JP2011246747A - Electrolysis electrode and electrolyzer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrolysis electrode and an electrolyzer, in which the intrusion of a molten salt to the side of a gas flow passage caused by hydraulic pressure is prevented, an electrolyte and the gas flow passage are stably held, and which therefore has improved gas-liquid separating performance.SOLUTION: The electrolysis electrode includes: a conductive substrate 2 in which through-holes 2a are formed; and a porous membrane 3 which is arranged along the surface of the conductive substrate 2 in which the through-holes 2a are opened and which selectively permeates bubbles 5 from the through-holes 2a to the side of the gas flow passage without permeating an electrolyte. The bubblers 5 generated at the liquid contact face of the conductive substrate 2 are selectively permeated to the gas flow passage through the through-holes 2a by the porous membrane 3.

Description

  The present invention relates to an electrolysis electrode and an electrolysis apparatus capable of efficiently generating a desired gas by improving electrolysis efficiency.

  Patent Document 1 discloses a technique related to an electrolysis apparatus that uses a Laplace pressure acting on a fine through-hole to separate an electrolytic solution and a gas flow path. According to this method, when the hydraulic pressure is equal to or lower than the Laplace pressure, the electrolytic solution cannot pass through the through hole, and the interface between the electrolytic solution and the gas flow path is stably maintained.

International Publication WO2008 / 132818

  However, since the Laplace pressure is very small when the diameter of the through hole is about several tens of um, the immersion depth of the electrode depending on the hydraulic pressure is limited to about several centimeters to several tens of centimeters. In addition, there is a risk that the electrolyte may enter the gas flow path due to pressure fluctuations in the container.

  An object of the present invention is to provide an electrolysis electrode and an electrolysis device capable of preventing molten salt from entering the gas flow path due to liquid pressure, keeping the electrolyte and the gas flow path stable, and improving the gas-liquid separation performance. There is to do.

The electrolysis electrode of the present invention has a fine channel formed in the electrolysis electrode that separates the generated gas generated on the liquid contact surface during electrolysis of the electrolyte from the electrolyte and discharges it to the gas channel side. The conductive member is disposed along the surface of the conductive member where the fine channel opens, and the generated gas is selectively passed from the fine channel to the gas channel without passing through the electrolyte solution. And a porous membrane that is permeated through.
According to this electrolysis electrode, a conductive member in which a plurality of fine channels are formed, and a porous film that selectively transmits generated gas from the fine channels to the gas channel side are provided. By the porous membrane, the gas generated on the liquid contact surface of the conductive member is selectively permeated to the gas channel side. Therefore, the electrolyte solution can be prevented from entering the gas channel, and the electrolyte solution and the gas channel can be separated in a stable state. Further, by performing gas-liquid separation with a porous membrane separately from the electrode part, the effective area of the gas-liquid separation interface with which the gas comes into contact can be expanded and the contact frequency with the gas can be improved.

  The fine channel may be a through hole penetrating the conductive member, and the pore diameter of the porous membrane may be smaller than the diameter of the through hole.

  You may comprise so that the liquid-contact surface with the said electrolyte solution may become lyophobic among the surfaces of the said electroconductive member.

  You may comprise so that the liquid-contact surface with the said electrolyte solution in the said porous film may become lyophobic.

  A flow path through which the generated gas that permeates from the fine flow path to the gas flow path side is formed, and a backing substrate that holds the porous film from the gas flow path side may be provided.

The electrolysis apparatus of the present invention is characterized in that the electrolysis electrode is used as an anode or a cathode.
According to this electrolysis apparatus, the electrolysis electrode is provided with a conductive member in which a plurality of fine flow paths are formed, and a porous film that selectively permeates the generated gas from the fine flow path to the gas flow path side. Configure. By the porous membrane, the gas generated on the liquid contact surface of the conductive member is selectively permeated to the gas channel side. Therefore, the electrolyte solution can be prevented from entering the gas channel, and the electrolyte solution and the gas channel can be separated in a stable state. Further, by performing gas-liquid separation with a porous membrane separately from the electrode part, the effective area of the gas-liquid separation interface with which the gas comes into contact can be expanded and the contact frequency with the gas can be improved. Further, it is not necessary to attach a skirt or the like for gas separation in the electrolytic bath, and the apparatus can be downsized.

  A molten salt containing a fluorine compound may be used as the electrolytic solution, and fluorine gas may be generated using the electrolysis electrode as an anode.

  According to the electrolysis electrode of the present invention, the conductive member in which a plurality of fine channels are formed and the porous film that selectively transmits the generated gas from the fine channels to the gas channel side are provided. By the porous membrane, the gas generated on the liquid contact surface of the conductive member is selectively permeated to the gas channel side. Therefore, the electrolyte solution can be prevented from entering the gas channel, and the electrolyte solution and the gas channel can be separated in a stable state. Further, by performing gas-liquid separation with a porous membrane separately from the electrode part, the effective area of the gas-liquid separation interface with which the gas comes into contact can be expanded and the contact frequency with the gas can be improved.

  According to the electrolysis apparatus of the present invention, the electrolysis electrode includes a conductive member in which a plurality of fine channels are formed, and a porous film that selectively transmits generated gas from the micro channels to the gas channel side. Is provided and configured. By the porous membrane, the gas generated on the liquid contact surface of the conductive member is selectively permeated to the gas channel side. Therefore, the electrolyte solution can be prevented from entering the gas channel, and the electrolyte solution and the gas channel can be separated in a stable state. Further, by performing gas-liquid separation with a porous membrane separately from the electrode part, the effective area of the gas-liquid separation interface with which the gas comes into contact can be expanded and the contact frequency with the gas can be improved. Further, it is not necessary to attach a skirt or the like for gas separation in the electrolytic bath, and the apparatus can be downsized.

It is a figure which shows the gas-liquid separation electrode 1 of one Embodiment, FIG. 1 (a) is a figure which shows a front view, FIG.1 (b) is a figure which shows Ib-Ib sectional drawing of Fig.1 (a), FIG. (C) is a figure which shows the front view of an electroconductive board | substrate, FIG.1 (d) is a figure which shows Id-Id sectional drawing of FIG.1 (c). It is a figure which shows the modification of a gas-liquid separation electrode, FIG.2 (a)-(c) is a figure which shows the modification of the gas-liquid separation electrode shown to FIG.1 (a) and (b), FIG.2 (d). (F) is a figure which shows the modification of the electroconductive board | substrate shown to FIG.1 (c) and (d). It is a figure which shows the structure of the electrode unit 10 which provided the gas-liquid separation electrode 1, FIG.3 (a) is a front view, FIG.3 (b) is IIIb-IIIb sectional drawing of Fig.3 (a), FIG.3 (c). ) Is a side view. FIG. 4A is a diagram showing a separation state of bubbles 5 generated on the surface of the gas-liquid separation electrode 1, and FIG. 4A shows the bubbles when the bubbles are generated by electrolysis using the electrode unit 10 shown in FIG. 3. FIG. 4B is a diagram showing a state of separation, FIG. 4B is a diagram showing a gas-liquid separation electrode whose surface is subjected to surface treatment with a lyophobic material, and FIG. 4C is a gas-liquid fixed by a backing substrate. The figure which shows a separation electrode. It is a figure which shows the electrolyzer of one Embodiment, FIG. 5 (a) is a figure which shows a top view, FIG.5 (b) is a figure which shows Vb-Vb sectional drawing of Fig.5 (a). It is a figure which shows the other example of an electrolyzer, FIG. 6 (a) is a figure which shows a top view, FIG.6 (b) is a figure which shows VIb-VIb sectional drawing of Fig.6 (a), FIG.6 (c) ) Is a view showing the arrangement of the anode and cathode viewed from the direction of the arrow in FIG. 6B, and FIG. 6D is an external view when the anode and cathode in FIG. 6C are immersed in an electrolytic cell.

  Hereinafter, an embodiment of the electrode according to the present invention will be described. In all the drawings, the same reference numerals are given to the same components, and the description will be omitted as appropriate.

  FIG. 1 is a view showing a gas-liquid separation electrode 1 according to an embodiment, FIG. 1 (a) is a front view, and FIG. 1 (b) is a sectional view taken along line Ib-Ib of FIG. 1 (a). 1 and FIG. 1C are diagrams showing a front view of the conductive substrate 2, and FIG. 1D is a diagram showing a cross-sectional view taken along line Id-Id of FIG. 1C.

  As shown in FIG. 1, the gas-liquid separation electrode 1 includes a conductive substrate 2 in which a plurality of through holes 2a are formed, and a porous film 3 attached to the surface of the conductive substrate 2 in which the through holes 2a are open. It consists of

  The conductive substrate 2 is made of pure nickel, for example. The plurality of through holes 2 a provided in the conductive substrate 2 function as fine flow paths through which gas (bubbles) generated on the liquid contact surface of the conductive substrate 2 passes. The shape of the fine channel is not limited to the through hole, and various structures such as a mesh structure and a porous structure shown in FIG.

  The porous membrane 3 is composed of, for example, a PTFE (tetrafluoroethylene resin) porous membrane. The perforations are formed as a mesh structure, a porous structure, a structure having a plurality of through holes, or the like. Further, it is possible to adopt a structure in which the pores formed in the porous film 3 are not independent of each other and have a plurality of through holes connected to each other. The porous film 3 is used to selectively permeate only gas (bubbles) generated on the liquid contact surface of the conductive substrate 2 to the gas flow path side described later through the through hole 2a. That is, even when a pressure (fluid pressure) corresponding to the depth is generated in the electrolytic solution, the electrolytic solution is prevented from flowing out to the gas flow path side.

  FIG. 2 is a diagram showing a modification of the gas-liquid separation electrode 1, and FIGS. 2A to 2C are cross-sectional views showing modifications of the gas-liquid separation electrode 1 shown in FIGS. 1A and 1B. 2 (d) to 2 (f) are cross-sectional views showing modifications of the conductive substrate 2 shown in FIGS. 1 (c) and 1 (d).

  In the example shown in FIGS. 2 (a) and 2 (d), a shape in which the cross-sectional area of the through hole 2b of the conductive substrate 2B gradually decreases as the distance from the electrolyte solution side increases, and expands again on the porous membrane 3 side. Take. Here, the electrolyte solution side is the side of the surface facing the surface to which the porous film 3 is attached.

  In the example shown in FIG. 2B and FIG. 2E, the cross-sectional area of the through hole 2c of the conductive substrate 2C gradually increases as the distance from the electrolyte solution side increases, and the maximum shape is obtained on the porous membrane 3 side. Take. Although not shown, the cross-sectional area of the through hole may gradually decrease as the distance from the electrolyte solution side increases, and the shape may be minimized on the porous membrane 3 side.

  In the example shown in FIG. 2C and FIG. 2F, the plurality of through holes described above are not independent of each other, but a flat conductive substrate 2D having a plurality of through holes 2d connected to each other. An example of using is shown. Such a conductive substrate 2D is formed of, for example, a foam metal, a single pore monolith structure, a double pore monolith structure, a powder sintered noble metal, a fiber sintered body, or the like.

  (Structure of electrode holder)

  FIG. 3 is a diagram showing the configuration of the electrode unit 10 provided with the gas-liquid separation electrode 1, FIG. 3 (a) is a front view, FIG. 3 (b) is a cross-sectional view taken along line IIIb-IIIb in FIG. FIG. 3C is a side view.

  The electrode unit 10 includes a gas-liquid separation electrode 1, an electrode cover 11, an electrode holder 12, a gas channel 13, a conductive wire 14, and the like. As shown in FIG. 3, the gas-liquid separation electrode 1 is fixed in a state of being sandwiched between an electrode cover 11 and an electrode holder 12. By tightening the electrode cover 11 with the fastening screw 15, the gas-liquid separation electrode 1 is brought into close contact with the electrode holder 12 and the electrolyte solution 18 is prevented from entering the gas chamber 16.

  The gas-liquid separation electrode 1 is installed with the surface on which the porous membrane 3 is attached facing the gas chamber 16 and the facing surface facing the electrolyte 18. The electrolytic solution 18 permeates into the through hole 2 a, but the electrolytic solution 18 and the gas chamber 16 are isolated from each other by the porous film 3. In particular, when the surface of the porous membrane 3 is lyophobic, the penetration of the electrolytic solution 18 is more effectively suppressed. Here, when the contact angle of the gas-liquid separation electrode 1 with respect to the electrolyte is α and the contact angle of the porous membrane 3 is β, lyophobic is 90 ° <α, 90 ° <β, or lyophilic. Is defined as a relationship of 90 °> α and 90 °> β.

  The application of the voltage is performed through a conductive wire 14 connected to the gas-liquid separation electrode 1. The gas separated into the gas chamber 16 passes through the gas channel 13 and is discharged from the electrode unit 10.

  FIG. 4 shows the separation state of the bubbles 5 generated on the surface of the gas-liquid separation electrode 1, and FIG. 4 (a) shows the generation of the bubbles 5 by electrolysis using the electrode unit 10 shown in FIG. It is a figure which shows the mode of bubble separation when letting it be made. At least a part of the bubbles 5 generated on the surface where the gas-liquid separation electrode 1 and the electrolyte 18 are in contact with each other is discharged to the gas chamber 16 through the through hole 2 a and the porous membrane 3. The porous film 3 has a fine porosity and allows gas to pass through but not liquid to pass through. By allowing the electrolytic solution 18 to enter the inside of the through hole 2a, the bubbles 5 can be generated efficiently.

  FIG. 4B is a cross-sectional view showing a gas-liquid separation electrode 1 </ b> A in which the surface of the conductive substrate 2 is surface-treated with the lyophobic material 4. The state of bubble separation when electrolysis is performed using the electrode unit 10 shown in FIG. 3 to generate bubbles 5 is shown. In addition, after the surface of the conductive substrate 2 is surface-treated with the lyophobic material 4, the gas-liquid separation electrode 1A can be formed by attaching the porous film 3.

  This lyophobic surface treatment is preferably applied to at least the surface of the conductive substrate 2 that is in contact with the electrolytic solution 18. In the case of the lyophobic property, it is easier to become familiar with the bubbles 5 generated than the electrolytic solution 18. Therefore, the bubbles 5 generated on the surface of the conductive substrate 2 in contact with the electrolytic solution 18 are not easily separated by buoyancy. Further, the electrolytic solution 18 enters the through hole 2a due to the hydraulic pressure, and a large amount of bubbles 5 generated by electrolysis adhere to the wall surface in the through hole 2a. Thereby, the generated bubbles 5 are continuously separated into the gas flow paths through the through holes 2 a by the gas-liquid separation function of the porous membrane 3. With such a configuration, since the back surface separation of the generated bubbles 5 into the gas chamber 16 is almost completely performed, it is possible to contribute to downsizing of the apparatus and stable gas-liquid separation performance.

  FIG. 4C shows the gas-liquid separation electrode 1 </ b> A fixed by the backing substrate 6. The backing substrate 6 is formed with a flow path through which the bubbles 5 that pass from the through hole 2a to the gas flow path side are transmitted. In this embodiment, a through hole 6a, which is an example of a flow path, is formed. The backing substrate 6 holds the porous membrane 3 from the gas flow path side. According to this configuration, since the porous membrane 3 can be supported in a state where the conductive substrate 2 and the porous membrane 3 are in close contact with each other, the gas-liquid separation electrode 1 can be configured firmly and stably. Gas-liquid separation can be performed.

(Gas generation by electrolysis)

FIG. 5 is a diagram showing an electrolysis apparatus according to an embodiment, FIG. 5 (a) is a diagram showing a top view, and FIG. 5 (b) is a diagram showing a Vb-Vb sectional view of FIG. 5 (a). .
The electrolysis apparatus includes an electrode unit 10 that holds the gas-liquid separation electrode 1 shown in FIG. 4 and a counter electrode 20 that does not have a gas-liquid separation function. The electrode unit 10 and the counter electrode 20 face each other and are immersed in the electrolytic solution 18 in the electrolytic bath 19, and a voltage is applied using an electrolysis power source 21, whereby the electrode unit 10 functions as an anode and the counter electrode 20 functions as a cathode. Let me.

  When a voltage equal to or higher than the gas generation voltage is first applied to both electrodes using the electrolysis power supply 21, different gases are generated on the surfaces of the anode and the cathode depending on the electrolyte type. The gas generated on the surface of the gas-liquid separation electrode 1 in the electrode unit 10 used as the anode is separated into the gas chamber 16 according to the principle described above. On the other hand, a different kind of gas is generated on the surface of the counter electrode 20 used as the cathode, but it does not have a gas-liquid separation mechanism, so that it adheres to the surface or is separated from the electrode surface by buoyancy. By performing electrolysis in this way, it becomes possible to separate the gas generated at the anode and the gas generated at the cathode into separate spaces, and it is necessary to attach a skirt or the like for gas separation in the electrolytic cell 19 This contributes to downsizing of the device.

In this embodiment, pure nickel is used as the material of the conductive substrate 2 to be an electrode, but other materials may be used. For example, as a metal electrode, Pt (platinum), Au (gold), Ag (silver), Pd (palladium), Rh (rhodium), Ir (iridium), W (tungsten) alone or the above as a main component Alloy, or Ni (nickel) -Cu (copper) alloy, Ni (nickel) -Cr (chromium) -Fe (iron) alloy, Ni (nickel) -Mo (molybdenum) alloy, Ni (nickel) -Cr (chromium) -Mo (molybdenum) alloys, etc. are carbon electrodes such as glassy carbon, pyrolytic graphite, basal plain pyrolytic graphite, carbon paste, HOPG (Highly Oriented Pyrolytic Graphite), carbon fiber, BDD (Boron Doped Diamond), ECR (Electron Cyclotron) Resonance (deposition carbon), conductive DLC (Diamond Like Carbon) electrodes, etc. are transparent electrodes with Nesa (Sb (antimony) doped SnO ₂ ) and Nesatoron (Sn (tin)) In ₂ O ₃ ) etc., TiO ₂ , MnO ₂ , PbO ₂ , perovskite oxide, bronze oxide etc. as oxide electrodes, Si, Ge, ZnO, CdS, GaAs, TiO ₂ etc. as semiconductor electrodes Other examples include solid polymer electrolyte electrodes. As the combination of the anode and the cathode, the material may be a single material or a combination of two or more materials. Especially Ni (nickel), Ni (nickel) -Cu (copper) alloy, Ni (nickel) -Cr (chromium) -Fe (iron) alloy, Ni (nickel) -Mo (molybdenum) alloy, Ni (nickel) -Cr (Chromium) -Mo (molybdenum) alloy, glassy carbon, BDD (Boron Doped Diamond), ECR (Electron Cyclotron Resonance) deposited carbon, and conductive DLC (Diamond Like Carbon) electrode are suitable.

  In the present embodiment, a PTFE (tetrafluoroethylene resin) porous film is used as the porous film 3, but a porous film made of other materials may be used. Examples include ETFE (tetrafluoroethylene-ethylene copolymer resin), PFA (ethylene tetrafluoride-perfluoroalkyl vinyl ether copolymer resin), FEP (tetrafluoroethylene-hexafluoropropylene copolymer resin), PCTFE (Ethylene trifluoride chloride resin), PVDF (vinylidene fluoride resin), modified PTFE, ECTFE (chlorotrifluoroethylene-ethylene copolymer resin), perfluoroalkenyl vinyl ether polymer (trade name CYTOP (registered trademark)), THV (Tetrafluoroethylene-hexafluoropropene-vinylidene fluoride copolymer), PC (polycarbonate), PP (polypropylene), HDPE (high density polyethylene), LDPE (low density polyethylene), PMMA (polymethyl methacrylate), PVC (polychlorinated) Vinyl), nylon, and PET (polyester). In particular, PTFE (tetrafluoroethylene resin), ETFE (tetrafluoroethylene-ethylene copolymer resin), PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin), FEP (ethylene tetrafluoride) are fluororesins. -Propylene hexafluoride copolymer resin), PCTFE (ethylene trifluoride chloride resin), PVDF (vinylidene fluoride resin), modified PTFE, ECTFE (chlorotrifluoroethylene-ethylene copolymer resin), perfluoroalkenyl vinyl ether polymer (Trade name CYTOP (registered trademark)) and THV (tetrafluoroethylene-hexafluoropropene-vinylidene fluoride copolymer) are preferable.

(Example 1)
In order to confirm whether gas-liquid separation was performed on the bubbles 5 generated on the electrode surface, the surface of the gas-liquid separation electrode 1 where the bubbles 5 were generated on the electrode surface by electrolysis was observed. A transparent PC (polycarbonate) window material 22 was attached to the electrolytic cell 19A so that the surface of the gas-liquid separation electrode 1 during electrolysis could be observed.

  In this embodiment, the through holes 2a of the gas-liquid separation electrode 1 are formed as a plurality of through holes having a hole diameter of 47 um and a pitch of 135 um and arranged on a staggered lattice. Then, on the back surface of the Ni (nickel) porous substrate subjected to conductive DLC (Diamond Like Carbon) surface treatment, PTFE membrane / Poeflon (registered trademark) FP-500-100 (pore diameter: 5 μm, thickness: 100 μm) as the porous film 3 , Manufactured by Sumitomo Electric Fine Polymer Co., Ltd.). Further, the pore-flon (registered trademark) is sandwiched and fixed by a Ni (nickel) backing substrate 6 having a hole diameter of 47um, a pitch of 135um, and a plurality of through holes 6a arranged on a staggered lattice. Further, molten salt KF · n HF (n is a coefficient and n value is not limited, but preferably 1 ≦ n ≦ 3) is used as the electrolytic solution 18, and a Ni (nickel) electrode is used as the cathode. Observation was performed using a long-focus lens MX-5040RZ and a digital microscope KH-1300 (both manufactured by Hilox).

When a voltage equal to or higher than the gas generation voltage at both electrodes is applied between the gas-liquid separation electrode 1 in the electrode unit 10 serving as the anode and the counter electrode 20 serving as the cathode, the surfaces of the anode and the cathode differ depending on the electrolyte type. Gas is generated. The gas generated on the surface of the gas-liquid separation electrode 1 in the electrode unit 10 used as the anode is not separated from the electrode surface by buoyancy, and is stably separated to the back surface in the gas chamber 16. I confirmed the state. The chemical reaction formula of gas generation at the anode and the cathode is shown below.

_{^{Anode: 2F - → F 2 + 2e}} -
^{Cathode: 2H + + 2e - → H} 2

  6A and 6B are diagrams illustrating another example of the electrolysis apparatus, in which FIG. 6A is a diagram illustrating a top view, and FIG. 6B is a diagram illustrating a cross-sectional view taken along line VIb-VIb in FIG. is there. 6 (c) is a view showing the arrangement of the anode and the cathode as viewed from the direction of the arrow in FIG. 6 (b), and FIG. 6 (d) is an immersion of the anode and the cathode in FIG. 6 (c) in the electrolytic cell 19A. It is an external view when doing. As shown in FIGS. 6A to 6D, an electrode unit 10 that holds the gas-liquid separation electrode 1 and a counter electrode 20A that does not have a gas-liquid separation function are installed, and immersed in the electrolyte 18 to apply a voltage. Assemble the electrolyzer. The counter electrode 20A has such a shape that the gas-liquid separation electrode 1 can be observed through the window member 22 from the outside of the electrolytic cell 19A.

  Even when such an apparatus is used, the gas generated on the surface of the gas-liquid separation electrode 1 in the electrode unit 10 that is also used as the anode is not seen to be separated from the electrode surface by buoyancy. It can be seen that the chamber 16 is stably separated into the back surface.

(Example 2)
Using an electrolyzer shown in FIG. 5, a flat substrate made of GC (glassy carbon) that has been subjected to conductive DLC (Diamond Like Carbon) surface treatment as an anode, and molten salt KF · n HF (where n is a coefficient) The n value is not limited, but it is preferable that 1 ≦ n ≦ 3). Thereafter, the GC substrate subjected to the conductive DLC surface treatment was taken out, and the contact angle of the electrolytic surface was measured. In the measurement method, a 1 [uL] water droplet was dropped on the electrode surface, the shape of the droplet was observed from the side, and the contact angle was calculated by the θ / 2 method. As a result, the contact angle was changed to 75 ° (before electrolysis) and 98.2 ° (after electrolysis), and the electrode surface became a hydrophobic surface by an electrolytic reaction using molten salt KF · n HF. In the case of the conductive DLC surface, the so-called anodic effect was not generated, and electrolysis could be continued stably.

  From this, it can be seen that the use of conductive DLC in Example 1 makes it easier to become familiar with the bubbles 5 than the electrolytic solution 18. Therefore, the generated bubbles 5 are not easily separated by buoyancy. In addition, the electrolytic solution 18 efficiently penetrates into the through hole 2a, and bubbles 5 generated by electrolysis adhere to the wall surface in the through hole 2. Thereby, the generated bubbles 5 are continuously separated into the gas flow paths through the through holes 2a by the gas-liquid separator function of the porous membrane 3.

  As described above, the gas-liquid separation electrode 1 of the present embodiment is disposed along the surface of the conductive substrate 2 in which the through holes 2a are formed and the conductive substrate 2 in which the through holes 2a are opened. And a porous membrane 3 that allows the bubbles 5 to selectively permeate from the through hole 2a to the gas flow path side without passing through. Therefore, the electrolyte solution 18 can be prevented from entering the gas channel side, and the electrolyte solution 18 and the gas channel can be separated in a stable state. Further, by performing gas-liquid separation on the porous membrane 3 separately from the electrode portion, the effective area of the gas-liquid separation interface with which the bubbles 5 come into contact can be expanded and the contact frequency with the bubbles 5 can be improved.

  In addition, according to the gas-liquid separation electrode 1 of the present embodiment, since the pore diameter of the porous membrane 3 is configured to be smaller than the pore diameter of the through hole 2 a of the conductive substrate 2, the bubbles 5 are in contact with the porous membrane 3. It becomes possible to increase the Laplace pressure that is applied. For this reason, gas-liquid separation performance can be improved.

  In the gas-liquid separation electrode 1 </ b> A of this embodiment, the liquid contact surface of the surface of the conductive substrate 2 with the electrolytic solution 18 is made lyophobic with the lyophobic material 4. For this reason, the surface of the conductive substrate 2 is easily compatible with the bubbles 5, and separation of the bubbles 5 due to buoyancy is difficult. For this reason, the generated bubbles 5 can be attached to the conductive substrate 2 in a large amount and efficiently separated to the gas chamber 16 side.

  Moreover, according to the gas-liquid separation electrode 1 of this embodiment, the liquid-contact surface with the electrolyte solution 18 in the porous membrane 3 is made lyophobic. For this reason, it is possible to easily separate the bubbles 5 toward the gas chamber 16 without bringing the electrolyte solution 18 close to the porous membrane 3.

  Moreover, according to the gas-liquid separation electrode 1 of this embodiment, the back substrate 6 which has the some through-hole 6a which permeate | transmits the bubble 5 to the gas flow path side, and hold | maintains the porous membrane 3 from the gas flow path side is provided. ing. Thereby, the gas-liquid separation electrode 1 can be comprised firmly and it becomes possible to perform gas-liquid separation stably.

  Moreover, according to the electrolyzer of this embodiment, it arrange | positions along the surface of the electroconductive board | substrate 2 in which the through-hole 2a was formed, and the electroconductive board | substrate 2 in which the through-hole 2a opens, and does not permeate | transmit electrolyte solution. A gas-liquid separation electrode 1 having a porous membrane 3 that selectively allows bubbles 5 to permeate from the through hole 2a to the gas flow path side is used as an anode or a cathode. For this reason, the electrolyte solution 18 can be prevented from entering the gas channel, and the electrolyte solution 18 and the gas channel can be separated in a stable state. Further, by performing gas-liquid separation on the porous membrane 3 separately from the electrode part, the effective area of the gas-liquid separation interface with which the bubbles 5 come into contact can be expanded and the contact frequency with the bubbles 5 can be improved.

  Further, according to the electrolysis apparatus of the present embodiment, a fluorine compound is used as the electrolytic solution 18 and the gas-liquid separation electrode 1 is used as an anode. Even in this case, the generated fluorine gas can be quickly moved to the gas flow path side opposite to the electrolytic surface, and there is no need to provide a separate space for avoiding mixing with the hydrogen gas generated at the cathode. Therefore, it is not necessary to attach a skirt or the like for performing gas separation in the electrolytic cell 19, and the apparatus can be miniaturized.

  The scope of application of the present invention is not limited to the above embodiment. In the present embodiment, the electrode unit 10 that holds the gas-liquid separation electrode 1 is used as an anode, but may be used as a cathode. Moreover, although the electrode unit 10 and the electrolytic cell 19 are made independent in this embodiment, you may comprise as one unit with which the electrode unit 10 and the electrolytic cell 19 were combined.

DESCRIPTION OF SYMBOLS 1, 1A Gas-liquid separation electrode 2, 2B, 2C, 2D Conductive board | substrate 2a, 2b, 2c, 2d Through-hole 3 Porous film | membrane 4 Liquidphobic material 5 Air bubble 6 Backing board | substrate 6a Through-hole 10 Electrode unit 11 Electrode cover 12 Electrode holder 13 Gas channel 14 Conductor 15 Fastening screw 16 Gas chamber 18 Electrolytic solution 19, 19A Electrolytic tank 20, 20A Counter electrode 21 Power source for electrolysis 22 Window material

Claims (7)

In the electrolysis electrode for separating the generated gas generated on the liquid contact surface during the electrolysis of the electrolyte from the electrolyte and releasing it to the gas flow path side,
A conductive member having a fine channel formed thereon;
A porous material that is disposed along the surface of the conductive member where the fine channel is opened, and selectively transmits the generated gas from the fine channel to the gas channel side without allowing the electrolyte solution to permeate. A membrane,
An electrolysis electrode comprising:   2. The electrolytic electrode according to claim 1, wherein the fine channel is a through-hole penetrating the conductive member, and a pore diameter of the porous film is smaller than a diameter of the through-hole.   3. The electrolysis electrode according to claim 1, wherein a liquid contact surface of the surface of the conductive member with the electrolytic solution is lyophobic. 4.   4. The electrolysis electrode according to claim 1, wherein a liquid contact surface of the porous film with the electrolytic solution is lyophobic. 5.   A flow path through which the generated gas that permeates from the fine flow path to the gas flow path is formed, and a backing substrate that holds the porous film from the gas flow path is provided. The electrolysis electrode according to any one of claims 1 to 4.   6. An electrolysis apparatus using the electrolysis electrode according to any one of claims 1 to 5 as an anode or a cathode.   A molten salt containing a fluorine compound is used as an electrolytic solution, and the electrolysis electrode according to any one of claims 1 to 5 is used as an anode to generate fluorine gas as the generated gas. Electrolysis device.