JP6616438B2 - Feeder - Google Patents

Description

  The present invention relates to a power feeding body, and an electrolysis cell and an electrolysis apparatus using the same.

  In recent years, electrolyzers that electrolyze water to produce electrolyzed water having various functions and generate gas such as hydrogen have been used. For example, in a water electrolysis apparatus that generates hydrogen and oxygen by electrolyzing pure water or the like, a unit in which a predetermined set of electrolytic cells having solid electrolyte membranes are arranged is used. As a structure of the electrolytic cell, a structure including a solid electrolyte membrane and a power feeding body arranged so as to sandwich the solid electrolyte membrane is known.

  Conventionally, porous materials such as meshes and fiber bodies have been used as power supply bodies in water electrolysis apparatuses in order to release generated gases such as hydrogen and oxygen. For example, a power supply body having a porous structure in which a large number of holes are opened in a metal plate base material by expanding or punching is used. Patent Document 1 discloses a technique in which an unsintered titanium fiber body is interposed between a solid electrolyte membrane and an electrode.

JP 2004-315933 A

  When electrolysis is performed by continuously operating a water electrolysis apparatus, the solid electrolyte membrane may be damaged due to various factors, which may result in a decrease in electrolysis efficiency and a reduction in apparatus life. For example, there is an advantage that the larger the pores of the porous power supply body, the easier it is for gas to escape, but on the other hand, if the area of the part where the holes are not formed becomes smaller, the electric resistance increases, so the electrolytic efficiency decreases and heat generation May easily occur, leading to a reduction in the device life.

  Further, in a power supply body having a porous structure processed by expanding or punching, irregularities such as burrs and hole edges due to processing are likely to occur on the surface that contacts the solid electrolyte membrane, and thereby the area of the contact portion tends to be reduced. For this reason, there is a technical problem in that stress concentrates on the contact portion or current concentrates due to increase in contact resistance, which easily damages the solid electrolyte membrane and leads to a reduction in device life. Yes. Further, even in the configuration using the above-described fiber body, since the area where the fiber body and the solid electrolyte membrane are in contact with each other is small, there is a similar technical problem.

  This invention is made | formed in view of said technical subject, and makes it a subject to provide the electric power feeding body which can be used stably for a long time, and the electrolysis cell and electrolysis apparatus using the same.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have determined that the number of through-holes per unit area and the solid electrolyte in the power supply body disposed in contact with at least one surface of the solid electrolyte membrane of the electrolytic cell By setting the surface roughness of the surface arranged in contact with the membrane within a specific range, it is possible to suppress damage to the solid electrolyte membrane, achieve a long life of the electrolyzer, and provide a power supply that can be used stably for a long time. The present invention has been completed by finding out that it can be provided.

That is, the present invention is as follows.
1. A substrate made of Ti or a Ti alloy, and a noble metal layer made of a noble metal on one surface of the substrate, and the noble metal layer is disposed in contact with at least one surface of the solid electrolyte membrane of the electrolytic cell; A power feeder,
The power feeding body has 200 or more through holes penetrating from the surface of the noble metal layer to another surface facing the noble metal layer in one square cm square,
The surface roughness (Ra) of the surface disposed in contact with the solid electrolyte membrane is 0.5 μm or less.
Feeder.
2. 2. The power feeding body according to 1, wherein the through-hole is provided at 5000 or less in 1 square cm square.
3. 3. The power supply body according to 1 or 2 above, wherein the thickness is 0.05 mm or more and 0.35 mm or less.
4). The power feeding body according to any one of 1 to 3, wherein an aperture ratio represented by the following formula is 50% or more and 90% or less.
Opening ratio (%) = total through-hole area / substrate area × 100
5. The power feeding body according to any one of 1 to 4, wherein the noble metal layer has a thickness of 0.01 μm or more and 0.3 μm or less.
6). The power feeding body according to any one of 1 to 5, wherein the noble metal layer is a Pt layer made of Pt.
7). The power feeding body according to any one of 1 to 6, wherein the through hole has a tapered structure in which an opening area decreases from a surface disposed in contact with the solid electrolyte membrane toward a thickness direction of the power feeding body. .
8). 8. The power feeding body according to any one of 1 to 7, obtained by coating the noble metal on Ti or a Ti alloy in which the through hole is formed by an etching process.
9. The power supply body according to any one of 1 to 8,
A counter power supply disposed opposite to the power supply;
A solid electrolyte membrane sandwiched between the power feeding body and the counter power feeding body;
An electrolysis cell comprising:
10. The electrolysis cell according to 9,
An electrolytic cell that houses the electrolytic cell;
Means for passing electrolyzed water through the electrolytic cell;
Means for applying a voltage to the water to be electrolyzed in the electrolytic cell to flow current;
An electrolyzer provided with at least.

  In the power feeding body according to the present invention, the number of through holes per unit area and the surface roughness of the surface disposed in contact with the solid electrolyte membrane are set in a specific range. It is possible to suppress the damage of the electrolysis apparatus, to achieve a long life of the electrolysis apparatus, and to provide a power supply that can be used stably for a long time. In addition, by using the power feeding body according to the present invention for a water electrolysis device, electrolyzed water with good dissolved hydrogen content and dissolved efficiency can be obtained.

FIG. 1 is a schematic view showing an embodiment of a power feeding body according to the present invention. FIG. 1A is a view showing that the power supply body has a base material 11, a noble metal layer 12, and a through hole 13, and FIG. 1B is a view showing the through hole 13 of the power supply body. C) is a cross-sectional view showing a taper structure of the through hole 13 of the power feeding body. FIG. 2 is a schematic view simply showing a joined state of the power feeder and the solid electrolyte membrane according to the present invention. FIG. 3 is a schematic view simply showing one embodiment of the electrolysis cell according to the present invention. FIG. 4 is a schematic view showing an embodiment of the electrolysis apparatus according to the present invention. FIG. 5 is a photomicrograph of the power feeder of the example. FIG. 5A shows a power supply body of Example 1 manufactured by an etching method, FIG. 5B shows a power supply body of Example 2 manufactured by an etching method, and FIG. 5C shows Example 3 manufactured by an etching method. It is a microscope picture of this electric power feeder. FIG. 6 is a micrograph of a power feeder of a comparative example. 6A is a power supply of Comparative Example 1 manufactured by etching, FIG. 6B is a micrograph of an expanded power supply of Comparative Example 2 manufactured by machining, and FIG. 6C is mechanical processing. FIG. 6D is a photomicrograph of the power feeder that is a fiber sintered body of Comparative Example 4. FIG. FIG. 7 is a schematic view showing an electrolytic cell produced in the example.

  Below, the form for implementing this invention is demonstrated.

[Power feeder]
The power feeding body according to the present invention includes a base material made of Ti or a Ti alloy, and a noble metal layer made of a noble metal on one surface of the base material. The power supply body functions to energize the solid electrolyte membrane and the electrode, and contacts the supplied water with the solid electrolyte membrane and discharges the gas generated through the through hole.
As shown in FIG. 2, the power supply body according to the present invention is disposed and used in contact with at least one surface of the solid electrolyte membrane. That is, the power feeding body according to the present invention may be used as an anode power feeding body disposed on the anode side surface of the solid electrolyte membrane, or may be used as a cathode power feeding body disposed on the cathode side surface of the solid electrolyte membrane. Also good.
As will be described later, the power supply body according to the present invention has a noble metal layer containing a noble metal such as Pt. In this case, the power supply body according to the present invention is at least a solid electrolyte membrane through the noble metal layer. It is arranged and used in contact with one surface.

  As shown in FIG. 1A, an embodiment of the power supply body according to the present invention includes a base material 11 and a noble metal layer 12 made of a noble metal on at least one surface of the base material 11, and has a plurality of penetrations. This is a plate-like power supply body 1 provided with holes 13.

In the power supply body according to the present invention, the base material is made of Ti or a Ti alloy. Examples of the Ti alloy include alloys of Ti and at least one metal selected from Al, V, Mo, Pd, Mn, Sn, and Fe.
From the viewpoint of excellent electrical conductivity and corrosion resistance, it is preferable to be composed of only Ti.

  The power feeding body according to the present invention includes a noble metal layer made of a noble metal on a base material. By having the noble metal layer, deterioration of the substrate due to hydrogen embrittlement or the like can be suppressed. The noble metal layer is provided on at least the surface of the substrate surface that is in contact with the solid electrolyte membrane of the electrolytic cell. In addition, you may provide in the other surface as needed. Examples of the noble metal used for the noble metal layer include Pt, Au, Pd, Ru, Ir, Rh, and alloys thereof. Especially, it is preferable that a noble metal layer is a Pt layer which consists of Pt.

  As shown in FIG. 1B, an embodiment of the power supply body according to the present invention is provided with a through hole 13. The through-hole 13 penetrates from the surface of the noble metal layer to another surface facing it. In the power feeding body according to the present invention, by providing the through hole, it is possible to bring the supplied water into contact with the solid electrolyte membrane or to discharge the generated gas. In the power supply body according to the present invention, it is important that 200 or more through-holes are provided in 1 square cm square of the power supply body. As a result, the number of through holes provided in the power supply body increases, and the shape of the power supply body formed by the through holes becomes fine, so that a voltage is uniformly applied to the entire power supply body. Therefore, the electrolysis voltage is stabilized and damage to the solid electrolyte membrane is suppressed.

The through hole may have, for example, a circular shape, a square shape, or other rectangular shape, or may have some other shape. The plurality of through holes may be arranged in a matrix at regular intervals on the surface of the power supply body, or may be arranged irregularly.
In addition, it is preferable that the width | variety of the narrowest part pinched | interposed into a through-hole in an electric power feeding body is 20-150 micrometers. When the width is in the above range, stable electroconductivity can be ensured while ensuring the electrolytic area of the membrane. The width is preferably 20 μm or more, and more preferably 40 μm or more. The width is preferably 150 μm or less, and more preferably 100 μm or less. In FIG. 1B, the through holes are arranged in a matrix at regular intervals, and the width of the portion sandwiched between the through holes is also constant, so the wire diameter 14 corresponds to the above width.

  More than 200 through holes are provided in the power supply body 1 cm 2 square, and more preferably, 400 or more are provided. On the other hand, when the number of through holes increases, it may be technically difficult to form the through holes while maintaining the required quality such as shape. The through holes are preferably provided at 5000 places or less, more preferably at 4500 places or less, in a square 1 square centimeter of the power feeding body.

  FIG. 1C is a cross-sectional view of the through hole 13 of the power feeding body. As shown in FIG. 1C, the through-hole 13 provided in the power feeding body according to the present invention has an opening area that decreases from the surface arranged in contact with the solid electrolyte membrane in the thickness direction of the power feeding body. A taper structure is preferable. Since the through hole has the tapered structure, the opening area of the film can be increased and the cross-sectional area of the power feeder can be increased, so that a current can flow more stably. Further, since the tapered structure is eliminated, the sharp corner portion is eliminated, so that the film can be hardly damaged.

The power supply body according to the present invention preferably has an aperture ratio represented by the following formula of 50% or more and 90% or less. When the aperture ratio is in the above range, the gas generation area is increased and current concentration is less likely to occur, so that the life of the solid polymer membrane electrode can be kept long. Moreover, when the thing with an aperture ratio of the said range is used for an electrolyzed water manufacture use, the generation | occurrence | production efficiency of high dissolved hydrogen can be obtained. The aperture ratio is preferably 50% or more, and more preferably 60% or more. Moreover, it is preferable that an aperture ratio is 90% or less, and it is more preferable that it is 85% or less.
Opening ratio (%) = total through-hole area / substrate area × 100

  The “total through-hole area” means a value obtained by performing image processing on the power feeder surface image with the SEM and measuring the total area of the through-holes in the power feeder surface image. This means a value obtained by image-processing the power supply surface image with the SEM and measuring the area of the entire power supply surface image including the through hole.

  In the power feeding body according to the present invention, it is important that the surface disposed in contact with the solid electrolyte membrane has a surface roughness (Ra) of 0.5 μm or less. As described above, the power supply body according to the present invention has a low surface roughness in contact with the solid electrolyte membrane and is nearly flat, thereby suppressing pressure concentration and preventing physical membrane damage. it can.

  The surface roughness is 0.5 μm or less, preferably 0.4 μm or less. In order to realize a power supply body having a surface roughness in such a range, a planarization process may be performed in advance by performing a process such as polishing or electrolytic polishing on the surface of the substrate.

  The surface roughness can be calculated according to the following formula by drawing a roughness curve according to JIS B0601. In the following formula, L is the measurement length, and x is the deviation from the average line to the measurement curve.

  Specifically, the surface roughness Ra is obtained as follows. That is, a portion having a measurement length L (50 μm) is extracted from the cross-sectional curve of the power supply member in the direction of the average line, and the roughness curve with the average line of the extracted portion as the x axis and the direction of the vertical magnification as the y axis is y = f When represented by (x), the value given by the above equation is represented by [μm]. The surface roughness Ra is obtained by obtaining 10 roughness curves from the surface of the power supply body and expressing the average surface roughness of the extracted portions obtained from these roughness curves.

The above-described measurement can be performed using, for example, a scanning confocal laser microscope (manufactured by Olympus Corporation, product name: LEXT OLS3000). Details will be described later in Examples.
The surface roughness can also be measured by observing the surface using a scanning electron microscope and obtaining a roughness curve.

  The power feeding body according to the present invention preferably has a thickness of 0.05 mm or more and 0.35 mm or less. When the thickness of the power supply body is in the above range, the generated gas such as hydrogen can be dispersed in the supplied water without staying in the through-holes. The concentration of density is reduced and damage to the solid electrolyte membrane can be prevented. Moreover, the dissolution efficiency of the generated hydrogen gas can be increased. The thickness of the power feeding body is preferably 0.05 mm or more, and more preferably 0.07 mm or more. In addition, the thickness of the power feeding body is preferably 0.35 mm or less, and more preferably 0.20 mm or less.

  In the power supply body according to the present invention, the thickness of the noble metal layer provided on the substrate surface is preferably 0.01 μm or more and 0.3 μm or less. Oxidation and hydrogen embrittlement of the substrate can be suppressed when the thickness of the noble metal layer is in the above range. The thickness of the noble metal layer is preferably 0.01 μm or more, and more preferably 0.03 μm or more.

  If the electric power feeder which concerns on this invention can manufacture the electric power feeder which has the structure mentioned above, the manufacturing method in particular will not be restrict | limited, However, It is preferable to manufacture by the etching method. According to the etching method, since the surface of the power supply body can be finely processed, a through hole having a desired shape can be formed in the power supply body. Among the etching methods, the photoetching method is a pattern forming method using a photolithography method and an etching method.

In the photo-etching method, a photosensitive resist material is applied to a base material to be processed or a base material provided with a noble metal layer, and the power supply unit according to the present invention penetrates per unit area between the light-shielding portion and the light-transmitting portion. A photomask pattern on which a suitable pattern that satisfies the number of holes is formed is exposed and transferred to a photosensitive resist material. Either an exposed part in the case of a positive resist material or an unexposed part in the case of a negative resist material The resist material is removed from only to form a resist pattern. After that, the surface of the base material exposed at the opening of the resist pattern or the base material provided with the noble metal layer is etched to remove the plate material, and then the remaining resist is peeled off. A pattern identical or inverted to the mask pattern is formed on the plate material. Etching includes wet etching and dry etching, and any of them can be manufactured.
Further, the above-described through-hole having a tapered structure can be formed by, for example, a plurality of etchings with a changed mask area.

[Electrolysis cell]
The electrolytic cell according to the present invention includes a power feeding body according to the present invention, a counter power feeding body disposed to face the power feeding body, and a solid electrolyte membrane sandwiched between the power feeding body and the counter power feeding body. And at least.
FIG. 3 simply shows one embodiment of the electrolysis cell according to the present invention. The electrolytic cell 3 of the present embodiment includes a bipolar electrode plate that functions as an anode electrode plate 34 and a cathode electrode plate 35 on both sides of the solid electrolyte membrane 31, and between the solid electrolyte membrane 31 and the electrode plate, As the power feeding body according to the present invention, an anode power feeding body 32 and a cathode power feeding body 33 are interposed.
The anode power supply body 32 and the cathode power supply body 33 are arranged such that the surface having a surface roughness of 0.5 μm or less and the solid electrolyte membrane 31 are in contact with each other and the surface opposite to the surface is in contact with the electrode plate.

The solid electrolyte membrane is a cation exchange membrane having a role of moving hydrogen ions (H ⁺ ) generated on the anode side by electrolysis to the cathode side. As the solid electrolyte membrane, those conventionally used in the fields of electrodialysis and fuel cells can be applied. For example, hydrocarbon-based cation exchange membranes and fluorine-based heavy membranes described in Japanese Patent Application No. 2006-216376 are disclosed. Examples thereof include a cation exchange membrane made of a coalescence.

  The solid electrolyte membrane may be provided with an anode-side and cathode-side catalyst layer on the front and back sides as an electrocatalyst. Examples of the material for the catalyst layer include platinum group metals such as platinum, iridium, platinum oxide, and iridium oxide.

  The electrode plate may be provided with a terminal (not shown) for electrically connecting the external terminal and the electrode plate. For example, a terminal made of Ti can be used. As shown in the electrolytic cell of FIG. 7 produced in the example, the terminal is formed so as to rise substantially perpendicularly from the one side edge of the electrode plate to the main surface. May be.

[Electrolysis equipment]
The present invention also provides an electrolysis apparatus having the above electrolysis cell. The electrolytic apparatus according to the present invention applies a voltage to the electrolytic cell, the electrolytic cell containing the electrolytic cell, means for passing the electrolytic water through the electrolytic cell, and the electrolytic water in the electrolytic cell. And at least means for supplying current. The electrolytic cell has an anode chamber and a cathode chamber separated by a solid electrolyte membrane in the electrolytic cell. In the electrolytic cell, a desired flow path may be appropriately formed in order to efficiently decompose the water to be electrolyzed. Further, the means for passing the electrolyzed water to the electrolytic cell and the means for applying a voltage to the electrolyzed water in the electrolytic cell to flow the current are not particularly limited, and a conventionally known method Can be applied arbitrarily.

FIG. 4 shows an embodiment of the electrolysis apparatus according to the present invention.
The electrolysis apparatus 41 includes a water purification cartridge 42 that purifies electrolyzed water such as tap water, an electrolysis tank 43 that is supplied with purified water, and a control unit 419 that controls each part of the electrolysis apparatus 41. Note that the electrolysis apparatus 41 according to the present invention may not have the water purification cartridge 42, and in the case of not having the water purification cartridge 42, the electrolyzed water is directly passed through the electrolysis tank 43.

  The electrolyzed water passed through the electrolytic bath 43 is electrolyzed there. A means for passing the electrolyzed water through the electrolytic bath 43 will be described later. The electrolytic cell 43 includes an anode power supply body 416a and a cathode power supply body 416b disposed to face each other, and a solid electrolyte membrane 415 disposed between the anode power supply body 416a and the cathode power supply body 416b.

  The solid electrolyte membrane 415 divides the electrolytic cell 43 into a cathode chamber 44 and an anode chamber 410. The solid electrolyte membrane 415 allows cations generated by electrolysis of water to be electrolyzed to pass from the anode chamber 410 to the cathode chamber 44, and the cathode 47 and the anode 49 are electrically connected via the solid electrolyte membrane 415. . When a voltage is applied between the cathode 47 and the anode 49, the water to be electrolyzed is electrolyzed in the electrolytic cell 43 to obtain electrolyzed water. That is, electrolytic hydrogen water is generated in the cathode chamber 44, and acidic water is generated in the anode chamber 410.

  The polarity of the cathode 47 and the anode 49 and the voltage applied to the electrolyzed water in the electrolytic cell 43 are controlled by the control unit 419.

In addition, the electrolysis apparatus according to the present invention preferably further includes means for switching polarity of a voltage applied to the anode power supply body 416a and the cathode power supply body 416b in the electrolytic cell 43. For example, the control unit 419 may be provided with a polarity switching circuit (not shown) for switching the polarity of the cathode 47 and the anode 49. That is, the electrolysis apparatus 41 may include a polarity switching unit for a voltage applied to the anode power supply body 416a and the cathode power supply body 416b in the solid electrolyte membrane 415 in the electrolytic cell 43. By providing the voltage polarity switching means, it is possible to suppress the scale from adhering to the solid electrolyte membrane 415 when electrolysis is performed using the electrolyzed water such as tap water.

  An example of means for passing the electrolyzed water through the electrolytic bath 43 will be described. A first flow path switching valve 418 is provided on the upstream side of the electrolytic bath 43 into which the water to be electrolyzed flows. The first flow path switching valve 418 is provided in a water supply path 417 that communicates the water purification cartridge 42 and the electrolytic cell 43. The water purified by the water purification cartridge 42 flows into the first flow path switching valve 418 via the first water supply path 417a and the second water supply path 417b of the water supply path 417, and is supplied to the anode chamber 410 or the cathode chamber 44. .

  The electrolytic hydrogen water generated in the cathode chamber 44 is passed through the first channel 431 from the cathode chamber outlet 46 and is collected from the water outlet 431 b via the channel switching valve 422. The acidic water generated in the anode chamber 410 is passed from the anode chamber outlet 412 to the second flow path 432 and discharged from the drain outlet 432a via the flow path switching valve 422.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not restrict | limited to the following example.

[Measurement of thickness of feed body (mm) and thickness of precious metal layer (μm)]
Using a fluorescent X-ray film thickness analyzer (SEA6000VX, manufactured by Hitachi High-Tech Science), the thickness of the Pt layer, which is the power feeder and the noble metal layer, was measured nondestructively.

[Measurement of wire diameter]
The wire diameter was measured by image-processing each power feeder surface image with SEM (VE-8800 manufactured by KEYENCE).

[Measurement of aperture ratio (%)]
As for the aperture ratio, each power feeder surface image was subjected to image processing with SEM (VE-8800 manufactured by KEYENCE), the through-hole area and the substrate area were measured, and the aperture ratio was determined by the following formula.
Opening ratio (%) = total through-hole area / substrate area × 100

[Measurement of the number of through holes per unit area (pieces / cm ² )]
The through-holes were image-processed on each power supply surface image with SEM (VE-8800 manufactured by KEYENCE), and the number per unit area was measured.

[Measurement of surface roughness (μm)]
The surface roughness of the power feeder was calculated according to the following formula using a scanning confocal laser microscope (manufactured by Olympus Corporation, product name: EXT OLS3000) in accordance with JIS B 0601 (2013). . In the following formula, L is the measurement length, and x is the deviation from the average line to the measurement curve.

  Specifically, the surface roughness of the power feeder was determined as follows. That is, a portion having a measurement length L (50 μm) is extracted from the cross-sectional curve of the power supply member in the direction of the average line, and the roughness curve with the average line of the extracted portion as the x axis and the direction of the vertical magnification as the y axis is y = f When represented by (x), the value given by the above equation is represented by [μm]. The surface roughness was expressed as an average value of the surface roughness of the extracted portion obtained from 10 roughness curves obtained from the surface of the power supply body.

[Measurement of dissolved hydrogen amount (ppb) and dissolved efficiency (%)]
The power feeding body was incorporated into the electrolytic cell, tap water was passed through the cell at 0.25 L / min, and electrolysis was performed by passing a current of 0.45 A (5 A / dm ² ). Dissolved hydrogen of tap water discharged from the cathode side was measured with a dissolved hydrogen meter (DH-35A, manufactured by Toa DKK Co., Ltd.).

[Measurement of electrolytic life (hours)]
The power feeding body was incorporated into the electrolytic cell, tap water was passed through the cell at 0.25 L / min, and electrolysis was performed by passing a current of 0.45 A (5 A / dm ² ). At this time, in order to remove the scale of the solid polymer film, the polarity of the positive electrode and the negative electrode was switched once every 10 minutes. In the life test, when the voltage value increased to 5 V or more from the initial voltage, or when the membrane was damaged and the anode-side and cathode-side power feeders were short-circuited and the voltage value became 0.1 V or less, the operation was started. The elapsed time was measured as the lifetime.

Next, a sample manufacturing method will be described.
[Example 1]
(Etching process)
A pure titanium plate (manufactured by Kobe Steel Co., Ltd.) having a size of 5 cm × 5 cm and an average thickness of 1 mm was used as the substrate. A high chemical resistance dry film resist (KN15 manufactured by Mitsubishi Paper Industries Co., Ltd.) was used on this pure titanium plate and laminated on both sides. This was exposed at 300 mj / cm ² with an exposure machine, immersed in a 1 wt% Na ₂ CO ₂ aqueous solution for 5 minutes, and developed. Thereafter, a baking process was performed at 150 ° C. for 30 minutes to form an etching resist. The Ti plate on which the resist was formed was etched with a fluorine etching solution (ammonium hydrogen fluoride 5 wt%, nitric acid 5 wt%) at 30 ° C. for 20 minutes, and then an organic ammine stripping solution (cleaned by Mitsubishi Gas Chemical Co., Ltd.) Etching (R-100)) was performed at 50 ° C. for 1 minute to remove the resist.

(Formation of noble metal layer)
The base material after the etching treatment was subjected to Pt plating under the following conditions, a noble metal layer made of Pt was formed on the base material surface, and a power feeding body was produced. The substrate surface was degreased with an ultrasonic degreasing solution, and the Ti surface was etched with a 5 wt% ammonium fluoride aqueous solution. Thereafter, the Ti material was put in a Pt plating solution (Pt 5 wt%, sulfuric acid 50 g / L, pH = 1), and Pt was electroplated under the conditions of 0.5 A / dm ² and 15 minutes to form a platinum layer. .
Each physical property value of the obtained power feeding body is as shown in Table 1. A micrograph is shown in FIG.

[Example 2]
A power feeder was produced in the same manner as in Example 1 except that the points shown in Table 1 were changed. Each physical property value of the obtained power feeding body is as shown in Table 1. A micrograph is shown in FIG.

[Example 3]
A power feeder was produced in the same manner as in Example 1 except that the points shown in Table 1 were changed. Each physical property value of the obtained power feeding body is as shown in Table 1. A micrograph is shown in FIG.

[Comparative Example 1]
A power feeder was produced in the same manner as in Example 1 except that the points shown in Table 1 were changed. Each physical property value of the obtained power feeding body is as shown in Table 1. A micrograph is shown in FIG.
[Comparative Examples 2 and 3]
As a power feeder, a power feeder obtained by performing Pt plating on a titanium expand manufactured by machining was used. The physical properties of the power feeder are as shown in Table 1. Micrographs are shown in FIGS. 6B and 6C.

[Comparative Example 4]
As a power feeding body, a power feeding body obtained by performing Pt plating on a Ti fiber sintered body (manufactured by Bekato Toshin Metal Fiber Co., Ltd.) was used. The physical properties of the power feeder are as shown in Table 1. A micrograph is shown in FIG.

Using the power feeders of Examples 1 to 3 and Comparative Examples 1 to 4 prepared above, the electrolytic cell shown in FIG.
The power feeding body (30 × 30 mm ² ) is applied from both sides to a solid polymer membrane electrode manufactured by providing a Pt catalyst layer having a thickness of 0.5 μm on both sides of a central portion (30 × 30 mm ² ) of Nafion 117 (manufactured by Dupont). Were placed in contact. At this time, the power feeding body is provided with a titanium terminal for power supply on the surface opposite to the surface in contact with the solid polymer membrane electrode. Further, on both sides of the power supply body, vinyl chloride cases having flow paths capable of flowing in and out of water in the directions indicated by arrows in the figure were arranged.
A DC power source (not shown) was connected to the terminal portion. In addition, a water supply source such as tap water is connected to the flow path provided in the case via a water introduction tube (not shown), and a flow meter capable of measuring the amount of water flowing into the electrolysis cell is provided. .

Using the produced electrolytic cell, water was electrolyzed under the following conditions, and the amount of dissolved hydrogen was measured.
・ Electrolytic part size: 30 × 30mm ²
Current density: 5.0 A / dm ²
・ Flow rate: 0.25 L / min
・ Water temperature (tap water): 21-22 ° C
The results are shown in Table 1.

  As is clear from the above results, long-life and high dissolved hydrogen generation occurs when the number of through-holes in the power supply is 200 or more in 1 square cm square and the surface roughness (Ra) of the power supply is 0.5 μm or less. Efficiency can be obtained.

DESCRIPTION OF SYMBOLS 1,21 Feed body 11 Base material 12 Precious metal layer 13 Through-hole 14 Wire diameter 22, 31, 413, 415 Solid electrolyte membrane 3 Electrolytic cell 32, 416a Anode feed body 33, 416b Cathode feed body 34 Anode electrode plate 35 Cathode electrode plate 41 Electrolyzer 42 Water purification cartridge 43 Electrolytic tank 44 Cathode chamber 45 Cathode chamber inlet 46 Cathode chamber outlet 47 Cathode 49 Anode 410 Anode chamber 411 Anode chamber inlet 412 Anode chamber outlet 417 Water supply path 417a First water supply path 417b Second water supply path 418 First 1 channel switching valve 419 Control unit 422 Channel switching valve 431 1st channel 431b Water outlet 432 2nd channel 432a Drain port

Claims (9)

A substrate made of Ti or a Ti alloy, and a noble metal layer made of a noble metal on one surface of the substrate, and the noble metal layer is disposed in contact with at least one surface of the solid electrolyte membrane of the electrolytic cell; A power feeder,
The power supply body has a thickness of 0.05 mm or more and 0.35 mm or less,
The power feeding body has 200 or more through holes penetrating from the surface of the noble metal layer to another surface facing the noble metal layer in one square cm square,
The surface roughness (Ra) of the surface disposed in contact with the solid electrolyte membrane is 0.5 μm or less.
Feeder.   The power feeding body according to claim 1, wherein the through-hole is provided at 5000 or less in 1 square cm square. The power feeding body according to claim 1 or 2, wherein the aperture ratio represented by the following formula is 50% or more and 90% or less.
Opening ratio (%) = total through-hole area / substrate area × 100 The power feeding body according to any one of claims 1 to 3 , wherein a thickness of the noble metal layer is 0.01 µm or more and 0.3 µm or less. The power feeding body according to any one of claims 1 to 4 , wherein the noble metal layer is a Pt layer made of Pt. The said through-hole is a taper structure from which the opening area becomes small toward the thickness direction of the said electric power feeding body from the surface arrange | positioned in contact with the said solid electrolyte membrane, The any one of Claims 1-5 . Feeder. Of Ti or Ti alloy to form the through hole by etching, obtained by coating the precious metal, the feed body according to any one of claims 1-6. The power feeding body according to any one of claims 1 to 7 ,
A counter power supply disposed opposite to the power supply;
A solid electrolyte membrane sandwiched between the power feeding body and the counter power feeding body;
An electrolysis cell comprising: Electrolysis cell according to claim 8 ,
An electrolytic cell that houses the electrolytic cell;
Means for passing electrolyzed water through the electrolytic cell;
Means for applying a voltage to the water to be electrolyzed in the electrolytic cell to flow current;
An electrolyzer provided with at least.