Patent Literature 1 (National Patent Publication No. 2005-536639) describes an electrode body. A wire mesh is used for the electrode body described in Patent Literature 1. Patent Literature 2 (Patent Publication No. 61-57397) describes an electrode for water electrolysis. A metal porous body having a three-dimensional mesh structure is used for the electrode for water electrolysis described in Patent Literature 2.
The metal porous body sheet according to the present disclosure includes a metal porous body having a three-dimensional mesh structure and has a first main surface and a second main surface that is a reverse surface to the first main surface. The first main surface is formed with multiple holes extending from the first main surface toward the second main surface along a first direction.
The wire mesh used in the electrode body described in Patent Literature 1 has a small surface area. Therefore, when the electrode body described in Patent Literature 1 is used for water electrolysis, the electrolysis voltage increases.
On the other hand, the metal porous body used for the electrode for water electrolysis described in Patent Literature 2 has a large surface area. However, in the metal porous body used in the electrode for water electrolysis described in Patent Literature 2, air bubbles generated by water electrolysis are likely to adhere to the inside. The portion to which bubbles adhere does not contribute to the electrolytic reaction. Therefore, even if the surface area is large, the metal porous body used in the electrode for water electrolysis described in Patent Literature 2 cannot reduce the electrolysis voltage when water electrolysis is performed.
The present disclosure has been accomplished in view of the above-described problems of the prior art. More specifically, the present disclosure provides a metal porous body sheet and a water electrolysis device capable of reducing an electrolysis voltage during water electrolysis.
According to the metal porous body sheet and the water electrolysis device of the present disclosure, it is possible to lower the electrolysis voltage during water electrolysis.
First, embodiments will be listed and described.
(1) A metal porous body sheet according to one embodiment includes a metal porous body having a three-dimensional mesh structure and has a first main surface and a second main surface that is a reverse surface to the first main surface. The first main surface is formed with multiple holes extending from the first main surface toward the second main surface along a first direction.
In the metal porous body sheet of (1), air bubbles generated during water electrolysis are easily discharged from the inside of the metal porous body sheet through the holes. Thus, according to the metal porous body sheet of (1), it is possible to lower the electrolysis voltage during water electrolysis.
(2) In the metal porous body sheet of (1), each of the multiple holes may penetrate the metal porous body sheet along the first direction.
(3) In the metal porous body sheet of (1) or (2), each of the multiple holes may have an inner diameter that decreases from a first main surface side toward a second main surface side.
In the metal porous body sheet of (3), air bubbles generated during water electrolysis are more easily discharged from the first main surface side than from the second main surface side. Therefore, in a case where a diaphragm of a water electrolysis device is disposed on the second main surface, the metal porous body sheet of (4) can suppress accumulation of air bubbles generated during water electrolysis in the vicinity of the diaphragm.
(4) In the metal porous body sheets of (1) to (3), the first main surface may be divided into multiple regions along a second direction orthogonal to the first direction. Inner diameters of the multiple holes located in a first region that is one of the multiple regions may be smaller than inner diameters of the multiple holes located in a second region that is another one of the multiple regions.
Air bubbles generated inside the metal porous body during water electrolysis are likely to remain on an upper side in the vertical direction. In the metal porous body sheet of (4). the second region is located vertically above the first region, so that the inner diameters of the holes on the vertically upper side is larger than the inner diameters of the holes on the vertically lower side. As a result, a larger amount of air bubbles generated during water electrolysis are easily released from the inside of the metal porous body sheet. Thus, according to the metal porous body sheet of (4), it is possible to further lower the electrolysis voltage during water electrolysis.
(5) In the metal porous body sheets of (1) to (3), the first main surface may be divided into multiple regions along a second direction orthogonal to the first direction. A value obtained by dividing a number of the multiple holes located in a first region that is one of the multiple regions by the area of the first region may be smaller than a value obtained by dividing a number of the multiple holes located in a second region that is another one of the multiple regions by an area of the second region.
In the metal porous body sheet of (5), the second region is located vertically above the first region, so that the number density of the holes is larger on the vertically upper side than on the vertically lower side. As a result, a larger amount of air bubbles generated during water electrolysis are easily released from the inside of the metal porous body sheet. Thus, according to the metal porous body sheet of (5), it is possible to further lower the electrolysis voltage during water electrolysis.
(6) A water electrolysis device according to an embodiment includes an electrolysis electrode having the metal porous body sheet of any one of (1) to (5).
In the water electrolysis device of (6), the metal porous body sheet of any one of (1) to (5) is used for the electrolysis electrode. Thus, according to the water electrolysis device of (6), it is possible to lower the electrolysis voltage during water electrolysis.
(7) A metal porous body sheet according to another embodiment includes a first main surface and a second main surface that is a reverse surface to the first main surface. The first main surface is formed with multiple holes penetrating the metal porous body sheet along a first direction from the first main surface toward the second main surface. The metal porous body sheet has a porosity of greater than or equal to 80%. A value obtained by dividing a total opening area of the multiple holes in the first main surface by an area of the first main surface is greater than or equal to 0.05 and less than or equal to 0.35.
According to the metal porous body sheet of (7), it is possible to lower the electrolysis voltage during water electrolysis.
(8) The metal porous body sheet of (7) may include a metal porous body having a three-dimensional mesh structure. An average pore diameter of the pores in the metal porous body sheet when viewed in a direction orthogonal to the first main surface may be greater than or equal to 100 μm.
(9) In the metal porous body sheet of (7) or (8), the multiple holes may be arranged along a second direction orthogonal to the first direction so as to form multiple columns. The multiple holes included in each of the multiple columns may be periodically arranged at a first interval in the second direction. Each of the multiple columns may be periodically arranged at a second interval in a third direction orthogonal to the first direction and the second direction.
(10) In the metal porous body sheet of (9), each of the multiple holes may have a first width in the second direction and a second width in the third direction. The first width may be greater than or equal to 0.5 mm. The second width may be larger than the first width and may be greater than or equal to 1.5 mm.
According to the metal porous body sheet of (10), it is possible to further lower the electrolysis voltage during water electrolysis.
(11) In the metal porous body sheet of (10), the second width may be greater than or equal to twice the first width.
According to the metal porous body sheet of (11), it is possible to further lower the electrolysis voltage during water electrolysis.
(12) In the metal porous body sheet of (11), the multiple columns may include multiple first columns and multiple second columns. The multiple first columns and the multiple second columns may be alternately arranged in the third direction. The multiple first columns may be located at positions shifted from the multiple second columns by 0.5 times the first interval in the second direction.
(13) In the metal porous body sheet of (12), a value obtained by dividing, by the second interval, a value obtained by subtracting the second width from the second interval may be greater than or equal to 0.5.
According to the metal porous body sheet of (13), it is possible to further lower the electrolysis voltage during water electrolysis.
(14) An electrode according to still another embodiment includes the metal porous body sheet of (13) and a support that has a plate shape and that is disposed on the first main surface. The support includes multiple rhombic holes penetrating the support along the first direction and a strand that is located around each of the multiple rhombic holes. The multiple rhombic holes are arranged in a staggered pattern in such a manner that two diagonals extend along the second direction and the third direction, respectively. Each of the multiple rhombic holes includes a first vertex and a second vertex adjacent to the first vertex. The strand includes a first intersection adjacent to the first vertex and a second intersection adjacent to the second vertex. The metal porous body sheet is disposed such that the second direction coincides with a vertical direction. The support is disposed such that a portion of the strand at an intermediate position between the first intersection and the second intersection overlaps the multiple holes.
According to the electrode of (14), it is possible to lower the electrolysis voltage during water electrolysis.
Next, details of the embodiment will be described with reference to the drawings. In the following drawings, the same or corresponding parts are denoted by the same reference numerals, and redundant description will not be repeated.
(Configuration of Metal Porous Body Sheet according to First Embodiment) A metal porous body sheet (hereinafter referred to as “metal porous body sheet 10”) according to the first embodiment will now be described.
A direction from first main surface 10a to second main surface 10b is referred to as first direction DR1. In plan view (that is, as viewed in a direction orthogonal to first main surface 10a), metal porous body sheet 10 has, for example, a rectangular shape. This rectangular shape includes a first side 10c, a second side 10d, a third side 10e, and a fourth side 10f.
First side 10c and second side 10d extend along a second direction DR2. Second direction DR2 is one of directions orthogonal to first direction DR1. Third side 10e and fourth side 10f extend along a third direction DR3. Third direction DR3 is orthogonal to first direction DR1 and second direction DR2.
First main surface 10a is formed with multiple holes 10g. Each of holes 10g penetrates metal porous body sheet 10 along, for example, first direction DR1. Each of holes 10g is, for example, circular in plan view. Each of holes 10g has an inner diameter d. Inner diameter d is constant from first main surface 10a side to second main surface 10b side, for example.
In the following, the width of hole 10g in second direction DR2 is referred to as a width W1, and the width of hole 10g in third direction DR3 is referred to as a width W2. When hole 10g has a circular shape in plan view, inner diameter d is equal to width W1 and width W2.
The area of hole 10g in plan view is defined as an area S1 The area of first main surface 10a in plan view is defined as an area S2. A value obtained by dividing the total value of areas S1 of all holes 10g by area S2 (hereinafter referred to as “opening ratio”) is greater than or equal to 0.01, for example. The opening ratio is, for example, less than or equal to 0.40. The opening ratio is preferably greater than or equal to 0.01 and less than or equal to 0.40.
Multiple holes 10g are arranged along second direction DR2 so as to form multiple columns in plan view. In the example of
Multiple holes 10g are arranged along third direction DR3 so as to form multiple rows in plan view. In the example of
Multiple holes 10g are arranged in, for example, a square lattice pattern in plan view. Multiple holes 10g may be arranged in a rectangular lattice pattern in plan view.
The distance between two adjacent holes 10g in second direction DR2 is defined as a pitch P1. The distance between two adjacent holes 10g in third direction DR3 is defined as a pitch P2. Pitch P1 may be equal to or different from pitch P2.
When inner diameter d (width W1, width W2), area S1, and area S2 are measured, firstly, image data of metal porous body sheet 10 is obtained by capturing an image of metal porous body sheet 10 from first direction DR1. Secondly, binarization processing is performed on the captured image data, whereby a region where holes 10g are formed and other regions are identified. The area and dimension of each region are measured on the basis of the result of the identification process, whereby the values of inner diameter d, area S1, and area S2 are obtained.
(Configuration of Water Electrolysis Device According to First Embodiment)
A configuration of a water electrolysis device (hereinafter referred to as “water electrolysis device 100”) according to the first embodiment will now be described.
Water electrolysis device 100 is, for example, a device for generating hydrogen gas (H2) and oxygen gas (O2).
Electrode 30a is, for example, a hydrogen generating electrode. Electrode 30b is, for example, an oxygen generating electrode. Each of electrodes 30a and 30b includes metal porous body sheet 10 and a support 20. In metal porous body sheet 10 constituting electrode 30a (electrode 30b), first side 10c and second side 10d extend along the vertical direction, and third side 10e and fourth side 10f extend along the horizontal direction, for example.
In metal porous body sheet 10 constituting electrode 30a (electrode 30b), first side 10c and second side 10d may extend along the vertical direction, and third side 10e and fourth side 10f may extend along the horizontal direction, for example. Note that metal porous body sheet 10 may not be used for either electrode 30a or electrode 30b.
Support 20 is disposed on metal porous body sheet 10 (more specifically, on first main surface 10a). Support 20 is, for example, expanded metal. Support 20 is formed with an opening. The opening formed in support 20 penetrates support 20 along the thickness direction (along first direction DR1). When viewed in the direction orthogonal to first main surface 10a, holes 10g are exposed from the opening of support 20.
Diaphragm 40 allows hydrogen ions (H+) or hydroxide ions (OH−) to pass therethrough. As diaphragm 40, a material having low gas permeability and low electron conductivity is used. As diaphragm 40, an ion exchange membrane, a porous diaphragm, or a cloth is used, for example. Diaphragm 40 may be, for example, a membrane formed of a hydrophilic polyethylene nonwoven fabric. Diaphragm 40 is sandwiched between electrode 30a and electrode 30b. Second main surface 10b of metal porous body sheet 10 constituting electrode 30a and second main surface 10b of metal porous body sheet 10 constituting electrode 30b face diaphragm 40.
Frame 70a is formed with an opening 70aa. Opening 70aa penetrates frame 70a along the thickness direction. Frame 70a is further formed with a hole 70ab and a hole 70ac. Hole 70ab extends downward in the vertical direction, and hole 70ac extends upward in the vertical direction. Holes 70ab and 70ac connect opening 70aa and the outside of frame 70a.
Frame 70b is formed with an opening 70ba. Opening 70ba penetrates frame 70b along the thickness direction. Frame 70b is further formed with a hole 70bb and a hole 70bc. Hole 70bb extends downward in the vertical direction, and hole 70bc extends upward in the vertical direction. Holes 70bb and 70bc connect opening 70ba and the outside of frame 70b.
Frame 70a and frame 70b are located such that opening 70aa and opening 70ba overlap each other. Diaphragm 40 is sandwiched between frame 70a and frame 70b so as to be exposed from opening 70aa and opening 70ba.
Frame 70a and frame 70b are sandwiched between two bipolar plates 50. Bipolar plates 50 are made of a material having electron conductivity (having conductivity) for electrical connection with adjacent unit cell. Bipolar plates 50 are made of, for example, nickel (Ni). Although not illustrated, bipolar plates 50 are electrically connected to a power supply at a terminal part of water electrolysis device 100. Bipolar plate 50 is disposed so as to face support 20 included in electrode 30a (electrode 30b).
Electrode 30a is placed in a space defined by diaphragm 40, bipolar plate 50, and opening 70aa. Electrode 30b is placed in a space defined by diaphragm 40, bipolar plate 50, and opening 70ba.
Leaf spring 60a is disposed between bipolar plate 50 and support 20 included in electrode 30a. Leaf spring 60b is disposed between bipolar plate 50 and support 20 included in electrode 30b. As a result, metal porous body sheet 10 included in electrode 30a and metal porous body sheet 10 included in electrode 30b are pressed against diaphragm 40.
An alkaline aqueous solution is supplied from hole 70ab into the space defined by diaphragm 40, bipolar plate 50, and opening 70aa. An alkaline aqueous solution is supplied from hole 70bb into the space defined by diaphragm 40, bipolar plate 50, and opening 70ba. Thus, the space defined by diaphragm 40, bipolar plate 50, and opening 70aa and the space defined by diaphragm 40, bipolar plate 50, and opening 70ba are filled with the alkaline aqueous solution as an electrolytic solution. This alkaline aqueous solution is, for example, an aqueous potassium hydroxide solution (KOH).
During operation of water electrolysis device 100, a voltage is applied between bipolar plates 50 at both ends of the unit cell so that the potential at electrode 30a is lower than the potential at electrode 30b. Thus, in electrode 30a, water in the alkaline aqueous solution is reduced, and hydrogen gas is generated. The hydrogen gas generated at electrode 30a is discharged together with the alkaline aqueous solution from the space defined by diaphragm 40, bipolar plate 50, and opening 70aa through hole 70ac. At this time, hydroxide ions in the alkaline aqueous solution move from the electrode 30a side to the electrode 30b side through diaphragm 40.
The hydroxide ions having moved to the electrode 30b side are oxidized in electrode 30b. As a result, oxygen gas is generated at electrode 30b. The oxygen gas generated at electrode 30b is discharged together with the alkaline aqueous solution from the space defined by diaphragm 40, bipolar plate 50, and opening 70ba through hole 70bc. As such a reaction continues, water electrolysis device 100 generates hydrogen gas and oxygen gas.
Water electrolysis device 100 may be a device for producing chlorine gas (Cl2), hydrogen gas, and an aqueous sodium hydroxide (NaOH). In this case, a sodium chloride (NaCl) aqueous solution is used as the electrolytic solution.
(Effects of Metal Porous Body Sheet 10 and Water Electrolysis Device 100 According to First Embodiment)
The effects of metal porous body sheet 10 and water electrolysis device 100 will be described below.
Bubbles B move vertically upward by the action of buoyancy and reach holes 10g. Bubbles B reaching holes 10g are discharged to the outside of metal porous body sheet 10 through holes 10g. In metal porous body sheet 10, bubbles B are easily discharged to the outside, whereby generated bubbles B are less likely to interfere with the reaction in electrode 30a (electrode 30b). As described above, according to metal porous body sheet 10 and water electrolysis device 100, it is possible to lower the electrolysis voltage during water electrolysis.
The volume ratio of hydrogen gas in metal porous body sheet 10 constituting electrode 30a under the conditions shown in Table 1 was obtained by simulation. In a case where holes 10g were not formed in metal porous body sheet 10 constituting electrode 30a, the volume ratio of hydrogen gas in metal porous body sheet 10 constituting electrode 30a was 19.7 vol %.
On the other hand, in a case where holes 10g were formed in metal porous body sheet 10 constituting electrode 30a, the volume ratio of hydrogen gas in metal porous body sheet 10 constituting electrode 30a was 17.6 vol %. This also reveals that the formation of holes 10g in metal porous body sheet 10 decreases the electrolysis voltage during water electrolysis.
The electrolysis test was conducted using simple water electrolysis device 110.
Plate member 50a is disposed so as to face support 20 included in electrode 30a. Plate member 50b is disposed so as to face support 20 constituting electrode 30b. Plate members 50a and 50b are formed of, for example, a resin material.
Leaf spring 60a is disposed between plate member 50a and support 20 included in electrode 30a. Leaf spring 60b is disposed between plate member 50b and support 20 included in electrode 30b. Plate members 50a and 50b are fixed to each other by, for example, screwing. As a result, metal porous body sheet 10 included in electrode 30a and metal porous body sheet 10 included in electrode 30b are pressed against diaphragm 40.
Connection line 80a has one end electrically connected to metal porous body sheet 10 included in electrode 30a. Connection line 80b has one end electrically connected to metal porous body sheet 10 included in electrode 30b. The other end of connection line 80a and the other end of connection line 80b are electrically connected to a power supply (not illustrated). Connection lines 80a and 80b are formed of, for example, platinum (Pt).
On the other hand, the metal porous body does not present at the portion where hole 10g is formed. Thus, the surface area of metal porous body sheet 10 decreases as the opening ratio increases. For example, when metal porous body sheet 10 having an average pore diameter of 0.8 mm has an opening ratio of less than or equal to 0.40, this metal porous body sheet 10 has a surface area larger than that of common expanded metal. Therefore, when the opening ratio is greater than or equal to 0.01 and less than or equal to 0.40, it is possible to lower the electrolysis voltage during water electrolysis while maintaining the reactivity of metal porous body sheet 10.
(First Modification)
Metal porous body sheet 10 according to a first modification (hereinafter referred to as “metal porous body sheet 10A”) will be described below. Here, differences from metal porous body sheet 10 will be mainly described, and redundant description will not be repeated.
In the example of
Each of holes 10g belonging to second column CL2 is located between two adjacent holes 10g belonging to first column CL1 and is located between two adjacent holes 10g belonging to third column CL3 in second direction DR2. In metal porous body sheet 10A, each of holes 10g belonging to fourth column CL4 is located between two adjacent holes 10g belonging to third column CL3 and is located between two adjacent holes 10g belonging to fifth column CL5 in second direction DR2.
In metal porous body sheet 10A, multiple holes 10g are arranged along third direction DR3 so as to form multiple rows. In the example of
(Second Modification and Third Modification)
Metal porous body sheet 10 according to a second modification (hereinafter referred to as “metal porous body sheet 10B”) and metal porous body sheet 10 according to a third modification (hereinafter referred to as “metal porous body sheet 10C”) will be described below. Here, differences from metal porous body sheet 10A will be mainly described, and redundant description will not be repeated.
(Fourth Modification and Fifth Modification)
Metal porous body sheet 10 according to a fourth modification (hereinafter referred to as “metal porous body sheet 10D”) and metal porous body sheet 10 according to a fifth modification (hereinafter referred to as “metal porous body sheet 10E”) will be described below. Here, differences from metal porous body sheet 10A will be mainly described, and redundant description will not be repeated.
In metal porous body sheet 10D, first main surface 10a is divided into a first region R1 and a second region R2. The width of first region R1 in second direction DR2 is equal to 1/3 of the distance between third side 10e and fourth side 10f. The width of second region R2 in second direction DR2 is equal to 2/3 of the distance between third side 10e and fourth side 10f.
First region R1 includes holes 10g belonging to first row RO1 to third row RO3. Second region R2 includes holes 10g belonging to fourth row RO4 to ninth row RO9. Second region R2 is located closer to fourth side 10f than first region R1. Inner diameter d in second region R2 is larger than inner diameter d in first region R1.
In metal porous body sheet 10E, first main surface 10a is divided into first region R1, second region R2, and a third region R3. First region R1 includes holes 10g belonging to first row RO1 to third row RO3. Second region R2 includes holes 10g belonging to fourth row RO4 to sixth row RO6. Third region R3 includes holes 10g belonging to seventh row RO7 to ninth row RO9.
First region R1, second region R2, and third region R3 are arranged in this order from third side 10e toward fourth side 10f. Inner diameter d in third region R3 is larger than inner diameter d in second region R2, and inner diameter d in second region R2 is larger than inner diameter d in first region R1.
In water electrolysis device 100 using metal porous body sheet 10D, metal porous body sheet 10D is preferably disposed such that second region R2 is positioned vertically above first region R1. The same applies to water electrolysis device 100 using metal porous body sheet 10E.
Bubbles B generated inside metal porous body sheet 10D easily accumulate on the vertically upper side. However, when metal porous body sheet 10D is disposed such that second region R2 is vertically above first region R1, bubbles B are easily discharged from the inside of metal porous body sheet 10D on the vertically upper side, because inner diameter d in second region R2 is larger than inner diameter d in first region R1. Thus, according to water electrolysis device 100 using metal porous body sheet 10D, it is possible to further lower the electrolysis voltage during water electrolysis. The same applies to water electrolysis device 100 using metal porous body sheet 10E.
(Sixth Modification and Seventh Modification)
Metal porous body sheet 10 according to a sixth modification (hereinafter referred to as “metal porous body sheet 10F”) and metal porous body sheet 10 according to a seventh modification (hereinafter referred to as “metal porous body sheet 10G”) will be described below. Here, differences from metal porous body sheet 10A will be mainly described, and redundant description will not be repeated.
In metal porous body sheet 10F, first main surface 10a is divided into first region R1 and second region R2.
The arrangement of holes 10g belonging to first row RO1 to third row RO3 in metal porous body sheet 10F is the same as the arrangement of holes 10g belonging to first row RO1 to third row RO3 in metal porous body sheet 10A. The arrangement of holes 10g belonging to fourth row RO4 to ninth row RO9 in metal porous body sheet 10F is the same as the arrangement of holes 10g belonging to fourth row RO4 to ninth row RO9 in metal porous body sheet 10B. Therefore, the number density of holes 10g in second region R2 is larger than the number density of holes 10g in first region R1.
In metal porous body sheet 10G, first main surface 10a is divided into first region R1, second region R2, and third region R3.
The arrangement of holes 10g belonging to first row RO1 to third row RO3 in metal porous body sheet 10G is the same as the arrangement of holes 10g belonging to first row RO1 to third row RO3 in metal porous body sheet 10A. The arrangement of holes 10g belonging to fourth row RO4 to sixth row RO6 in metal porous body sheet 10G is the same as the arrangement of holes 10g belonging to fourth row RO4 to sixth row RO6 in metal porous body sheet 10B. The arrangement of holes 10g belonging to seventh row RO7 to ninth row RO9 in metal porous body sheet 10G is the same as the arrangement of holes 10g belonging to seventh row RO7 to ninth row RO9 in metal porous body sheet 10C.
Therefore, the number density of holes 10g in third region R3 is larger than the number density of holes 10g in second region R2, and the number density of holes 10g in second region R2 is larger than the number density of holes 10g in first region R1.
Bubbles B generated inside metal porous body sheet 10F easily accumulate on the vertically upper side. However, when metal porous body sheet 10F is disposed such that second region R2 is located vertically above first region R1, bubbles B are easily discharged from the inside of metal porous body sheet 10F on the vertically upper side, because the number density of holes 10g in second region R2 is larger than the number density of holes 10g in first region R1. Thus, according to water electrolysis device 100 using metal porous body sheet 10F, it is possible to further lower the electrolysis voltage during water electrolysis. The same applies to water electrolysis device 100 using metal porous body sheet 10G.
(Eighth to Tenth Modifications)
Metal porous body sheet 10 according to an eighth modification, metal porous body sheet 10 according to a ninth modification, and metal porous body sheet 10 according to a tenth modification (hereinafter referred to as “metal porous body sheet 10H”, “metal porous body sheet 10I”, and “metal porous body sheet 103”, respectively) will be described below. Here, differences from metal porous body sheet 10A will be mainly described, and redundant description will not be repeated.
As a result, bubbles B reaching holes 10g are easily discharged from the first main surface 10a side to the outside of metal porous body sheet 10H along the inclination. Therefore, water electrolysis device 100 using metal porous body sheet 10H can suppress accumulation of bubbles B in the vicinity of diaphragm 40 by placing metal porous body sheet 10I in such a manner that second main surface 10b faces diaphragm 40. The same applies to water electrolysis device 100 using metal porous body sheet 10I or metal porous body sheet 10J.
(Eleventh to Fourteenth Modifications)
Metal porous body sheet 10 according to an eleventh modification, metal porous body sheet 10 according to a twelfth modification, metal porous body sheet 10 according to a thirteenth modification, and metal porous body sheet 10 according to a fourteenth modification (hereinafter referred to as “metal porous body sheet 10K”, “metal porous body sheet 10L”, “metal porous body sheet 10M”, and “metal porous body sheet ION”, respectively) will be described below. Here, differences from metal porous body sheet 10A will be mainly described, and redundant description will not be repeated.
As illustrated in
This triangular shape is, for example, an isosceles triangle whose vertical angle is directed to fourth side 10f. This triangular shape is, for example, an isosceles triangle whose vertical angle is directed to third side 10e.
(Fifteenth Modification)
Metal porous body sheet 10 according to a fifteenth modification (hereinafter referred to as “metal porous body sheet 10O”) will be described below. Here, differences from metal porous body sheet 10A will be mainly described, and redundant description will not be repeated.
(Sixteenth Modification)
Metal porous body sheet 10 according to a sixteenth modification (hereinafter referred to as “metal porous body sheet 10P”) will be described below. Here, differences from metal porous body sheet 10A will be mainly described, and redundant description will not be repeated.
(Seventeenth Modification) Metal porous body sheet 10 according to a seventeenth modification (hereinafter referred to as “metal porous body sheet 10Q”) will be described below.
Here, differences from metal porous body sheet 10A will be mainly described, and redundant description will not be repeated.
(Eighteenth Modification)
Metal porous body sheet 10 according to an eighteenth modification (hereinafter referred to as “metal porous body sheet 10R”) will be described below. Here, differences from metal porous body sheet 10A will be mainly described, and redundant description will not be repeated.
(Nineteenth Modification)
Metal porous body sheet 10 according to a nineteenth modification (hereinafter referred to as “metal porous body sheet 10S”) will be described below. Here, differences from metal porous body sheet 10A will be mainly described, and redundant description will not be repeated.
Hereinafter, results of a water electrolysis test will be described.
As illustrated in Tables 3, 4, 5, and 6, Samples 1 to 47 were prepared as metal porous body sheets used for electrode 30a and electrode 30b. The planar dimensions of Samples 1 to 47 were all 20 mm×20 mm. The thicknesses of Samples 1 to 47 were all 0.5 mm.
The water electrolysis test was conducted using simple water electrolysis device 110 illustrated in
In the water electrolysis test, firstly, an electrolytic current was increased from 0 A to 2 A at 5 mA/s (the electrolytic current was increased from 0 A to 2 A over 4000 seconds). Secondly, constant current electrolysis was performed with the electrolytic current of 2 A. Then, the electrolysis voltage was measured at the time point at which 10 minutes have elapsed from the start of constant voltage electrolysis. Tables 7 and 8 show the measurement results of the electrolysis voltage for each Sample.
As shown in Table 7, the electrolysis voltage was reduced in all Samples (Sample 3 to Sample 47) having holes 10g formed therein. Thus, it has been experimentally revealed that the electrolysis voltage is decreased by forming holes 10g in metal porous body sheet 10.
Sample 5 and Sample 7 were formed under the same conditions except for the cross-sectional shape of hole 10g. Sample 7 had a lower electrolysis voltage than Sample 5. Sample 6 and Sample 8 were formed under the same conditions except for the cross-sectional shape of hole 10g. Sample 8 had a lower electrolysis voltage than Sample 6. Sample 11 and Sample 13 were formed under the same conditions except for the cross-sectional shape of hole 10g. Sample 13 had a lower electrolysis voltage than Sample 11. It has been experimentally reveled from the comparison described above that the electrolysis voltage is decreased by providing a taper shape on hole 10g.
The electrolysis voltages in Sample 44 and Sample 45 were lower than the electrolysis voltage in Sample 9. From this comparison, it has been experimentally revealed that the electrolysis voltage is decreased by setting the number density of holes 10g included in each of the multiple regions formed by dividing first main surface 10a along second direction DR2 to be larger on the other side in second direction DR2 than on one side in second direction DR2.
The electrolysis voltages in Sample 46 and Sample 47 were lower than the electrolysis voltage in Sample 9. From this comparison, it has been experimentally revealed that the electrolysis voltage is decreased by setting inner diameter d of hole 10g included in each of the multiple regions formed by dividing first main surface 10a along second direction DR2 to be larger on the other side in second direction DR2 than on one side in second direction DR2.
(Configuration of Metal Porous Body Sheet according to Second Embodiment)
A configuration of a metal porous body sheet (hereinafter referred to as “metal porous body sheet 10T”) according to the second embodiment will now be described. Here, differences from the configuration of metal porous body sheet 10 will be mainly described, and redundant description will not be repeated.
Metal porous body sheet 10T is constituted by, for example, a metal porous body having a three-dimensional mesh structure. It is to be noted, however, that the metal porous body constituting metal porous body sheet 10T may not have a three-dimensional mesh structure. Metal porous body sheet 10T may be, for example, a woven fabric or a nonwoven fabric made of metal fibers.
The metal porous body constituting metal porous body sheet 10T may be formed of an alloy containing an element dissolved in an alkali and metal having alkali resistance or a composite in which an element dissolved in an alkali is dispersed in metal having alkali resistance. Examples of the element dissolved in an alkali include zinc (Zn), aluminum (Al), and tin (Sn). Examples of the metal having alkali resistance include nickel. In this case, fine irregularities are generated on the surface of the metal porous body due to elution of element by the treatment in an alkali. As a result, the surface area of the metal porous body is increased, and the characteristics of generating hydrogen and oxygen are improved. However, the metal porous body constituting metal porous body sheet 10T may be formed of a metal material other than the above materials.
A catalyst may be supported on the surface of the metal porous body constituting metal porous body sheet 10T. The catalyst is, for example, a noble metal oxide such as ruthenium dioxide (RuO2) or a cobalt oxide. In this case, the characteristics of generating hydrogen and oxygen on the surface of the metal porous body are improved.
The average pore diameter of pores in metal porous body sheet 10T in plan view is greater than or equal to 100 μm. The average pore diameter of pores in metal porous body sheet 10T in plan view is preferably greater than or equal to 400 μm.
The average pore diameter of the pores in metal porous body sheet 10T in plan view is measured by the following method. Firstly, the surface of metal porous body sheet 10T is observed with a microscope or the like. The surface is observed on at least ten fields. Secondly, an average value (nc) of the number of unit cells per 1 inch (25.4 mm=25400 μm) is obtained on the basis of the above observation results. Thirdly, the obtained nc is substituted into the following formula, by which the average pore diameter of pores in metal porous body sheet 10T in plan view is obtained.
<Calculation Formula of Average Pore Diameter of Pores in Metal Porous Body Sheet 10T in Plan View>
(Average pore diameter of pores in metal porous body sheet 10T in plan view (unit. μm))=25400 μm/nc
An opening ratio of metal porous body sheet 10T is greater than or equal to 0.05 and less than or equal to 0.35. The opening ratio of metal porous body sheet 10T is calculated by dividing the total opening area of holes 10g in first main surface 10a by the area of first main surface 10a.
The porosity of metal porous body sheet 10T is greater than or equal to 80%. The porosity of metal porous body sheet 10T is preferably greater than or equal to 85%. The porosity (unit: percent) of metal porous body sheet 10 is calculated by 1−(1−porosity of metal porous body sheet 10T)×(1−opening ratio of metal porous body sheet 10T). The porosity of metal porous body sheet 10T is calculated by [1−{M/(V×d)}]×100 (unit: percent) where the mass of metal porous body sheet 10T is M (unit: g), the external volume of metal porous body sheet 10T is V (unit: cm3), and the density of the metal constituting metal porous body sheet 10T is d (unit: g/cm3).
Multiple holes 10g are arranged so as to form multiple columns CL along second direction DR2, for example. Each of multiple columns CL is periodically arranged along third direction DR3. From another point of view, multiple columns CL are equally spaced along third direction DR3. Multiple columns CL include multiple columns CLa and multiple columns CLb. Columns CLa and columns CLb are alternately arranged in third direction DR3.
Holes 10g belonging to each of multiple columns CL are periodically arranged along second direction DR2. A distance between two adjacent holes 10g in second direction DR2 is defined as a pitch P3. Pitch P3 is a center-to-center distance in second direction DR2 between two adjacent holes 10g.
A distance between two adjacent columns CL in third direction DR3 is defined as a pitch P4. Pitch P4 is a center-to-center distance in third direction DR3 of holes 10g belonging to column CLa and column CLb adjacent to each other.
Column CLa is at a position shifted from column CLb by 0.5 times pitch P3 in second direction DR2. From another point of view, multiple holes 10g are arranged in a staggered pattern.
The width of hole 10g in second direction DR2 is defined as a width W4, and the width of hole 10g in third direction DR3 is defined as a width W5. Width W5 is preferably larger than width W4. Width W4 is preferably greater than or equal to 0.5 mm. Width W5 is preferably greater than or equal to 1.5 mm. Width W5 is more preferably greater than or equal to twice width W4.
A value obtained by dividing a value obtained by dividing width W5 from pitch P4 by pitch P4 is preferably less than or equal to 0.5. From another point of view, it is preferable that the sum of the widths in third direction DR3 of the regions between column CLa and column CLb where holes 10g are not formed is less than or equal to 50% of the width of metal porous body sheet 10T in third direction DR3.
The value obtained by dividing a value obtained by dividing width W5 from pitch P4 by pitch P4 is more preferably less than 0 (width W5 is larger than pitch P4). From another point of view, the position of hole 10g belonging to one column CLa in third direction DR3 preferably partially overlaps the position of hole 10g belonging to column CLb adjacent to one column CLa in third direction DR3.
(Configuration of Water Electrolysis Device According to Second Embodiment)
A configuration of a water electrolysis device (hereinafter referred to as “water electrolysis device 100A”) according to the second embodiment will now be described. Here, differences from the configuration of water electrolysis device 100 will be mainly described, and redundant description will not be repeated.
It is to be noted, however, that, unlike water electrolysis device 100, water electrolysis device 100A uses metal porous body sheet 10T for electrode 30a and electrode 30b instead of metal porous body sheet 10. In metal porous body sheet 10T, first side 10c and second side 10d are along the vertical direction (top-bottom direction in the figure), and third side 10e and fourth side 10f are along the horizontal direction.
Support body 20 is disposed on first main surface 10a.
Multiple rhombic holes 20a are arranged in a staggered pattern. A portion of support 20 where rhombic holes 20a are not formed (a portion around rhombic holes 20a) is a strand 20b. Each of rhombic holes 20a has a vertex 20aa, a vertex 20ab, a vertex 20ac, and a vertex 20ad. Vertex 20aa is adjacent to vertex 20ab and vertex 20ad. Vertex 20ac is adjacent to vertex 20ab and vertex 20ad. Vertex 20aa and vertex 20ac face each other in second direction DR2. Vertex 20ab and vertex 20ad face each other in third direction DR3.
Strand 20b has an intersection 20ba, an intersection 20bb, an intersection 20bc, and an intersection 20bd. Intersection 20ba, intersection 20bb, intersection 20bc, and intersection 20bd are adjacent to vertex 20aa, vertex 20ab, vertex 20ac, and vertex 20ad, respectively.
An intermediate position between intersection 20ba and intersection 20bb is defined as an intermediate position CP1, an intermediate position between intersection 20bb and intersection 20bc is defined as an intermediate position CP2, an intermediate position between intersection 20bc and intersection 20bd is defined as an intermediate position CP3, and an intermediate position between intersection 20bd and intersection 20ba is defined as an intermediate position CP4. Support 20 is disposed on first main surface 10a so as to overlap holes 10g at intermediate position CP1, intermediate position CP2, intermediate position CP3, and intermediate position CP4.
Although not illustrated, support 20 used for electrode 30b also has the same structure as support 20 used for electrode 30a. Although not illustrated, also in electrode 30b, the positional relationship between metal porous body sheet 10T and support 20 is similar to that of electrode 30a.
(Effect of Water Electrolysis Device According to Second Embodiment)
Hereinafter, effects of water electrolysis device 100A will be described.
When the porosity of metal porous body sheet 10T is greater than or equal to 80% and the opening ratio of holes 10g is greater than or equal to 0.05 and less than or equal to 0.35, bubbles B are less likely to stay inside metal porous body sheet 10T, so that the electrolysis voltage of water electrolysis device 100A can be reduced.
A region where hole 10g is not formed may remain between hole 10g belonging to column CLa and hole 10g belonging to column CLb. When width W5 is larger than width W4 (more specifically, w % ben width W4 is greater than or equal to 0.5 mm, and width W5 is greater than or equal to 1.5 mm, and when width W5 is greater than or equal to twice width W4), this region is narrowed, so that bubbles B are further less likely to stay inside metal porous body sheet 10T. As a result, the electrolysis voltage of water electrolysis device 10A can be further reduced.
In particular, when the value obtained by dividing the value obtained by dividing width W5 from pitch P4 by pitch P4 is less than or equal to 0.5, the total width of the region is less than or equal to 50% of the width of metal porous body sheet 10T, and when the value obtained by dividing the value obtained by dividing width W5 from pitch P4 by pitch P4 is less than 0, the region is not present. Therefore, in these cases, the electrolysis voltage of water electrolysis device 100A can be further reduced.
As a result of intensive studies by the present inventors, bubbles B are likely to remain in the portion of metal porous body sheet 10T overlapping intermediate positions CP1 to CP4. Therefore, when hole 10g is formed in the portion of metal porous body sheet 10T overlapping intermediate position CP1 to intermediate position CP4, bubbles B easily escape from metal porous body sheet 10T, so that the electrolysis voltage of water electrolysis device 100A can be further reduced.
(Water Electrolysis Test)
A water electrolysis test using water electrolysis device 100A will be described below.
In the water electrolysis test, the dimensions of electrode 30a and electrode 30b were 55 mm×45 mm, and the thickness of support 20 was 0.8 mm. In the water electrolysis test, the distance between intersection 20ba and intersection 20bc was set to 4 mm, and the distance between intersection 20bb and intersection 20bd was set to 8 mm. In the water electrolysis test, the width of strand 20b was set to 1 mm.
The electrolytic solution used in the water electrolysis test was a 7 mol/L aqueous potassium hydroxide solution. In the water electrolysis test, a hydrophilized polyethylene nonwoven fabric was used for diaphragm 40. In the water electrolysis test, a supply amount of the electrolytic solution was 50 cc/min.
The water electrolysis test was conducted at 60° C. The water electrolysis test was carried out after ten preliminary electrolysis runs. The preliminary electrolysis was performed by passing a steady current of 12.5 A for 5 minutes while switching the positive and negative of electrode 30a and electrode 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 had elapsed was evaluated.
Samples 1 to 37 were prepared as samples to be subjected to the water electrolysis test. In Samples 1 to 37, the average pore diameter of metal porous body sheet 10T w % ben viewed in the direction orthogonal to first main surface 10a, the porosity of metal porous body sheet 10T, the arrangement of holes 10g, the planar shape of holes 10g, the opening ratio of holes 10g, width W4, width W5, pitch P4, and whether holes 10g overlap intermediate positions CP1 to CP4 were changed as shown in Table 9. Samples 1 to 35 are made of a metal porous body having a three-dimensional mesh structure. Sample 36 and Sample 37 are formed of a nonwoven fabric and a woven fabric (knit) of metal fibers, respectively.
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, Samples 16 to 20, Sample 22, Samples 24 to 30, and Samples 32 to 37 exhibited lower electrolysis voltages than Sample 1.
On the other hand, Samples 1 to 6, Sample 10, Sample 13, Sample 15, Sample 21, Sample 23, and Sample 31 exhibited an electrolysis voltage greater than or equal to that of Sample 1.
As shown in Table 9, in Samples 7 to 9, Sample 11, Sample 12, Sample 14, Samples 16 to 20. Sample 22. Samples 24 to 30, and Samples 32 to 37, the porosity of metal porous body sheet 10T was greater than or equal to 80%, and the opening ratio of holes 10g was greater than or equal to 0.05 and less than or equal to 0.35.
On the other hand, in Samples 1 to 6, no hole 10g was formed. In addition, Sample 10, Sample 13, Sample 15, Sample 21, Sample 23, and Sample 31 did not satisfy any of the conditions that the porosity of metal porous body sheet 10T was greater than or equal to 80% and that the opening ratio of holes 10g was greater than or equal to 0.05 and less than or equal to 0.35.
From this comparison, it has been experimentally revealed that the electrolysis voltage of water electrolysis device 100A is lowered by setting the porosity of metal porous body sheet 10T to be greater than or equal to 80% and setting the opening ratio of holes 10g to be greater than or equal to 0.05 and less than or equal to 0.35.
It should be understood that the embodiments disclosed herein are illustrative in all respects and not restrictive. The scope of the present invention is defined not by the above description of the embodiments but by the claims, and is intended to include meanings equivalent to the claims and all modifications within the scope.
10
a: First main surface, 10b: Second main surface, 10c: first side, 10d: second side, 10e: third side, 10f: fourth side, 10g, 10ga, 10gb, 10gc, 10gd, 10ge, 10gf, 10gg: hole, 10h: bottom portion, 10i: first portion. 10j: second portion, 11: skeleton, 11a: skeleton body, 11b: internal space, 20: support, 20a: rhombic hole, 20b: strand, 20aa, 20ab, 20ac, 20ac: vertex, 20ba, 20bb, 20bc, 20bd: intersection, 30a. 30b: electrode, 40: diaphragm, 50: bipolar plate, 50a: plate member, 50b: plate member, 60a, 60b: leaf spring, 70a: frame, 70aa: opening, 70ab, 70ac: hole, 70b: frame, 70ba: opening, 70bb, 70bc: hole, 80a, 80b: connection line, 90: container, 91: electrolytic solution 100, 100A: water electrolysis device, 110: simple water electrolysis device, 10, 10A, 10B, 10C, 10D, 10E, 10F, 10G, 10H, 10I, 10J, 10K, 10L, 10M, ION, 10O, 10P, 10Q, 10R, 10S, 10T: metal porous body sheet B: bubble, CL1: first column. CL2: second column. CL3: third column, CL4: fourth column, CL5: fifth column. CL, CLa, CLb: column, CP1, CP2, CP3, CP4: intermediate position, DR1: first direction, DR2: second direction, DR3: third direction, L1. L2: length, P1, P2, P3, P4: pitch, R1: first region, R2: second region, R3: third region, RO1: first row, RO2: second row, RO3: third row, RO4: fourth row, RO5: fifth row, RO6: sixth row, RO7: seventh row, RO8: eighth row, RO9: ninth row, S1: area, S2: area, W1, W2, W3, W4, W5: width, d: inner diameter, DE: depth
Number | Date | Country | Kind |
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PCT/JP2020/002739 | Jan 2020 | JP | national |
The present disclosure relates to a metal porous body sheet and a water electrolysis device. The present application claims priority based on PCT/JP2020/002739, which is an international patent application filed on Jan. 27, 2020. All the contents described in the international patent application are incorporated herein by reference.
Filing Document | Filing Date | Country | Kind |
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PCT/JP2021/001983 | 1/21/2021 | WO |