WO2021153406A1 - 金属多孔体シート及び水電解装置 - Google Patents

金属多孔体シート及び水電解装置 Download PDF

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Publication number
WO2021153406A1
WO2021153406A1 PCT/JP2021/001983 JP2021001983W WO2021153406A1 WO 2021153406 A1 WO2021153406 A1 WO 2021153406A1 JP 2021001983 W JP2021001983 W JP 2021001983W WO 2021153406 A1 WO2021153406 A1 WO 2021153406A1
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WIPO (PCT)
Prior art keywords
metal porous
porous sheet
holes
main surface
along
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2021/001983
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English (en)
French (fr)
Japanese (ja)
Inventor
孝浩 東野
奥野　一樹
博匡 俵山
真嶋　正利
宗一郎 奥村
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Sumitomo Electric Industries Ltd
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Sumitomo Electric Industries Ltd
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Application filed by Sumitomo Electric Industries Ltd filed Critical Sumitomo Electric Industries Ltd
Priority to EP21748456.7A priority Critical patent/EP4098774A4/en
Priority to CN202180010040.2A priority patent/CN115003861A/zh
Priority to JP2021574688A priority patent/JPWO2021153406A1/ja
Priority to US17/793,541 priority patent/US20230080341A1/en
Publication of WO2021153406A1 publication Critical patent/WO2021153406A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
    • C25B11/031—Porous 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
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • 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 disclosure relates to a metal porous sheet and a water electrolyzer.
  • This application claims priority based on the international patent application PCT / JP2020 / 00239 filed on January 27, 2020. All statements contained in the international patent application are incorporated herein by reference.
  • Patent Document 1 Japanese Patent Publication No. 2005-536639 describes an electrode body. A wire mesh is used for the electrode body described in Patent Document 1.
  • Patent Document 2 Japanese Patent Publication No. 61-57397) describes an electrode for water electrolysis. A metal porous body having a three-dimensional network structure is used for the electrode for water electrolysis described in Patent Document 2.
  • the metal porous body sheet of the present disclosure is made of a metal porous body having a three-dimensional network structure, and includes a first main surface and a second main surface which is an opposite surface of the first main surface. A plurality of holes extending along a first direction from the first main surface to the second main surface are formed on the first main surface.
  • FIG. 1 is a plan view of the metal porous sheet 10.
  • FIG. 2 is a cross-sectional view taken along the line II-II of FIG.
  • FIG. 3 is a schematic view showing the internal structure of the metal porous sheet 10.
  • FIG. 4 is an enlarged cross-sectional view showing the internal structure of the metal porous sheet 10.
  • FIG. 5 is a cross-sectional view taken along the line VV of FIG.
  • FIG. 6 is a schematic view showing the unit cell structure of the metal porous body defined by the skeleton 11.
  • FIG. 7 is a schematic cross-sectional view of the unit cell of the water electrolyzer 100.
  • FIG. 8 is a schematic view for explaining the effect of the water electrolyzer 100 using the metal porous sheet 10.
  • FIG. 9 is a schematic view of the simplified water electrolyzer 110.
  • FIG. 10 is a graph showing the results of measuring the electrolytic voltage by changing the aperture ratio in the simple water electrolyzer 110.
  • FIG. 11 is a plan view of the metal porous sheet 10A.
  • FIG. 12 is a plan view of the metal porous sheet 10B.
  • FIG. 13 is a plan view of the metal porous sheet 10C.
  • FIG. 14 is a plan view of the metal porous sheet 10D.
  • FIG. 15 is a plan view of the metal porous sheet 10E.
  • FIG. 16 is a plan view of the metal porous sheet 10F.
  • FIG. 17 is a plan view of the metal porous sheet 10G.
  • FIG. 18 is a cross-sectional view of the metal porous sheet 10H along the first direction DR1.
  • FIG. 11 is a plan view of the metal porous sheet 10A.
  • FIG. 12 is a plan view of the metal porous sheet 10B.
  • FIG. 13 is a plan view of the metal porous sheet 10C.
  • FIG. 14 is
  • FIG. 19 is a cross-sectional view of the metal porous sheet 10I along the first direction DR1.
  • FIG. 20 is a cross-sectional view of the metal porous sheet 10J along the first direction DR1.
  • FIG. 21 is a schematic view for explaining the effect of the water electrolyzer 100 using the metal porous sheet 10H.
  • FIG. 22 is a plan view of the metal porous sheet 10K.
  • FIG. 23 is a plan view of the metal porous sheet 10L.
  • FIG. 24 is a plan view of the metal porous sheet 10M.
  • FIG. 25 is a plan view of the metal porous sheet 10N.
  • FIG. 26 is a plan view of the metal porous sheet 10O.
  • FIG. 27 is a plan view of the metal porous sheet 10P.
  • FIG. 28 is a plan view of the metal porous sheet 10Q.
  • FIG. 29 is a plan view of the metal porous sheet 10R.
  • FIG. 30 is a plan view of the metal porous sheet 10S.
  • FIG. 31 is a plan view of the metal porous sheet 10T.
  • FIG. 32 is a cross-sectional view taken along the line XXXII-XXXII of FIG.
  • FIG. 33 is a schematic cross-sectional view of the unit cell of the water electrolyzer 100A.
  • FIG. 34 is a plan view of the electrode 30a.
  • FIG. 35 is a plan view showing the first arrangement of the holes 10 g in the water electrolysis test.
  • FIG. 36 is a plan view showing a second arrangement of the holes 10 g in the water electrolysis test.
  • FIG. 37 is a plan view showing a third arrangement of the holes 10 g in the water electrolysis test.
  • the wire mesh used for the electrode body described in Patent Document 1 has a small surface area. Therefore, when the electrode body described in Patent Document 1 is used for water electrolysis, the electrolysis voltage becomes high.
  • the metal porous body used for the electrode for water electrolysis described in Patent Document 2 has a large surface area.
  • gas bubbles generated by water electrolysis tend to adhere to the inside. Since the portion to which the bubbles are attached does not contribute to the electrolysis reaction, even if the surface area is large, the metal porous body used for the electrode for water electrolysis described in Patent Document 2 has an electrolytic voltage when performing water electrolysis. Cannot be lowered.
  • the present disclosure provides a metal porous sheet and a water electrolysis apparatus capable of lowering the electrolysis voltage when performing water electrolysis.
  • the metal porous body sheet according to the first embodiment is made of a metal porous body having a three-dimensional network structure, and includes a first main surface and a second main surface which is an opposite surface of the first main surface. A plurality of holes extending along a first direction from the first main surface to the second main surface are formed on the first main surface.
  • each of the plurality of holes may penetrate the metal porous sheet along the first direction.
  • the inner diameter of each of the plurality of holes may decrease from the first main surface side to the second main surface side.
  • the first main surface may be divided into a plurality of regions along the second direction orthogonal to the first direction.
  • the inner diameter of the plurality of holes located in the first region, which is one of the plurality of regions, is smaller than the inner diameter of the plurality of holes located in the second region, which is the other one of the plurality of regions. May be good.
  • the metal porous sheet of (4) is arranged so that the second region is located vertically above the first region, so that the inner diameter of the hole on the vertically upper side is the inner diameter of the hole on the vertically lower side. Will be larger than. As a result, more gas bubbles generated during water electrolysis are likely to be released from the inside of the metal porous sheet. Therefore, according to the metal porous sheet of the above (4), the electrolysis voltage at the time of performing water electrolysis can be further lowered.
  • the first main surface may be divided into a plurality of regions along the second direction orthogonal to the first direction.
  • the value obtained by dividing the number of holes located in the first region, which is one of the plurality of regions, by the area of the first region is located in the second region, which is the other one of the plurality of regions. It may be smaller than the number of inner diameters of the holes divided by the area of the second region.
  • the metal porous sheet of the above (5) By arranging the metal porous sheet of the above (5) so that the second region is located vertically above the first region, the number density of the holes becomes larger on the vertically upper side than on the vertically lower side. .. As a result, more gas bubbles generated during water electrolysis are likely to be released from the inside of the metal porous sheet. Therefore, according to the metal porous sheet of the above (5), the electrolysis voltage at the time of performing water electrolysis can be further lowered.
  • the water electrolyzer according to the embodiment includes an electrolytic electrode having the metal porous sheets of (1) to (5) above.
  • the metal porous sheets of (1) to (5) above are used for the electrolytic electrode. Therefore, according to the water electrolysis device of the above (6), the electrolysis voltage at the time of performing water electrolysis can be lowered.
  • the metal porous sheet according to another embodiment includes a first main surface and a second main surface which is an opposite surface of the first main surface.
  • the first main surface is formed with a plurality of holes penetrating the metal porous sheet along the first direction from the first main surface to the second main surface.
  • the porosity of the metal porous sheet is 80% or more.
  • the value obtained by dividing the total opening area of the plurality of holes on the first main surface by the area of the first main surface is 0.05 or more and 0.35 or less.
  • the metal porous body sheet of the above (7) may be made of a metal porous body having a three-dimensional network structure.
  • the average pore diameter in the metal porous sheet when viewed from a direction orthogonal to the first main surface may be 100 ⁇ m or more.
  • the plurality of holes may be arranged in a plurality of rows along the second direction orthogonal to the first direction.
  • the plurality of holes included in each of the plurality of rows may be periodically arranged at the first interval in the second direction.
  • Each of the plurality of rows may be periodically arranged at a second interval in a third direction orthogonal to the first direction and the second direction.
  • each of the plurality of holes may have a first width in the second direction and a second width in the third direction.
  • the first width may be 0.5 mm or more.
  • the second width may be larger than the first width and may be 1.5 mm or more.
  • the second width may be twice or more the first width.
  • the plurality of rows may be composed of a plurality of first rows and a plurality of second rows.
  • the plurality of first rows and the plurality of second rows may be arranged alternately in the third direction.
  • the plurality of first rows may be located at positions offset by 0.5 times the first interval with respect to the plurality of second rows in the second direction.
  • the value obtained by subtracting the second width from the second interval divided by the second interval may be 0.5 or more.
  • the electrode according to another embodiment includes the metal porous sheet of (13) above and a plate-shaped support arranged on the first main surface.
  • the support is composed of a plurality of diamond-shaped holes penetrating the support along the first direction and strands around each of the plurality of diamond-shaped holes.
  • the plurality of diamond holes are arranged in a houndstooth pattern so that the two diagonal lines are along the second direction and the third direction, respectively.
  • Each of the plurality of diamond holes contains a first vertex and a second vertex adjacent to the first vertex.
  • the strand includes a first intersection next to the first vertex and a second intersection next to the second vertex.
  • the metal porous sheet is arranged so that the second direction is along the vertical vertical direction.
  • the support is arranged so that the portion of the strand at an intermediate position between the first intersection and the second intersection overlaps the plurality of holes.
  • metal porous sheet 10 (Structure of metal porous sheet according to the first embodiment)
  • metal porous sheet 10 the metal porous sheet according to the first embodiment
  • FIG. 1 is a plan view of the metal porous sheet 10.
  • FIG. 2 is a cross-sectional view taken along the line II-II of FIG.
  • FIG. 2 shows a cross section of the metal porous sheet 10 along the first direction DR1 described later.
  • the metal porous sheet 10 has a sheet-like shape.
  • the metal porous sheet 10 has a first main surface 10a and a second main surface 10b.
  • the second main surface 10b is the opposite surface of the first main surface 10a.
  • the direction from the first main surface 10a to the second main surface 10b is called the first direction DR1.
  • the metal porous sheet 10 has, for example, a rectangular shape. This rectangular shape is composed of a first side 10c, a second side 10d, a third side 10e, and a fourth side 10f.
  • the first side 10c and the second side 10d are along the second direction DR2.
  • the second direction DR2 is one of the directions orthogonal to the first direction DR1.
  • the third side 10e and the fourth side 10f are along the third direction DR3.
  • the third direction DR3 is a direction orthogonal to the first direction DR1 and the second direction DR2.
  • a plurality of holes 10g are formed on the first main surface 10a.
  • Each of the holes 10g penetrates the metal porous sheet 10 along, for example, the first direction DR1.
  • the hole 10g is, for example, circular in a plan view.
  • the hole 10g has an inner diameter d.
  • the inner diameter d is, for example, constant from the first main surface 10a side to the second main surface 10b side.
  • the width of the hole 10g in the second direction DR2 is defined as the width W1
  • the width of the hole 10g in the third direction DR3 is defined as the width W2.
  • the area of the hole 10 g in a plan view is defined as the area S1.
  • the area of the first main surface 10a in a plan view is defined as the area S2.
  • the value obtained by dividing the total value of the areas S1 of all the holes 10 g by the area S2 (hereinafter referred to as “aperture ratio”) is, for example, 0.01 or more.
  • the aperture ratio is, for example, 0.40 or less.
  • the aperture ratio is preferably 0.01 or more and 0.40 or less.
  • the plurality of holes 10g are arranged along the second direction DR2 so as to form a plurality of rows in a plan view.
  • the plurality of holes 10g form a first row CL1, a second row CL2, a third row CL3, a fourth row CL4, and a fifth row CL5.
  • the first row CL1 to the fifth row CL5 are arranged in this order from the first side 10c side to the second side 10d side.
  • the plurality of holes 10g are arranged along the third direction DR3 so as to form a plurality of rows in a plan view.
  • the plurality of holes 10g form a first row RO1, a second row RO2, a third row RO3, a fourth row RO4, and a fifth row RO5.
  • the first row RO1 to the fifth row RO5 are arranged in this order from the third side 10e side to the fourth side 10f side.
  • the plurality of holes 10g are arranged in a square grid, for example, in a plan view.
  • the plurality of holes 10g may be arranged in a rectangular grid pattern in a plan view.
  • the distance between two adjacent holes 10g in the second direction DR2 is defined as the pitch P1.
  • the distance between two adjacent holes 10g in the third direction DR3 is defined as the pitch P2.
  • the pitch P1 may be equal to or different from the pitch P2.
  • the image data of the metal porous sheet 10 is obtained by photographing the metal porous sheet 10 from the first direction DR1. .. Secondly, the region where the hole 10g is formed and the other region are specified by performing the binarization process on the captured image data. By measuring the area and dimensions of each region based on the specific result, the values of the inner diameter d, the area S1 and the area S2 can be obtained.
  • FIG. 3 is a schematic view showing the internal structure of the metal porous sheet 10.
  • the metal porous sheet 10 is formed of a metal porous body.
  • the metal porous body has a skeleton 11 having a three-dimensional network structure.
  • FIG. 4 is an enlarged cross-sectional view showing the internal structure of the metal porous sheet 10.
  • FIG. 5 is a cross-sectional view taken along the line VV of FIG.
  • the skeleton 11 has a hollow tubular shape. That is, the skeleton 11 has a skeleton body 11a and an internal space 11b defined by the skeleton body 11a.
  • the skeleton body 11a is made of a metal material.
  • the metal material is, for example, nickel (Ni) or a nickel alloy.
  • the skeleton body 11a has a triangular shape in a cross-sectional view intersecting in the extending direction. This triangular shape does not have to be a mathematically exact triangular shape.
  • the skeleton 11 may be solid.
  • FIG. 6 is a schematic view showing the unit cell structure of the metal porous body defined by the skeleton 11.
  • the space between the skeletons 11 is pores.
  • the space defined by the skeleton 11 has a regular dodecahedron structure.
  • the diameter of the circumscribed sphere of this regular dodecahedron structure (indicated by the alternate long and short dash line in FIG. 6) is regarded as the pore diameter of the pores in the metal porous body.
  • the average value of the pore diameters in the metal porous body is called the average pore diameter.
  • the inner diameter d is 1.5 times or more the average pore diameter of the metal porous body.
  • water electrolyzer 100 Structure of water electrolyzer according to the first embodiment
  • water electrolyzer 100 the configuration of the water electrolyzer according to the first embodiment
  • the water electrolyzer 100 is, for example, a hydrogen gas (H 2 ) and oxygen gas (O 2 ) generating device.
  • FIG. 7 is a schematic cross-sectional view of the unit cell of the water electrolyzer 100.
  • the unit cell of the water electrolyzer 100 includes an electrode 30a and an electrode 30b, a diaphragm 40, a multi-pole plate 50, a leaf spring 60a and a leaf spring 60b, and a frame 70a and a frame 70b.
  • the upper and lower parts in FIG. 7 correspond to the vertically upper part and the vertically lower part, respectively.
  • the unit cell is electrically connected to an adjacent unit cell through the multi-pole plate 50.
  • a plurality of unit cells are arranged in the water electrolyzer 100.
  • the electrode 30a is, for example, a hydrogen generating electrode.
  • the electrode 30b is, for example, an oxygen-evolving electrode.
  • the electrode 30a and the electrode 30b each have a metal porous sheet 10 and a support 20.
  • the first side 10c and the second side 10d are along the vertical direction, and the third side 10e and the fourth side 10f are horizontal. Along the direction.
  • the first side 10c and the second side 10d are along the vertical direction, and the third side 10e and the fourth side 10f are along the horizontal direction. You may be.
  • the metal porous sheet 10 may not be used for either the electrode 30a or the electrode 30b.
  • the support 20 is arranged on the metal porous sheet 10 (more specifically, on the first main surface 10a).
  • the support 20 is, for example, an expanded metal.
  • An opening is formed in the support 20.
  • the opening of the support 20 penetrates the support 20 along the thickness direction (along the first direction DR1).
  • a hole 10g is exposed from the opening of the support 20 when viewed from the direction orthogonal to the first main surface 10a.
  • the diaphragm 40 allows hydrogen ions (H + ) or hydroxide ions (OH ⁇ ) to pass through.
  • the diaphragm 40 one having low gas permeability and low electron conductivity is used.
  • an ion exchange membrane, a porous diaphragm, or a cloth is used.
  • the diaphragm 40 may be, for example, a membrane formed of a hydrophilic polyethylene non-woven fabric.
  • the diaphragm 40 is sandwiched between the electrodes 30a and 30b.
  • the second main surface 10b of the metal porous sheet 10 constituting the electrode 30a and the second main surface 10b of the metal porous sheet 10 forming the electrode 30b face the diaphragm 40, respectively.
  • An opening 70aa is formed in the frame 70a.
  • the opening 70a penetrates the frame 70a along the thickness direction.
  • a hole 70ab and a hole 70ac are further formed in the frame 70a.
  • the holes 70ab and 70ac are formed along the vertically lower portion and the vertically upper portion, respectively.
  • the holes 70ab and 70ac connect the opening 70aa to the outside of the frame 70a.
  • An opening 70ba is formed in the frame 70b.
  • the opening 70ba penetrates the frame 70b along the thickness direction.
  • a hole 70bb and a hole 70bc are further formed in the frame 70b.
  • the hole 70bb and the hole 70bc are formed along the vertically lower portion and the vertically upper portion, respectively.
  • the holes 70bb and 70bc connect the opening 70ba to the outside of the frame 70b.
  • the frame 70a and the frame 70b are arranged so that the opening 70aa and the opening 70ba overlap each other.
  • the diaphragm 40 is sandwiched between the frame 70a and the frame 70b so as to be exposed from the opening 70aa and the opening 70ba.
  • the frame 70a and the frame 70b are sandwiched by two double electrode plates 50.
  • the multi-pole plate 50 is made of an electron-conducting (conductive) material for electrical connection with adjacent unit cells.
  • the multi-pole plate 50 is made of, for example, nickel (Ni).
  • Ni nickel
  • the multi-pole plate 50 is electrically connected to a power source at the end of the water electrolyzer 100.
  • the double electrode plate 50 is arranged so as to face the support 20 included in the electrode 30a (electrode 30b).
  • the electrode 30a is arranged in the space defined by the diaphragm 40, the double electrode plate 50, and the opening 70aa.
  • the electrode 30b is arranged in the space defined by the diaphragm 40, the double electrode plate 50, and the opening 70ba.
  • a leaf spring 60a is arranged between the double electrode plate 50 and the support 20 included in the electrode 30a.
  • a leaf spring 60b is arranged between the double electrode plate 50 and the support 20 included in the electrode 30b.
  • An alkaline aqueous solution is supplied from the hole 70ab into the space defined by the diaphragm 40, the double electrode plate 50, and the opening 70aa.
  • An alkaline aqueous solution is supplied from the hole 70bb into the space defined by the diaphragm 40, the double electrode plate 50, and the opening 70ba.
  • the space defined by the diaphragm 40, the dipole plate 50 and the opening 70aa and the space demarcated by the diaphragm 40, the dipole plate 50 and the opening 70ba are filled with the alkaline aqueous solution as the electrolytic solution.
  • This alkaline aqueous solution is, for example, a potassium hydroxide aqueous solution (KOH).
  • a voltage is applied between the dipole plates 50 at both ends of the unit cell so that the potential at the electrode 30a is lower than the potential at the electrode 30b.
  • the water in the alkaline aqueous solution is reduced and hydrogen gas is generated.
  • the hydrogen gas generated at the electrode 30a is discharged together with the alkaline aqueous solution through the hole 70ac from the space defined by the diaphragm 40, the double electrode plate 50 and the opening 70aa.
  • the hydroxide ion in the alkaline aqueous solution moves from the electrode 30a side to the electrode 30b side through the diaphragm 40.
  • the hydroxide ion that has moved to the electrode 30b side is oxidized at the electrode 30b.
  • oxygen gas is generated at the electrode 30b.
  • the oxygen gas generated at the electrode 30b is discharged together with the alkaline aqueous solution through the hole 70bc from the space defined by the diaphragm 40, the double electrode plate 50 and the opening 70ba.
  • the water electrolyzer 100 produces hydrogen gas and oxygen gas.
  • the water electrolyzer 100 may be a device for producing an aqueous solution of chlorine gas (Cl 2 ), hydrogen gas, and sodium hydroxide (NaOH).
  • an aqueous solution of sodium chloride (NaCl) is used as the electrolytic solution.
  • FIG. 8 is a schematic view for explaining the effect of the water electrolyzer 100 using the metal porous sheet 10.
  • hydrogen gas oxygen gas
  • FIG. 8 hydrogen gas (oxygen gas) is generated inside the metal porous sheet 10 constituting the electrode 30a (electrode 30b) as the electrolytic solution is electrolyzed.
  • This hydrogen gas (oxygen gas) becomes bubbles B.
  • Bubble B moves vertically upward due to the action of buoyancy and reaches a hole of 10 g.
  • the bubbles B that have reached the holes 10 g are discharged to the outside of the metal porous sheet 10 through the holes 10 g.
  • the generated bubbles B are less likely to interfere with the reaction at the electrode 30a (electrode 30b).
  • the electrolysis voltage at the time of performing water electrolysis can be lowered.
  • the volume ratio of hydrogen gas in the metal porous sheet 10 constituting the electrode 30a was obtained by simulation under the conditions shown in Table 1.
  • the volume ratio of hydrogen gas in the metal porous sheet 10 constituting the electrode 30a was 19.7% by volume.
  • the volume ratio of hydrogen gas in the metal porous sheet 10 constituting the electrode 30a is 17.6 volume percent. Met. From this, it was clarified that the electrolysis voltage at the time of performing water electrolysis is lowered by forming the holes 10 g in the metal porous sheet 10.
  • FIG. 9 is a schematic view of the simplified water electrolyzer 110.
  • the simplified water electrolyzer 110 includes electrodes 30a and 30b, a diaphragm 40, a plate member 50a and a plate member 50b, a leaf spring 60a and a leaf spring 60b, a connecting line 80a and a connection. It has a wire 80b and a container 90.
  • the upper and lower parts in FIG. 10 correspond to the vertically upper part and the vertically lower part, respectively.
  • a potassium hydroxide solution as an electrolytic solution 91 is stored in the container 90.
  • the electrode 30a, the electrode 30b, the diaphragm 40, the plate member 50a and the plate member 50b, and the leaf spring 60a and the leaf spring 60b are immersed in the electrolytic solution 91.
  • the plate member 50a is arranged so as to face the support 20 included in the electrode 30a.
  • the plate member 50b is arranged so as to face the support 20 constituting the electrode 30b.
  • the plate member 50a and the plate member 50b are made of, for example, a resin material.
  • a leaf spring 60a is arranged between the plate member 50a and the support 20 included in the electrode 30a.
  • a leaf spring 60b is arranged between the plate member 50b and the support 20 included in the electrode 30b.
  • the plate member 50a and the plate member 50b are fixed to each other by, for example, screwing. As a result, the metal porous sheet 10 contained in the electrode 30a and the metal porous sheet 10 contained in the electrode 30b are pressed against the diaphragm 40.
  • the connecting wire 80a is electrically connected to the metal porous sheet 10 included in the electrode 30a at one end.
  • the connecting wire 80b is electrically connected to the metal porous sheet 10 included in the electrode 30b.
  • the other end of the connecting line 80a and the other end of the connecting line 80b are electrically connected to a power source (not shown).
  • the connecting line 80a and the connecting line 80b are made of, for example, platinum (Pt).
  • FIG. 10 is a graph showing the results of measuring the electrolytic voltage by changing the aperture ratio in the simple water electrolyzer 110.
  • the horizontal axis is the aperture ratio and the vertical axis is the electrolytic voltage (unit: V).
  • the measurements in FIG. 10 were performed under the conditions shown in Table 2.
  • the electrolytic voltage decreases as the aperture ratio increases. From this result, it can be said that it is preferable to increase the aperture ratio (for example, 0.01 or more) in order to reduce the electrolytic voltage.
  • the surface area of the metal porous body sheet 10 decreases as the aperture ratio increases.
  • the opening ratio is 0.40 or less, the surface area is larger than that of general expanded metal. Therefore, when the aperture ratio is 0.01 or more and 0.40 or less, the electrolytic voltage at the time of performing water electrolysis can be lowered while maintaining the reactivity of the metal porous sheet 10.
  • metal porous sheet 10A (hereinafter referred to as “metal porous sheet 10A”) according to the first modification will be described.
  • the differences from the metal porous sheet 10 will be mainly described, and the overlapping description will not be repeated.
  • FIG. 11 is a plan view of the metal porous sheet 10A. As shown in FIG. 11, in the metal porous sheet 10A, in the metal porous sheet 10A, a plurality of holes 10 g are arranged in a houndstooth pattern in a plan view.
  • the holes 10 g belonging to the first row CL1, the third row CL3, and the fifth row CL5 are arranged in a square lattice or a rectangular lattice, and the first row is formed.
  • the holes 10 g belonging to the second row CL2 and the fourth row CL4 are arranged in a square grid pattern or a rectangular grid pattern.
  • Each of the holes 10g belonging to the second row CL2 is arranged between two adjacent holes 10g belonging to the first row CL1 in the second direction DR2 and belongs to the third row CL3. It is arranged between two adjacent holes (10 g).
  • each of the holes 10g belonging to the fourth row CL4 is arranged between two adjacent holes 10g belonging to the third row CL3 in the second direction DR2, and is also arranged. It is arranged between two adjacent holes 10g belonging to the fifth row CL5.
  • a plurality of holes 10 g are arranged along the third direction DR3 so as to form a plurality of rows.
  • a plurality of holes 10g have the first row RO1, the second row RO2, the third row RO3, the fourth row RO4, the fifth row RO5, the sixth row RO6, the seventh row RO7, and the eighth row. It is arranged so as to form RO8 and RO9 in the 9th row.
  • metal porous sheet 10B the metal porous sheet 10 according to the second modification
  • metal porous sheet 10C the metal porous sheet 10 according to the third modification
  • FIG. 12 is a plan view of the metal porous sheet 10B.
  • each of the holes 10g in the metal porous sheet 10A is replaced with two holes 10g (holes 10ga and holes 10gb). Therefore, the number density of the holes 10g in the metal porous sheet 10B (the value obtained by dividing the number of holes 10g by the area S2) is higher than the number density of the holes 10g in the metal porous sheet 10A. Therefore, in the metal porous sheet 10B, bubbles B are more likely to be released to the outside than in the metal porous sheet 10A.
  • FIG. 13 is a plan view of the metal porous sheet 10C.
  • each of the holes 10g belonging to the first row CL1 and the fifth row CL5 in the metal porous sheet 10A is replaced with two holes (holes 10ga and holes 10gb), and the second row CL2.
  • Each of the holes 10g belonging to the fourth row CL4 is replaced with three holes 10g (holes 10ga, holes 10gb and holes 10gc). Therefore, the number density of the holes 10g in the metal porous sheet 10C is larger than the number density of the holes 10g in the metal porous sheet 10A and the number density of the holes 10g in the metal porous sheet 10B. Therefore, in the metal porous sheet 10C, bubbles B are more likely to be released to the outside than in the metal porous sheet 10A.
  • metal porous sheet 10D the metal porous sheet 10 according to the fourth modification
  • metal porous sheet 10E the metal porous sheet 10 according to the fifth modification
  • FIG. 14 is a plan view of the metal porous sheet 10D.
  • FIG. 15 is a plan view of the metal porous sheet 10E.
  • the first main surface 10a is divided into a plurality of regions along the second direction DR2.
  • Each of the plurality of regions has a strip-like shape extending along the third direction DR3.
  • the first main surface 10a is divided into a first region R1 and a second region R2.
  • the width of the first region R1 in the second direction DR2 is equal to 1/3 of the distance between the third side 10e and the fourth side 10f.
  • the width of the second region R2 in the second direction DR2 is equal to 2/3 of the distance between the third side 10e and the fourth side 10f.
  • the first region R1 includes holes 10 g belonging to the first row RO1 to the third row RO3.
  • the second region R2 includes holes 10 g belonging to the fourth row RO4 to the ninth row RO9.
  • the second region R2 is located closer to the fourth side 10f than the first region R1.
  • the inner diameter d in the second region R2 is larger than the inner diameter d in the first region R1.
  • the first main surface 10a is divided into a first region R1, a second region R2, and a third region R3.
  • the first region R1 includes holes 10 g belonging to the first row RO1 to the third row RO3.
  • the second region R2 includes holes 10 g belonging to the fourth row RO4 to the sixth row RO6.
  • the third region R3 includes holes 10 g belonging to the 7th row RO7 to the 9th row RO9.
  • the first region R1, the second region R2, and the third region R3 are arranged in this order from the third side 10e side to the fourth side 10f side.
  • the inner diameter d in the third region R3 is larger than the inner diameter d in the second region R2, and the inner diameter d in the second region R2 is larger than the inner diameter d in the first region R1.
  • the metal porous sheet 10D is arranged so that the second region R2 is located vertically above the first region R1. The same applies to the water electrolyzer 100 using the metal porous sheet 10E.
  • Bubbles B generated inside the metal porous sheet 10D tend to accumulate on the vertically upper side.
  • the metal porous sheet 10D is arranged so that the second region R2 is vertically above the first region R1.
  • bubbles B are likely to be released from the inside of the metal porous sheet 10D on the vertically upper side. Therefore, according to the water electrolysis apparatus 100 using the metal porous sheet 10D, the electrolysis voltage at the time of performing water electrolysis can be further reduced. This also applies to the water electrolyzer 100 using the metal porous sheet 10E.
  • metal porous sheet 10F 6th modified example and 7th modified example
  • metal porous sheet 10G the metal porous sheet 10 according to the seventh modification
  • metal porous sheet 10A the differences from the metal porous sheet 10A will be mainly described, and the overlapping description will not be repeated.
  • FIG. 16 is a plan view of the metal porous sheet 10F.
  • FIG. 17 is a plan view of the metal porous sheet 10G.
  • the first main surface 10a is divided into a plurality of regions along the second direction DR2.
  • Each of the plurality of regions has a strip-like shape extending along the third direction DR3.
  • the first main surface 10a is divided into a first region R1 and a second region R2.
  • the arrangement of the holes 10g belonging to the first row RO1 to the third row RO3 on the metal porous body sheet 10F is the same as the arrangement of the holes 10 g belonging to the first row RO1 to the third row RO3 on the metal porous body sheet 10A. ..
  • the arrangement of the holes 10g belonging to the 4th row RO4 to the 9th row RO9 on the metal porous sheet 10F is the same as the arrangement of the holes 10g belonging to the 4th row RO4 to the 9th row RO9 on the metal porous body sheet 10B. .. Therefore, the number density of the holes 10g in the second region R2 is higher than the number density of the holes 10g in the first region R1.
  • the first main surface 10a is divided into a first region R1, a second region R2, and a third region R3.
  • the arrangement of the holes 10g belonging to the first row RO1 to the third row RO3 on the metal porous sheet 10G is the same as the arrangement of the holes 10g belonging to the first row RO1 to the third row RO3 on the metal porous body sheet 10A. ..
  • the arrangement of the holes 10g belonging to the 4th row RO4 to the 6th row RO6 on the metal porous sheet 10G is the same as the arrangement of the holes 10g belonging to the 4th row RO4 to the 6th row RO6 on the metal porous body sheet 10B. ..
  • the arrangement of the holes 10g belonging to the 7th row RO7 to the 9th row RO9 on the metal porous sheet 10G is the same as the arrangement of the holes 10g belonging to the 7th row RO7 to the 9th row RO9 on the metal porous body sheet 10C. ..
  • the number density of the holes 10g in the third region R3 is higher than the number density of the holes 10g in the second region R2, and the number density of the holes 10g in the second region R2 is higher than the number density of the holes 10g in the first region R1. big.
  • Bubbles B generated inside the metal porous sheet 10F tend to accumulate on the vertically upper side.
  • the number density of the holes 10g in the second region R2 is higher than the number density of the holes 10g in the first region R1, the metal porous so that the second region R2 is vertically above the first region R1. If the body sheet 10F is arranged, the bubbles B are likely to be released from the inside of the metal porous sheet 10F on the vertically upper side. Therefore, according to the water electrolysis apparatus 100 using the metal porous sheet 10F, the electrolysis voltage at the time of performing water electrolysis can be further reduced. This also applies to the water electrolyzer 100 using the metal porous sheet 10G.
  • metal porous sheet 10 according to the eighth modification the metal porous sheet 10 according to the ninth modification, and the metal porous sheet 10 according to the tenth modification (hereinafter, these are referred to as “metal porous sheets”, respectively. 10H ”,“ metal porous sheet 10I ”and“ metal porous sheet 10J ”) will be described.
  • the differences from the metal porous sheet 10A will be mainly described, and the overlapping description will not be repeated.
  • FIG. 18 is a cross-sectional view of the metal porous sheet 10H along the first direction DR1.
  • the inner diameter d becomes smaller from the first main surface 10a side toward the second main surface 10b side (from the second main surface 10b side to the first). It becomes larger toward the main surface 10a side).
  • the hole 10g has a tapered shape.
  • the inner wall surface of the hole 10 g is formed of a straight line in a cross-sectional view along the first direction DR1.
  • FIG. 19 is a cross-sectional view of the metal porous sheet 10I along the first direction DR1.
  • the inner diameter d becomes smaller from the first main surface 10a side to the second main surface 10b side.
  • the inner wall surface of the hole 10 g is formed by a curved line in a cross-sectional view along the first direction DR1.
  • FIG. 20 is a cross-sectional view of the metal porous sheet 10J along the first direction DR1.
  • the inner diameter d becomes smaller from the first main surface 10a side to the second main surface 10b side.
  • the hole 10g is composed of a first portion 10i and a second portion 10j located on the second main surface 10b side of the first portion 10i.
  • the inner diameter d in the first portion 10i is larger than the inner diameter d in the second portion 10j.
  • FIG. 21 is a schematic view for explaining the effect of the water electrolyzer 100 using the metal porous sheet 10H.
  • the inner diameter d increases from the second main surface 10b side toward the first main surface 10a side, so that the inner wall of the hole 10g moves vertically upward as it approaches the first main surface 10a. It will include the part that is inclined toward it.
  • the bubbles B that have reached the holes 10 g are likely to be discharged to the outside of the metal porous sheet 10H from the first main surface 10a side along the inclination. Therefore, according to the water electrolyzer 100 using the metal porous sheet 10H, by arranging the metal porous sheet 10I so that the second main surface 10b faces the diaphragm 40, bubbles B are accumulated in the vicinity of the diaphragm 40. It is possible to suppress the storage. This also applies to the water electrolyzer 100 using the metal porous sheet 10I or the metal porous sheet 10J.
  • metal porous sheet 10 according to the eleventh modification the metal porous sheet 10 according to the twelfth modification, the metal porous sheet 10 according to the thirteenth modification, and the metal porous sheet 10 according to the fourteenth modification are described below.
  • metal porous sheet 10K the differences from the metal porous sheet 10A will be mainly described, and the overlapping description will not be repeated.
  • FIG. 22 is a plan view of the metal porous sheet 10K.
  • the holes 10 g have a rhombic shape in a plan view.
  • the diagonal lines of this rhombus are along the second direction DR2 and the third direction DR3, respectively.
  • the width W2 is larger than, for example, the width W1.
  • FIG. 23 is a plan view of the metal porous sheet 10L.
  • the holes 10g have a regular hexagonal shape in a plan view. In this regular hexagonal shape, the diagonal line passing through the center of the regular hexagonal shape is along the second direction DR2.
  • FIG. 24 is a plan view of the metal porous sheet 10M.
  • the holes 10 g have a triangular shape in a plan view.
  • This triangular shape is, for example, an isosceles triangle whose apex angle faces the fourth side 10f side.
  • This triangular shape may be an isosceles triangle whose apex angle faces the third side 10e side.
  • FIG. 25 is a plan view of the metal porous sheet 10N. As shown in FIG. 25, in the metal porous sheet 10N, the holes 10 g have a quadrangular shape in a plan view. This quadrangular shape is a rectangular shape.
  • metal porous sheet 10O the metal porous sheet 10 according to the fifteenth modification.
  • the differences from the metal porous sheet 10A will be mainly described, and the overlapping description will not be repeated.
  • FIG. 26 is a plan view of the metal porous sheet 10O.
  • the holes 10 g have an elliptical shape in a plan view.
  • the minor axis and the major axis are along the second direction DR2 and the third direction DR3, respectively.
  • metal porous sheet 10P the metal porous sheet 10 according to the 16th modification will be described.
  • the differences from the metal porous sheet 10A will be mainly described, and the overlapping description will not be repeated.
  • FIG. 27 is a plan view of the metal porous sheet 10P.
  • the holes 10 g have a slit-like shape.
  • the hole 10 g extends linearly along the third direction DR3.
  • a plurality of holes 10g are arranged at intervals along the second direction DR2.
  • the slit-shaped hole 10 g has a width W3.
  • the width W3 is the width in the direction orthogonal to the extending direction of the hole 10g.
  • metal porous sheet 10Q (hereinafter referred to as “metal porous sheet 10Q”) according to the 17th modification will be described.
  • metal porous sheet 10A the difference from the metal porous sheet 10A will be mainly described, and the overlapping description will not be repeated.
  • FIG. 28 is a plan view of the metal porous sheet 10Q.
  • the holes 10 g have a slit-like shape.
  • the hole 10 g extends linearly along the third direction DR3.
  • the length of the hole 10 g belonging to the first row CL1, the third row CL3, and the fifth row CL5 in the third direction DR3 is defined as the length L1.
  • the length of the hole 10 g belonging to the second row CL2 and the fourth row CL4 in the third direction DR3 is defined as the length L2.
  • the length L2 is preferably larger than the length L1.
  • metal porous sheet 10R the metal porous sheet 10 according to the 18th modification.
  • metal porous sheet 10A the differences from the metal porous sheet 10A will be mainly described, and the overlapping description will not be repeated.
  • FIG. 29 is a plan view of the metal porous sheet 10R.
  • the holes 10 g have a slit-like shape.
  • the hole 10 g has a V shape. More specifically, the hole 10g is connected to a first portion extending linearly along a direction forming an acute angle with the direction from the first side 10c to the second side 10d, and the first portion. Moreover, it is composed of a second portion extending linearly along a direction forming an acute angle and a direction from the first side 10c to the second side 10d.
  • metal porous sheet 10S The metal porous sheet 10 (hereinafter referred to as “metal porous sheet 10S”) according to the 19th modification will be described.
  • metal porous sheet 10A the differences from the metal porous sheet 10A will be mainly described, and the overlapping description will not be repeated.
  • FIG. 30 is a plan view of the metal porous sheet 10S.
  • the holes 10 g have a slit-like shape in a plan view.
  • the plurality of holes 10g include a hole 10g (hole 10gd) extending linearly along the second direction DR2 and a direction forming an acute angle with the direction from the first side 10c to the second side 10d.
  • a hole 10g (hole 10ge) extending linearly and a hole 10g (hole 10gf) extending linearly along a direction forming an acute angle with the direction from the first side 10c to the second side 10d.
  • 10 g of V-shaped holes (10 gg holes) are included.
  • Samples 1 to 47 were prepared as metal porous sheets used for the electrodes 30a and 30b.
  • the plane dimensions of Samples 1 to 47 were all 20 mm ⁇ 20 mm.
  • the thicknesses of Samples 1 to 47 were all set to 0.5 mm.
  • the water electrolysis test was performed using the simplified water electrolysis device 110 shown in FIG.
  • An expanded metal made of nickel was used for the support 20.
  • the thickness of this expanded metal was set to 0.8 mm.
  • a separator for a nickel-metal hydride battery manufactured by Japan Vilene Company was used for the diaphragm 40.
  • a polypropylene plate having a thickness of 15 mm was used for the plate member 50a and the plate member 50b.
  • a platinum wire having a wire diameter of 0.3 mm was used for the connecting wire 80a and the connecting wire 80b.
  • the leaf spring 60a and the leaf spring 60b were adjusted so that a stress of 0.03 MPa acts between the electrode 30a and the electrode 30b and the diaphragm 40.
  • Sample 5 and sample 7 have the same other conditions except for the presence or absence of a cross-sectional shape of a hole of 10 g.
  • the electrolytic voltage of sample 7 was lower than that of sample 5.
  • the other conditions of the sample 6 and the sample 8 are the same except for the presence or absence of the cross-sectional shape of the hole 10 g.
  • the electrolytic voltage of sample 8 was lower than that of sample 6.
  • the other conditions of the sample 11 and the sample 13 are the same except for the presence or absence of the cross-sectional shape of the hole 10 g.
  • the electrolytic voltage of sample 13 was lower than that of sample 11. From these comparisons, it was clarified experimentally that the electrolytic voltage was lowered because the hole 10 g had a tapered shape.
  • the electrolytic voltage in the sample 44 and the sample 45 was lower than the electrolytic voltage in the sample 9. From this comparison, the number density of the holes 10g contained in each of the plurality of regions dividing the first main surface 10a along the second direction DR2 is higher than that of one side in the second direction DR2 in the second direction DR2. It was also experimentally clarified that the electrolytic voltage decreases due to the increase on the other side of the above.
  • the electrolytic voltage in the sample 46 and the sample 47 was lower than the electrolytic voltage in the sample 9. From this comparison, the inner diameter d of the hole 10g included in each of the plurality of regions dividing the first main surface 10a along the second direction DR2 is larger than that of one side in the second direction DR2 in the second direction DR2. It was also experimentally clarified that the electrolytic voltage decreases due to the increase on the other side of the above.
  • metal porous sheet 10T (Structure of metal porous sheet according to the second embodiment)
  • metal porous sheet 10T the configuration of the metal porous sheet according to the second embodiment
  • FIG. 31 is a plan view of the metal porous sheet 10T.
  • the metal porous sheet 10T has a first main surface 10a and a second main surface 10b.
  • the metal porous sheet 10T has a rectangular shape composed of a first side 10c, a second side 10d, a third side 10e, and a fourth side 10f in a plan view.
  • the metal porous sheet 10T is made of, for example, a metal porous body having a three-dimensional network structure. However, the metal porous body constituting the metal porous body sheet 10T does not have to have a three-dimensional network structure.
  • the metal porous sheet 10T may be, for example, a woven fabric or a non-woven fabric made of metal fibers.
  • the metal porous body constituting the metal porous body sheet 10T is an alloy containing an element that dissolves in an alkali and a metal having alkali resistance, or a composite in which an element that dissolves in an alkali is dispersed in a metal having alkali resistance. It may be formed by the body. Examples of elements that dissolve in alkali are zinc (Zn), aluminum (Al), tin (Sn), and the like. An example of a metal having alkali resistance is nickel or the like. In this case, fine irregularities are generated on the surface of the metal porous body due to element elution by the treatment in alkali. As a result, the surface area of the metal porous body is increased, and the characteristics of hydrogen and oxygen evolution are improved. However, the metal porous body constituting the metal porous body sheet 10T may be formed of a metal material other than the above.
  • a catalyst may be supported on the surface of the metal porous body constituting the metal porous body sheet 10T.
  • This catalyst is, for example, a noble metal oxide such as ruthenium dioxide (RuO 2) or a cobalt oxide. In this case, the characteristics of hydrogen and oxygen evolution are improved on the surface of the metal porous body.
  • the average pore diameter in the metal porous sheet 10T in a plan view is 100 ⁇ m or more.
  • the average pore diameter of the pores in the metal porous sheet 10T in a plan view is preferably 400 ⁇ m or more.
  • FIG. 32 is a cross-sectional view taken along the line XXXII-XXXII of FIG.
  • a plurality of holes 10 g are formed in the metal porous sheet 10T.
  • the hole 10g preferably penetrates the metal porous sheet 10T along the first direction DR1.
  • the hole 10g has, for example, a rectangular shape in a plan view.
  • the hole 10g may have a circular shape in a plan view.
  • the aperture ratio of the metal porous sheet 10T is 0.05 or more and 0.35 or less.
  • the aperture ratio of the metal porous sheet 10T is calculated by dividing the total opening area of the holes 10g in the first main surface 10a by the area of the first main surface 10a.
  • the porosity of the metal porous sheet 10T is 80% or more.
  • the porosity of the metal porous sheet 10T is preferably 85% or more.
  • the porosity (unit: percentage) of the metal porous sheet 10 is calculated by 1- (1-the porosity of the metal porous sheet 10T itself) x (1-the opening ratio of the metal porous sheet 10T).
  • the mass of the metal porous sheet 10T is M (unit: g), the external volume of the metal porous sheet 10T is V (unit: cm 3 ), and the density of the metals constituting the metal porous sheet 10T is d ( Assuming that the unit is g / cm 3 ), the porosity of the metal porous sheet 10T itself is calculated by [1- ⁇ M / (V ⁇ d) ⁇ ] ⁇ 100 (unit:%).
  • the plurality of holes 10g are arranged along the second direction DR2 so as to form a plurality of rows CL, for example.
  • Each of the plurality of rows CL is periodically arranged along the third direction DR3.
  • each of the plurality of columns CL is arranged at equal intervals along the third direction DR3.
  • the plurality of columns CL are composed of a plurality of columns CLa and a plurality of columns CLb.
  • the columns CLa and CLb are arranged alternately in the third direction DR3.
  • the plurality of holes 10g belonging to each of the plurality of rows CL are periodically arranged along the second direction DR2.
  • the distance between two adjacent holes 10g in the second direction DR2 is defined as the pitch P3.
  • the pitch P3 is the center-to-center distance in the second direction DR2 between two adjacent holes 10g.
  • the distance between two adjacent rows CL in the third direction DR3 is defined as pitch P4.
  • the pitch P4 is the distance between the centers of the holes 10 g belonging to the rows CLa and CLb adjacent to each other in the third direction DR3.
  • the row CLa is located at a position shifted by 0.5 times the pitch P3 with respect to the row CLb in the second direction DR2. From another point of view, the plurality of holes 10g are arranged in a houndstooth pattern.
  • the width of the hole 10g in the second direction DR2 is the width W4, and the width of the hole 10g in the third direction DR3 is the width W5.
  • the width W5 is preferably larger than the width W4.
  • the width W4 is preferably 0.5 mm or more.
  • the width W5 is preferably 1.5 mm or more.
  • the width W5 is more preferably twice or more the width W4.
  • the value obtained by dividing the value obtained by dividing the pitch P4 from the width W5 by the pitch P4 is preferably 0.5 or less.
  • the total width in the third direction DR3 of the region between the row CLa and the row CLb and in which the hole 10g is not formed is the total width of the metal porous sheet 10T in the third direction DR3. It is preferably 50% or less of the width in.
  • the value obtained by dividing the value obtained by dividing the pitch P4 from the width W5 by the pitch P4 is less than 0 (the width W5 is larger than the pitch P4).
  • the position of the hole 10g belonging to one row CLa in the third direction DR3 is the position of the hole 10g belonging to the row CLa adjacent to the one row CLa in the third direction DR3. It is preferable that it partially overlaps with the position in.
  • water electrolyzer 100A Structure of water electrolyzer according to the second embodiment
  • water electrolyzer 100A the configuration of the water electrolyzer according to the second embodiment
  • the points different from the configuration of the water electrolyzer 100 will be mainly described, and the duplicated description will not be repeated.
  • FIG. 33 is a schematic cross-sectional view of the unit cell of the water electrolyzer 100A.
  • the unit cell of the water electrolyzer 100A includes an electrode 30a and an electrode 30b, a diaphragm 40, a multi-pole plate 50, a leaf spring 60a and a leaf spring 60b, and a frame 70a and a frame 70b.
  • the top and bottom in FIG. 33 correspond to the vertically upper side and the vertical lower side, respectively.
  • the metal porous sheet 10T is used for the electrodes 30a and 30b instead of the metal porous sheet 10.
  • the first side 10c and the second side 10d are along the vertical direction (vertical direction in the drawing), and the third side 10e and the fourth side 10f are along the horizontal direction.
  • FIG. 34 is a plan view of the electrode 30a. As shown in FIG. 34, the support 20 is an expanded metal. A plurality of diamond-shaped holes 20a are formed in the support 20. The diamond-shaped hole 20a penetrates the support 20 along the thickness direction. The rhombic hole 20a has a rhombic shape in a plan view. The two diagonal lines of the diamond shape are along the second direction DR2 and the third direction DR3, respectively.
  • the plurality of diamond-shaped holes 20a are arranged in a houndstooth pattern.
  • the portion of the support 20 where the rhombus hole 20a is not formed is a strand 20b.
  • the diamond hole 20a has a vertex 20aa, a vertex 20ab, a vertex 20ac, and a vertex 20ad.
  • the apex 20aa is adjacent to the apex 20ab and the apex 20ad.
  • the apex 20ac is adjacent to the apex 20ab and the apex 20ad.
  • the vertices 20aa and the vertices 20ac face each other in the second direction DR2.
  • the vertices 20ab and the vertices 20ad face each other in the third direction DR3.
  • the strand 20b has an intersection 20ba, an intersection 20bb, an intersection 20bc, and an intersection 20bd.
  • the intersection 20ba, the intersection 20bb, the intersection 20bc, and the intersection 20bd are adjacent to the apex 20aa, the apex 20ab, the apex 20ac, and the apex 20ad, respectively.
  • the intermediate position between the intersection 20ba and the intersection 20bb is the intermediate position CP1, the intermediate position between the intersection 20bb and the intersection 20bc is the intermediate position CP2, and the intermediate position between the intersection 20bc and the intersection 20bb is intermediate.
  • the position is defined as the intermediate position CP3, and the intermediate position between the intersection 20bd and the intersection 20ba is defined as the intermediate position CP4.
  • the support 20 is arranged on the first main surface 10a so as to overlap the hole 10g at the intermediate position CP1, the intermediate position CP2, the intermediate position CP3, and the intermediate position CP4.
  • the support 20 used for the electrode 30b also has the same structure as the support 20 used for the electrode 30a. Further, although not shown, the positional relationship between the metal porous sheet 10T and the support 20 is the same as that of the electrode 30a in the electrode 30b.
  • the porosity of the metal porous sheet 10T is 80% or more and the opening ratio of the holes 10g is 0.05 or more and 0.35 or more, the bubbles B are difficult to stay inside the metal porous sheet 10T.
  • the electrolytic voltage of the water electrolyzer 100A can be lowered.
  • a region in which the hole 10g is not formed may remain between the hole 10g belonging to the row CLa and the hole 10g belonging to the row CLb.
  • the width W5 is larger than the width W4 (more specifically, when the width W4 is 0.5 mm or more, the width W5 is 1.5 mm or more, and the width W5 is twice or more the width W4). ), Since this region becomes narrower, it becomes more difficult for the bubbles B to stay inside the metal porous sheet 10T. As a result, the electrolytic voltage of the water electrolyzer 100A can be further reduced.
  • the total width of the above regions is 50% or less of the width of the metal porous sheet 10T.
  • the value obtained by dividing the value obtained by dividing the pitch P4 from the width W5 by the pitch P4 is less than 0, the above region does not exist. Therefore, in these cases, the electrolytic voltage of the water electrolyzer 100A can be further reduced.
  • the bubble B tends to stay in the portion of the metal porous sheet 10T that overlaps the intermediate position CP1 to the intermediate position CP4. Therefore, when the hole 10g is formed in the portion of the metal porous sheet 10T that overlaps the intermediate position CP1 to the intermediate position CP4, the bubbles B are easily removed from the metal porous sheet 10T, so that the water electrolyzer 100A The electrolytic voltage can be further reduced.
  • the dimensions of the electrodes 30a and 30b were 55 mm ⁇ 45 mm, and the thickness of the support 20 was 0.8 mm.
  • the distance between the intersection 20ba and the intersection 20bc was 4 mm, and the distance between the intersection 20bb and the intersection 20bd was 8 mm.
  • the width of the strand 20b was 1 mm.
  • the electrolytic solution used in the water electrolysis test was a 7 mL / L potassium hydroxide aqueous solution.
  • a hydrophilic polyethylene non-woven fabric was used for the diaphragm 40.
  • the supply amount of the electrolytic solution was 50 cc / min.
  • the water electrolysis test was conducted at 60 ° C. The water electrolysis test was performed after 10 preliminary electrolysiss. Preliminary electrolysis was performed by passing a steady current of 12.5 A for 5 minutes while exchanging the positive and negative electrodes 30a and 30b. The water electrolysis test was carried out by passing a steady current of 12.5 A for 1 hour, and the electrolysis voltage after 1 hour was evaluated.
  • Samples 1 to 37 were prepared as samples to be subjected to the water electrolysis test.
  • the average pore diameter of the metal porous sheet 10T when viewed from the direction orthogonal to the first main surface 10a, the porosity of the metal porous sheet 10T, the arrangement of the holes 10g, the planar shape of the holes 10g, Whether or not the opening ratio of the hole 10g, the width W4, the width W5, the pitch P4 and the hole 10g overlap with the intermediate position CP1 to the intermediate position CP4 was changed as shown in Table 9.
  • Samples 1 to 35 are made of a metal porous body having a three-dimensional network structure.
  • Sample 36 and Sample 37 are each made of a non-woven fabric of metal fibers and a woven fabric (knit).
  • FIG. 35 is a plan view showing the first arrangement of the holes 10 g in the water electrolysis test. As shown in FIG. 35, in the first arrangement, the pitch P3 was equal to the distance between the centers of two adjacent diamond holes 20a in the second direction DR2.
  • FIG. 36 is a plan view showing a second arrangement of the holes 10 g in the water electrolysis test. As shown in FIG. 36, in the second arrangement, the pitch P3 was twice the distance between the centers of the two adjacent diamond holes 20a in the second direction DR2.
  • FIG. 37 is a plan view showing a third arrangement of the holes 10 g in the water electrolysis test. As shown in FIG. 37, in the second arrangement, the pitch P3 was three times the distance between the centers of the two adjacent diamond holes 20a in the second direction DR2.
  • Table 10 shows the results of the water electrolysis test. As shown in Table 10, Samples 7 to 9, Sample 11, Sample 12, Sample 14, Sample 16 to Sample 20, Sample 22, Sample 24 to Sample 30, and Sample 32 to Sample 37 are lower than Sample 1. The electrolytic voltage is shown.
  • Samples 1 to 6 Sample 10, Sample 13, Sample 15, Sample 21, Sample 23 and Sample 31 showed an electrolytic voltage higher than that of Sample 1.
  • the metal porous sheet 10T As shown in Table 9, in Samples 7 to 9, Sample 11, Sample 12, Sample 14, Sample 16 to Sample 20, Sample 22, Sample 24 to Sample 30, and Sample 32 to Sample 37, the metal porous sheet 10T The porosity of the hole was 80% or more, and the opening ratio of the hole 10 g was 0.05 or more and 0.35 or less.
  • the electrolysis voltage of the water electrolyzer 100A is lowered by setting the porosity of the metal porous sheet 10T to 80% or more and the opening ratio of the hole 10g to 0.05 or more and 0.35 or less. It was clarified experimentally.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
PCT/JP2021/001983 2020-01-27 2021-01-21 金属多孔体シート及び水電解装置 Ceased WO2021153406A1 (ja)

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EP21748456.7A EP4098774A4 (en) 2020-01-27 2021-01-21 METAL POROUS BODY SHEET AND WATER ELECTROLYSIS DEVICE
CN202180010040.2A CN115003861A (zh) 2020-01-27 2021-01-21 金属多孔体片和水电解装置
JP2021574688A JPWO2021153406A1 (https=) 2020-01-27 2021-01-21
US17/793,541 US20230080341A1 (en) 2020-01-27 2021-01-21 Metal porous body sheet and water electrolysis device

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US20230080341A1 (en) 2023-03-16
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