar plates. ) are bipolar plates.
  • the anolyte inflow channels 81 (see FIG. 2) of the electrolytic cells (electrolyte cells) 100, 100'a, and 100'b communicate with each other to form an integral unit.
  • An anolyte inflow path 1081 is formed.
  • the anolyte/gas outflow channels 82 (see FIG. 2) of the electrolytic cells (electrolytic baths) 100, 100'a, and 100'b communicate with each other to form an integrated anolyte/gas outflow channel 1082. is doing.
  • the cathode chamber gas outflow passages 83 (see FIG. 3) of the electrolytic cells (electrolytic baths) 100, 100'a, and 100'b communicate with each other to form an integrated cathode chamber gas flow path.
  • An outflow channel 1083 is formed.
  • the first partition 10 is connected to the positive electrode of the DC power supply, and the second partition 50c is connected to the negative electrode of the DC power supply.
  • the anolyte that has flowed into each of the anode chambers of the electrolytic cells (electrolyte tanks) 100, 100'a, and 100'b from the anolyte inlet channel 1081 flows through each first conductive porous member 20 at least in the in-plane direction. , and out of the anolyte/gas outflow path 1082 .
  • the first conductive porous member 20 is in physical contact with the anion exchange membrane 30, and water permeates the anion exchange membrane 30 from the first conductive porous member 20 to the cathode chamber.
  • each anode chamber hydroxide ions are consumed by an anode reaction to generate oxygen gas and water
  • water is consumed by a cathode reaction to generate hydrogen gas and hydroxide ions.
  • Oxygen gas generated by the anode reaction in each anode chamber flows through the first conductive porous member 20 together with the anode liquid and flows out from the anode liquid/gas outflow path 1083 .
  • Hydrogen gas generated by the cathode reaction in each cathode chamber flows through the second conductive porous member 40 and flows out from the cathode chamber gas outflow path 1083 .
  • Hydroxide ions generated by the cathode reaction in each cathode chamber are transported to the anode chamber by the anion exchange ability of the anion exchange membrane 30 .
  • an electrolytic bath 1000 as well, it is possible to obtain the same effects as those described above for the electrolytic bath 100 .
  • the anion exchange membrane type water electrolytic cell 1000 including three electrolytic cells was taken as an example, but the present invention is not limited to this form.
  • FIG. 66 is a cross-sectional view schematically illustrating an anion exchange membrane type water electrolytic cell 2000 (hereinafter sometimes referred to as "electrolytic cell 2000") according to still another embodiment of the present invention
  • FIG. 49 is a diagram corresponding to FIG. 48;
  • the up-down direction on the paper surface is the vertical up-down direction, and the upper side on the paper surface is the vertical upper side.
  • FIG. 67 is a cross-sectional view taken along line AA of FIG. 66, which corresponds to FIG.
  • FIG. 68 is an exploded view of FIG. 66 and a view corresponding to FIG. As shown in FIGS.
  • the electrolytic bath 2000 includes two electrolytic baths (electrolytic cells) 400'a and 400'b which are stacked in this order and electrically connected in series.
  • Electrolysis cell 400 ′a differs from electrolysis cell 400 (FIG. 48) in that the second electrolysis element 450 of electrolysis cell 400 is replaced by electrolysis element 2460 .
  • Electrolysis cell 400′b differs from electrolysis cell 400 (FIG. 48) in that the first electrolysis element 410 of electrolysis cell 400 is replaced by electrolysis element 2460.
  • Electrolysis cell 400′b is shown in FIG.
  • FIG. 69 is a cross-sectional view schematically explaining the electrolytic element 2460, and is a view of the electrolytic element 2460 extracted from FIGS. 66 and 68.
  • FIG. In FIG. 69 the up-down direction on the paper surface is the vertical up-down direction, and the upper side on the paper surface is the vertical upper side.
  • FIG. 70 is a cross-sectional view taken along the line AA of FIG. 69.
  • the electrolytic element 2460 includes a conductive partition wall 2461 having a first surface 2461a and a second surface 2461b, and a first frame member (flange portion) 2462 provided on the outer peripheral portion of the partition wall 2461.
  • a frame member (flange portion) 2462 is provided so as to protrude from the outer peripheral portion of the partition wall 2461 toward both the first surface 2461a side and the second surface 2461b side of the partition wall 2461 .
  • the frame member 2462 holds the outer peripheral portion of the first conductive porous member 420 and defines the outer peripheral portion of the anode chamber.
  • the frame member 2462 holds the outer peripheral portion of the second conductive porous member 440 and defines the outer peripheral portion of the cathode chamber.
  • the frame member 2462 is the first frame member in the electrolytic cell (electrolyte tank) 400'b and also the second frame member in the electrolytic cell (electrolyte tank) 400'a.
  • the anolyte inflow channels 2081-1, 2081-2, and 2081-3 and the anolyte/gas outflow channel 2082 are formed by a first frame member (flange portion) 412 and a frame member (flange portion). 2462 is provided.
  • the cathode chamber gas outflow path 2083 is provided through the first frame member (flange portion) 412 , the frame member (flange portion) 2462 and the second frame member (flange portion) 452 .
  • the electrolytic cell 2000 includes electrolytic elements 410, 2460, and 450 in this order, and an electrolytic cell (electrolytic bath) 400'a is provided between the first partition 411 of the electrolytic element 410 and the partition 2461 of the electrolytic element 2460. Between the partition 2461 of the electrolytic element 2460 and the second partition 451 of the electrolytic element 450, an electrolytic cell (electrolytic bath) 400'b is defined.
  • the partition 411 and the partition 2461 are respectively the back partition of the anode chamber (first conductive partition) and the back partition of the cathode chamber (second conductive partition) in the electrolytic cell 400′a.
  • the partition 2461 and the partition 451 are respectively the back partition of the anode chamber (first conductive partition) and the back partition of the cathode chamber (second conductive partition) in the electrolytic cell (electrolytic bath) 400′b. be. That is, in the electrolytic cell 2000, the partition wall 2461 is the rear partition wall (second conductive partition wall) of the cathode chamber in the electrolytic cell (electrolyte chamber) 400'a, and at the same time, the cathode of the electrolytic cell (electrolytic chamber) 400'a. It is also the rear partition wall (conductive first partition wall) of the anode chamber in the electrolysis cell (electrolytic bath) 400'b adjacent to the chamber side. Thus, in electrolytic cell 2000, partition 2461 is a bipolar plate and electrolytic element 2460 with partition 2461 is a bipolar element.
  • FIG. 71 is a plan view of the electrolytic element 2460 (view taken along line BB in FIG. 69) and corresponds to FIG.
  • the frame member 2462 has a first side 2462a and a second side 2462b (Fig. 69). 71 shows the first surface 2462a of the frame member 2462 together with the first surface 2461a of the partition wall 2461.
  • FIG. FIG. 72 is a bottom view of the electrolytic element 2460 (view from arrow HH in FIG. 69), corresponding to FIG. 72 shows the second surface 2462b of the frame member 2462 together with the second surface 2461b of the partition wall 2461.
  • FIG. 71 is a plan view of the electrolytic element 2460 (view taken along line BB in FIG. 69) and corresponds to FIG.
  • the frame member 2462 has a first side 2462a and a second side 2462b (Fig. 69). 71 shows the first surface 2462a of the frame member 2462 together with the first surface 2461a of the partition wall 24
  • the frame member 2462 further includes through holes 2462h1-1, 2462h1-2, and 2462h1-3 for supplying anolyte, which are provided on the outer peripheral side of the partition wall 2461 through the first surface 2462a and the second surface 2462b. , an anolyte/gas recovery through hole 2462h2, and a cathode chamber gas recovery through hole 2462h3.
  • the anolyte supply through-holes 2462h1-1, 2462h1-2, and 2462h1-3 constitute parts of the anolyte inflow paths 2081-1, 2081-2, and 2081-3, respectively.
  • the anode liquid/gas recovery through hole 2462 h 2 constitutes a part of the anode liquid/gas outflow path 2082
  • the cathode chamber gas recovery through hole 2462 h 3 constitutes a part of the cathode chamber gas outflow path 2083 .
  • FIG. 73 is a CC cross-sectional view of the electrolytic element 2460 in FIG. 69, corresponding to FIG. FIG. 73 also shows anolyte supply through-holes 2462h1-1, 2462h1-2, and 2462h1-3, anolyte/gas recovery through-hole 2462h2, and cathode chamber gas recovery through-hole 2462h3.
  • FIG. 73 also shows the inner periphery of frame member 2462 . As shown in FIGS. 73 and 71, the frame member 2462 is provided to provide fluid communication between the anolyte supply through holes 2462h1-1 and the anode chamber and faces the first surface 2462a and the anode chamber.
  • the anolyte supply groove 2463-1 and the anolyte supply through hole 2462h1-2 are provided to provide fluid communication between the anode chamber and the anode chamber, and open toward the first surface 2462a and the anode chamber.
  • An anolyte supply groove 2463-3 is provided in the vicinity of the first surface 2462a.
  • Anolyte supply grooves 2463-1, 2463-2, and 2463-3 are each open toward the top of the anode chamber.
  • the frame member 2462 is provided in the vicinity of the first surface 2462a so as to provide fluid communication between the anolyte/gas recovery through-hole 2462h2 and the anode chamber, and is directed toward the first surface 2462a and the anode chamber.
  • An open anolyte and gas collection channel 2464 is further provided.
  • the anolyte/gas recovery groove 2464 opens toward the bottom of the anode chamber.
  • FIG. 74 is a DD cross-sectional view of the electrolytic element 2460 in FIG. 69, corresponding to FIG. FIG. 74 also shows anolyte supply through-holes 2462h1-1, 2462h1-2, and 2462h1-3, anolyte/gas recovery through-hole 2462h2, and cathode chamber gas recovery through-hole 2462h3.
  • FIG. 74 also shows the inner periphery of frame member 2462 .
  • FIG. 75 is an EE cross-sectional view of the electrolytic element 2460 in FIG. 69, corresponding to FIG. FIG. 75 also shows anolyte supply through-holes 2462h1-1, 2462h1-2, and 2462h1-3, anolyte/gas recovery through-hole 2462h2, and cathode chamber gas recovery through-hole 2462h3.
  • FIG. 76 is a FF cross-sectional view of the electrolytic element 2460 in FIG. FIG. 76 also shows anolyte supply through-holes 2462h1-1, 2462h1-2, and 2462h1-3, anolyte/gas recovery through-hole 2462h2, and cathode chamber gas recovery through-hole 2462h3.
  • FIG. 76 also shows the inner periphery of frame member 2462 .
  • FIG. 77 is a GG cross-sectional view of the electrolytic element 2460 in FIG. FIG. 77 also shows anolyte supply through-holes 2462h1-1, 2462h1-2, and 2462h1-3, anolyte/gas recovery through-hole 2462h2, and cathode chamber gas recovery through-hole 2462h3.
  • FIG. 77 also shows the inner periphery of frame member 2462 .
  • the frame member 2462 is further provided on the outer peripheral side of the partition wall 2461 so as to provide fluid communication between the cathode chamber gas recovery through hole 2462h3 and the cathode chamber. It has a cathode chamber gas recovery groove 2465 that opens toward the surface 2462a and the cathode chamber. Cathode chamber gas recovery groove 2465 constitutes a part of cathode chamber gas outflow path 2083 .
  • the conductive partition wall 2461 and the frame member 2462 form an integrated member, that is, the electrolytic element 2460.
  • the partition wall 2461 and the frame member 2462 of the electrolytic element 2460 may be integrally formed of the same material, or the electrolytic element 2460 may be formed by separately formed members fixed in a specific arrangement. good.
  • the rigid conductive material having alkali resistance described above in relation to the first partition wall 10 can be employed, and the preferred mode thereof is also the same as described above.
  • the materials described above in relation to the first frame member 412 can be employed, and the preferred aspects thereof are also the same as described above.
  • the frame member 2462 is made of an electrically insulating material
  • the frame member 2462 is preferably joined to the partition walls 2461 .
  • a known joining means such as bonding with an adhesive can be used.
  • the partition wall 2461 and the frame member 2462 may be joined or integrally formed.
  • known metal-to-metal joining means such as welding or brazing can be used.
  • known means for integrally forming the metal frame member 2462 and the partition wall 2461 known means such as casting, forging, and cutting can be used.
  • the anolyte inflow channels 481-1 (see FIG. 48) of the electrolytic cells (electrolyte) 400'a and 400'b communicate with each other to form an integral anode.
  • a liquid inflow path 2081-1 is formed.
  • the anolyte inflow channels 481-2 of the electrolytic cells (electrolytic baths) 400′a and 400′b communicate with each other to form an integrated anolyte inflow channel 2081-2.
  • the anolyte inlets 481-3 of 400'a and 400'b communicate with each other to form an integrated anolyte inlet 2081-3.
  • anolyte supply through hole 432h1-1 provided in the protective member 432 of the membrane element 430 an anolyte supply through hole 470h1-1 provided in each gasket 470 of the electrolytic cell (electrolytic bath) 400'a
  • the anolyte supply through hole 2462h1-1 and the anolyte supply groove 2463-1 provided in the frame member 2462 of the electrolytic element 2460 communicate with each other to form an integrated anolyte inflow path 2081-1.
  • anolyte supply through-hole 462h1-2 and the anolyte supply groove 463-2 provided in the first frame member 412 of the first electrolytic element 410 and the anions of the electrolysis cell (electrolyte) 400'a
  • the anolyte supply through hole 2462h1-2 and the anolyte supply groove 2463-2 provided in the frame member 2462 of the electrolytic element 2460 communicate with each other to form an integrated anolyte inflow path 2081-2.
  • the anolyte supply through hole 2462h1-3 and the anolyte supply groove 2463-3 provided in the frame member 2462 of the electrolytic element 2460 communicate with each other to form an integrated anolyte inflow path 2081-3.
  • the liquid/gas recovery through-hole 462h2, the anode liquid/gas recovery through-hole 2462h2 provided in the frame member 2462 of the electrolytic element 2460, and the anode liquid/gas recovery groove 2464 communicate with each other, An integrated anolyte/gas outflow path 2082 is formed.
  • the cathode chamber gas outflow paths 83 (see FIG. 49) of the electrolytic cells (electrolyte cells) 400'a and 400'b communicate with each other to form an integral unit.
  • a cathode chamber gas outflow path 2083 is formed.
  • the partition 411 of the first electrolytic element 410 is connected to the positive electrode of the DC power supply, and the partition 451 of the second electrolytic element is connected to the negative electrode of the DC power supply.
  • the anolyte that has flowed from the anolyte inflow channel 2081 into each of the anode chambers of the electrolytic cells (electrolytic baths) 400'a and 400'b flows through each first conductive porous member 420 at least in its in-plane direction. , out of the anolyte/gas outflow path 2082 .
  • the first conductive porous member 420 is in physical contact with the anion exchange membrane 431, and water permeates the anion exchange membrane 431 from the first conductive porous member 420 to the cathode chamber.
  • hydroxide ions are consumed by an anode reaction to generate oxygen gas and water
  • water is consumed by a cathode reaction to generate hydrogen gas and hydroxide ions.
  • Oxygen gas generated by the anode reaction in each anode chamber flows through the first conductive porous member 420 together with the anode liquid and flows out from the anode liquid/gas outflow path 2083 .
  • Hydrogen gas generated by the cathode reaction in each cathode chamber flows through the second conductive porous member 440 and out of the cathode chamber gas outflow path 2083 . Hydroxide ions generated by the cathode reaction in each cathode chamber are transported to the anode chamber by the anion exchange ability of the anion exchange membrane 431 . With such an electrolytic bath 2000 as well, it is possible to obtain the same effects as those described above for the electrolytic bath 400 .
  • the anion exchange membrane type water electrolyzers 1000 and 2000 which are equipped with a plurality of electrolysis cells electrically connected in series and are equipped with conductive partition walls that are bipolar plates, are taken as examples.
  • the invention is not limited to this form.
  • Anion exchange membrane type water electrolytic cell 10 210, 411, 910 (conductive) first Partition wall 410 First electrolytic element 412 First frame member (flange portion) 911 first channel groove 912 anolyte inflow channel 913 anolyte/gas outflow channel 20, 220, 320, 420 first conductive porous member 920 (conductive) first gas diffusion layers 30, 230, 330, 431, 930 anion exchange membrane 430 anion exchange membrane element 432 protective member 40, 240, 340, 440 second conductive porous member 940 (conductive) second gas diffusion layer 50, 50c, 250, 451 , 950 (conductive) second partitions 50a, 50b, 2461 (conductive) partitions (bipolar plates) 450 second electrolytic element 452 second frame member (flange portion) 2460 (bipolar type) electrolytic element 2462 frame member (flange) 951 second channel groove 953 cath

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CN115807237A (zh) * 2022-12-08 2023-03-17 厦门阿威尔技术有限公司 分散式电化学电解槽制氢电解室及制氢装置
WO2024175350A1 (de) * 2023-02-21 2024-08-29 Robert Bosch Gmbh Elektrochemische zelle mit einer beschichteten membran
WO2024185460A1 (ja) * 2023-03-03 2024-09-12 三菱重工業株式会社 電解セルおよび電解装置
WO2024243644A1 (en) * 2023-06-01 2024-12-05 The University Of Adelaide Hydrogen production from seawater
JP7661548B1 (ja) 2024-02-06 2025-04-14 三菱重工業株式会社 電解セル、及び電解装置
JP2025160544A (ja) * 2024-04-10 2025-10-23 本田技研工業株式会社 差圧式電解装置

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JPS59197585A (ja) * 1983-03-21 1984-11-09 レイリー・インダストリーズ・インコーポレーテッド フイルタ−プレス型電気化学セル
JPH06349508A (ja) * 1993-04-30 1994-12-22 De Nora Permelec Spa イオン交換膜と二極金属板が設けられた改良電気化学電池
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WO2024243644A1 (en) * 2023-06-01 2024-12-05 The University Of Adelaide Hydrogen production from seawater
JP7661548B1 (ja) 2024-02-06 2025-04-14 三菱重工業株式会社 電解セル、及び電解装置
JP2025121114A (ja) * 2024-02-06 2025-08-19 三菱重工業株式会社 電解セル、及び電解装置
JP2025160544A (ja) * 2024-04-10 2025-10-23 本田技研工業株式会社 差圧式電解装置

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