JP2011246748A - Electrolysis electrode and electrolytic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrolysis electrode and an electrolytic device which efficiently generate a desired gas by preventing the stay of the generated gas.SOLUTION: The electrolysis electrode includes: a porous membrane 6 which is arranged at and opposed to a liquid contact face via a gap 7, and which selectively permeates a generated gas to the side of a gas flow passage without permeating an electrolyte 18; and an electrolyte flow passage impregnating the gap 7 with the electrolyte 18 by introducing the electrolyte 18 into the gap 7. The gap 7 is formed in such a manner that the generated gas generated at the liquid contact face and formed in a bubble shape is contacted with the porous membrane 6.

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. In addition, when hydrogen gas is generated using the structure as a cathode, there is a problem that the gas-liquid separation function hardly works only at the lyophobic interface around the through hole, and the hydrogen gas adheres to the surface and stays there. is there.

  An object of the present invention is to provide an electrolysis electrode and an electrolysis apparatus capable of efficiently generating a desired gas by preventing retention of generated gas.

The electrolysis electrode of the present invention is an electrolysis electrode that separates the generated gas generated on the liquid contact surface during the electrolysis of the electrolyte from the electrolyte and discharges it to the gas flow path side. And a porous membrane that selectively permeates the generated gas to the gas flow path side without allowing the electrolyte solution to pass therethrough, and guiding the electrolyte solution to the gap, thereby An electrolyte flow path for impregnating the electrolytic solution, and the gap is formed so that the generated gas generated in the liquid contact surface and in the form of bubbles comes into contact with the porous membrane. Features.
According to this electrolysis electrode, the electrolytic membrane is provided with a porous membrane disposed opposite to the liquid contact surface via a gap during electrolysis, and the gap is impregnated with the electrolyte by introducing the electrolyte into the gap. . By the electrolyte flow path, the path to the liquid contact surface and the counter electrode contributing to electrolysis can be shortened, and the resistance can be reduced. By the porous membrane, the generated gas can be selectively permeated to the gas channel side without permeating the electrolyte solution, and the electrolyte solution and the gas channel can be completely separated in a stable state. For this reason, it is possible to suppress the retention of the generated gas.

  You may comprise so that the hole diameter of the said porous membrane may become smaller than the width | variety or hole diameter of the said electrolyte solution flow path.

  You may comprise the wall surface of the said electrolyte flow path with an insulating material.

  Of the surface of the electrolysis electrode, at least part of the region other than the liquid contact surface may be made of an insulating material.

  The insulating material may be lyophilic with respect to the electrolytic solution.

  The insulating material may be composed of a passive film of fluoride.

  The surface of the porous membrane in contact with the generated gas may be lyophobic with respect to the electrolytic solution.

  A backing substrate that supports the porous film may be provided.

The electrolysis apparatus of the present invention is characterized in that a molten salt containing a fluorine compound is used as the electrolytic solution, and the electrolysis electrode is used as a cathode.
According to this electrolysis apparatus, hydrogen gas generated at the cathode can be quickly moved to the gas flow path side, and there is no need to separately provide a space for avoiding mixing with fluorine gas generated at the anode. Contributes to downsizing of the device. In addition, since the electrolyte solution and the gas flow path are completely separated by the porous membrane, the molten salt does not enter the gas flow path due to the hydraulic pressure, and a stable interface can be formed.

The electrolysis apparatus of the present invention is characterized in that a molten salt containing a fluorine compound is used as the electrolytic solution, and the electrolysis electrode is used as an anode.
According to this electrolysis apparatus, fluorine gas generated at the anode can be quickly moved to the gas flow path side, and it is not necessary to separately provide a space for avoiding mixing with hydrogen gas generated at the cathode. Contributes to downsizing of the device. In addition, since the electrolyte solution and the gas flow path are completely separated by the porous membrane, the molten salt does not enter the gas flow path due to the hydraulic pressure, and a stable interface can be formed.

  According to the electrolysis electrode of the present invention, an electrolyte flow path is provided in which a porous membrane is disposed opposite to a liquid contact surface through a gap during electrolysis, and the gap is impregnated with the electrolyte by introducing the electrolyte into the gap. Is provided. By the electrolyte flow path, the path to the liquid contact surface and the counter electrode contributing to electrolysis can be shortened, and the resistance can be reduced. By the porous membrane, the generated gas can be selectively permeated to the gas channel side without permeating the electrolyte solution, and the electrolyte solution and the gas channel can be completely separated in a stable state. For this reason, it is possible to suppress the retention of the generated gas.

  According to the electrolysis apparatus of the present invention, if the electrolysis electrode is used at the cathode, the hydrogen gas generated at the cathode can be quickly moved to the gas flow path side, and mixing with the fluorine gas generated at the anode can be avoided. Therefore, it is not necessary to provide a space for this purpose, which contributes to downsizing of the apparatus. In addition, since the electrolyte solution and the gas flow path are completely separated by the porous membrane, the molten salt does not enter the gas flow path due to the hydraulic pressure, and a stable interface can be formed.

  According to the electrolysis apparatus of the present invention, if the electrolysis electrode is used at the anode, the fluorine gas generated at the anode can be quickly moved to the gas flow path side, avoiding mixing with the hydrogen gas generated at the cathode. Therefore, it is not necessary to provide a space for this purpose, which contributes to downsizing of the apparatus. In addition, since the electrolyte solution and the gas flow path are completely separated by the porous membrane, the molten salt does not enter the gas flow path due to the hydraulic pressure, and a stable interface can be formed.

It is a figure which shows the gas-liquid separation electrode 1 of one Embodiment, FIG. 1 (a) is a figure which shows sectional drawing of the gas-liquid separation electrode 1, FIG.1 (b) is a figure which shows sectional drawing of 1 A of gas-liquid separation electrodes. FIG.1 (c) is a figure which shows sectional drawing of the gas-liquid separation electrode 1B. It is a principal part figure which shows the structure of the electroconductive board | substrate 2 and the insulating film 3, FIG. 2 (a) is a figure which shows a front view, FIG.2 (b) shows the IIb-IIb sectional drawing of FIG. 2 (a). FIG. 2 and FIG. 2C are diagrams showing a front view of the conductive substrate 2, and FIG. 2D is a diagram showing a IId-IId sectional view of FIG. It is a figure which shows the modification of the electroconductive board | substrate 2 and the insulating film 3, FIG.3 (a)-(c) is a figure which shows the modification of the electroconductive board | substrate 2 shown to FIG. 2 (a) and (b), FIGS. 3D to 3F are views showing modifications of the conductive substrate 2 and the insulating film 3 shown in FIGS. 2C and 2D. It is a figure which shows the structure of the electrode unit 10 which provided the gas-liquid separation electrode 1, FIG.4 (a) is a front view, FIG.4 (b) is IVb-IVb sectional drawing of Fig.4 (a), FIG.4 (c). ) Is a side view. 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).

  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.

  1A and 1B are diagrams showing a gas-liquid separation electrode 1 according to an embodiment. FIG. 1A is a cross-sectional view of the gas-liquid separation electrode 1, and FIG. 1B is a cross-sectional view of the gas-liquid separation electrode 1A. 1 (c) is a cross-sectional view of the gas-liquid separation electrode 1B. 2A and 2B are main part views showing the configurations of the conductive substrate 2 and the insulating film 3, wherein FIG. 2A is a front view, FIG. 2B is a cross-sectional view taken along line IIb-IIb in FIG. 2C is a front view of the conductive substrate 2, and FIG. 2D is a sectional view taken along line IId-IId in FIG. 2C.

  As shown in FIG. 1A, a gas-liquid separation electrode 1 includes a conductive substrate 2 having a plurality of through holes 2a, an insulating film 3 made of an insulating material, a spacer 5, and a porous film 6 It consists of.

  The conductive substrate 2 is made of pure nickel, for example. The shape of the plurality of through holes 2a provided in the conductive substrate 2 is not limited to the illustrated one, and various structures such as a mesh structure and a porous structure can be adopted.

  The insulating film 3 is made of, for example, a fluoride passive film. Since the insulating coating 3 is coated on one surface of the conductive substrate 2 and the wall surface of the through hole 2a, no electrons are transferred from the surface coated with the insulating coating. Therefore, gas is generated on the surface during electrolysis. do not do. In addition, from the viewpoint of suppressing gas adhesion, the insulating coating 3 is preferably lyophilic. In the present embodiment, a bubble-like gas (hereinafter referred to as a bubble 4) on the liquid contact surface that does not cover the insulating film 3 among the surfaces (liquid contact surface) of the conductive substrate 2 that are in contact with the electrolyte solution 18. Will occur.

  As shown in FIG. 1A, the porous film 6 is disposed to face the liquid contact surface of the conductive substrate 2 with a gap 7 therebetween. In the present embodiment, the porous film 6 is disposed via the spacer 5 on the liquid contact surface side of the gas-liquid separation electrode 1 that is not covered with the insulating film 3, so that the size of the gap 7 is reduced by the spacer 5. It is prescribed.

  The porous membrane 6 allows the bubbles 4 to selectively permeate to the gas flow path side without allowing the electrolyte solution 18 to pass therethrough. The porous film 6 is made of, for example, a PTFE (tetrafluoroethylene resin) porous film. 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 6 are not independent of each other but have a plurality of through holes connected to each other. The porous membrane 6 can isolate the electrolytic solution 18 from the gas chamber 16.

  The pore diameter of the porous membrane 6 is preferably smaller than the width or the pore diameter of the through hole 2a. In particular, when the surface of the porous film 6 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 electrolytic solution 18 is α and the contact angle of the porous membrane 6 is β, lyophobic is 90 ° <α, 90 ° <β, and lyophilic Sex is defined as a relationship of 90 °> α and 90 °> β.

  The through hole 2 a of the conductive substrate 2 functions as an electrolyte flow path that guides the electrolyte solution 18 into the gap 7 between the liquid contact surface of the conductive substrate 2 formed by the spacer 5 and the porous film 6.

  Then, at least part of the bubbles 4 generated on the surface (liquid contact surface) with which the electrolytic solution 18 of the conductive substrate 2 comes into contact comes into contact with the porous film 6 facing the gas-liquid separation electrode 1 to thereby form the porous film. The gas is discharged to the gas chamber 16 through the minute holes formed in 6.

  A gas-liquid separation electrode 1 </ b> A shown in FIG. 1B is a configuration example including a backing substrate 8. The backing substrate 8 is formed with a channel through which the bubbles 4 that pass through the through hole 2a to the gas channel side are transmitted. In the present embodiment, a through hole 8a is formed as a flow path through which the bubbles 4 are transmitted. The backing substrate 8 holds the porous membrane 6 from the gas flow path side. By supplementing the mechanical strength of the porous membrane 6, the gap 7 between the gas-liquid separation electrode 1 and the porous membrane 6 can be kept constant.

  A gas-liquid separation electrode 1B shown in FIG. 1C is a configuration example including a first backing substrate 8B and a second backing substrate 8C. The porous film 6 is sandwiched and fixed between the first backing substrate 8B and the second backing substrate 8C. The first and second backing substrates 8B and 8C are formed with a channel through which bubbles 4 are transmitted from the through hole 2a to the gas channel side. In the present embodiment, through holes 8b and 8c are formed as flow paths through which the bubbles 4 are transmitted. Further, the surface of the second backing substrate 8C has been subjected to a lyophobic treatment, and the bubbles 4 are easily adapted. Thereby, the generated bubbles 4 are continuously separated into the gas flow path by the gas-liquid separator function of the porous membrane 6. Since the gas-liquid separation electrode 1B has a structure in which the porous membrane 6 is sandwiched from both sides, the gap between the gas-liquid separation substrate 1 and the porous membrane 6 can be kept constant even when pressure is applied from the gas chamber 16 side. Become.

  FIG. 3 is a view showing a modified example of the conductive substrate 2 and the insulating coating 3, and FIGS. 3A to 3C show the insulating substrate 2 and the insulating substrate shown in FIGS. 2A and 2B. It is sectional drawing which shows the modification of the membrane | film | coat 3, FIG.3 (d)-(f) is sectional drawing which shows the modification of the electroconductive board | substrate 2 shown to FIG.2 (c) and (d).

  In the example shown in FIGS. 3A and 3D, the cross-sectional area of the through hole 2b of the conductive substrate 2B gradually decreases as the distance from the surface not covering the insulating film 3B increases, and the insulating film 3B Take shape to enlarge again on the side.

  In the example shown in FIGS. 3B and 3E, the cross-sectional area of the through-hole 2c of the conductive substrate 2C gradually increases as the distance from the surface not covering the insulating film 3C increases. Take the maximum shape on the side.

  In the example shown in FIGS. 3C and 3F, the cross-sectional area of the through-hole 2d of the conductive substrate 2D gradually decreases as the distance from the surface not covering the insulating film 3D increases, and the insulating film 3D Take the smallest shape on the side.

  (Structure of electrode holder)

  4 is a diagram showing a configuration of the electrode unit 10 provided with the gas-liquid separation electrode 1, FIG. 4 (a) is a front view, FIG. 4 (b) is an IVb-IVb cross-sectional view of FIG. 4 (a), FIG. 4C 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. 4, the gas-liquid separation electrode 1 is fixed in a state of being sandwiched between the electrode cover 11 and the electrode holder 12. By tightening the electrode cover 11 with the fastening screw 15, the gas-liquid separation electrode 1, the spacer 5, and the porous membrane 6 are brought into close contact with the electrode holder 12, and the electrolytic solution 18 is prevented from entering the gas chamber 16.

  The gas-liquid separation electrode 1 is installed with the surface not covering the insulating coating 3 facing the gas chamber 16 and the facing surface facing the electrolyte 18.

  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.

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.

  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). .

As shown in FIGS. 5A and 5B, the electrolysis apparatus includes electrode units 10A and 10B that hold gas-liquid separation electrodes. Each of the electrode units 10A and 10B includes a gas-liquid separation electrode 1, an electrode cover 11, an electrode holder 12, a gas channel 13, and the like.
The gas-liquid separation electrode of the electrode unit 10A and the gas-liquid separation electrode of the electrode unit 10B are immersed in the electrolytic solution 18 in the electrolytic bath 19 in a state of facing each other, and the electrode unit 10A and the electrode unit 10A are connected via the lead wires 14 and 14C. The power supply 20 for electrolysis is connected to 10B.

  When a voltage that is equal to or higher than the gas generation voltage at both electrodes is applied using the electrolysis power supply 20, 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 in the electrode units 10 </ b> A and 10 </ b> B for both the anode and the cathode is separated into the gas chamber 16. By performing electrolysis in this way, it becomes possible to separate the gas generated at the anode and the gas generated at the cathode, and it is not necessary to attach a skirt for gas separation in the electrolytic cell. Contributes to downsizing.

  5 (c) and 5 (d) are diagrams showing another example of the electrolysis apparatus, FIG. 5 (c) is a diagram showing a top view, and FIG. 5 (d) is a diagram of Vd in FIG. 5 (b). It is a figure which shows -Vd sectional drawing.

  In the example shown in FIGS. 5C and 5D, the electrode unit 10 that holds the gas-liquid separation electrode 1 and the counter electrode 21 that does not have the gas-liquid separation function are immersed in the electrolytic solution 18 in a state of facing each other. Then, a voltage is applied using the electrolysis power supply 20 through the conductive wire 14 and the conductive wire 14C.

  When a voltage equal to or higher than the gas generation voltage is applied between the gas-liquid separation electrode 1 in the electrode unit 10 serving as the cathode and the counter electrode 21 serving as the anode, 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 cathode is separated into the gas chamber 16. On the other hand, another type of gas is generated on the surface of the counter electrode 21 used as the anode, 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.

  In the example shown in FIGS. 5C and 5D, the ion diffusion path from the electrolysis surface of the electrode unit 10 to the electrolysis surface of the counter electrode 21 serving as the anode is shown in FIGS. 5A and 5B. It can be shortened even in the case shown in FIG. That is, in the case shown in FIGS. 5A and 5B, both the anode and the cathode pass through the through-hole 2a of the conductive substrate 2 of the gas-liquid separation electrode 1 to the electrolytic surface of the gas-liquid separation electrode 1. In the example shown in FIGS. 5C and 5D, the increase in the path due to the through hole 2a is only on the cathode side, so that the resistance can be reduced. it can.

  In the above-described embodiment, the gas-liquid separation electrode 1 in the electrode unit 10 having the gas-liquid separation function is used as the cathode, and the counter electrode 21 not having the gas-liquid separation function is used as the anode. Alternatively, the gas-liquid separation electrode 1 in the electrode unit 10 having the above may be used as an anode, and the counter electrode 21 having no gas-liquid separation function may be used as a cathode. In addition, an electrode having an arbitrary structure can be used as an electrode used facing the electrode unit 10.

Example 1
Hereinafter, as Example 1, an example in which hydrogen gas is generated using the gas-liquid separation electrode 1 of the present embodiment will be described. Electrolysis is performed using a molten salt containing a fluorine compound as the electrolytic solution 18 and using the gas-liquid separation electrode 1 as a cathode. As the molten salt containing a fluorine compound, for example, a molten salt KF · n HF (n is a coefficient and n value is not limited, but preferably 1 ≦ n ≦ 3) dissolved by heating is used. When voltage is applied to both electrodes, hydrogen gas is generated as bubbles 4 by electrolysis. In general, since hydrogen gas tends to adhere to and stay on the electrode surface, the effective electrode area of the cathode is remarkably reduced, and the generation of gas at the opposite anode is suppressed by the reaction rate-limiting of the cathode. That is, the gas generation efficiency of the anode is reduced. However, in the gas-liquid separation electrode 1 of the present embodiment, when the generated hydrogen gas grows into bubbles having the same diameter as the gap 7 defined by the spacer 5, it contacts the porous membrane 6 and is separated into the gas chamber 16. The Therefore, it is possible to suppress the retention of bubbles on the surface of the electrolytic electrode, and it is possible to suppress the retention of hydrogen gas at the cathode. In addition, with such a configuration, the back surface separation of the generated bubbles 4 into the gas chamber 16 is performed almost completely, which can contribute to downsizing of the apparatus and stable gas-liquid separation performance.

  As described above, in the gas-liquid separation electrode 1 of the present embodiment, the porous membrane 6 is disposed so as to face the liquid contact surface of the conductive substrate 2 with the gap 7 therebetween. In addition, a through hole 2 a is provided as an electrolyte flow path for introducing the electrolyte solution 18 into the gap 7 so that the gap 7 is impregnated with the electrolyte solution 18. By the electrolyte flow path, the path to the liquid contact surface and the counter electrode contributing to electrolysis can be shortened, and the resistance can be reduced. Furthermore, the porous membrane 6 can selectively permeate the bubbles 4 to the gas flow path side without permeating the electrolytic solution, and completely separate the electrolytic solution 18 and the gas flow path in a stable state. Can do. Therefore, it is possible to suppress the retention of the bubbles 4. Thus, the effective area of the gas-liquid separation interface with which the bubbles 4 come into contact is expanded by dividing the electrode part constituted by the conductive substrate 2 and the gas-liquid separation part constituted by the porous membrane 6. Thus, the contact frequency with the bubbles 4 can be increased.

  In addition, according to the gas-liquid separation electrode 1 of the present embodiment, the pore diameter of the porous membrane 6 is configured to be smaller than the hole diameter of the through hole 2a as the electrolyte flow path. For this reason, since it becomes possible to enlarge the Laplace pressure added when the bubble 4 contacts with a porous membrane, gas-liquid separation performance can be improved.

  Moreover, according to the gas-liquid separation electrode 1 of this embodiment, while covering the wall surface of the through-hole 2a with the insulating film 3, among the surfaces of the conductive substrate 2 of the gas-liquid separation electrode 1, other than the liquid contact surface The region is covered with an insulating film 3. For this reason, it becomes possible to generate gas only on the wetted surface not coated with the insulating coating 3.

  Moreover, according to the gas-liquid separation electrode 1 of this embodiment, the insulating film 3 is made lyophilic. Therefore, the electrolytic solution 18 is well adapted to the insulating coating 3, and the electrolytic solution 18 is easily guided into the electrolytic solution flow path.

  In addition, according to the gas-liquid separation electrode 1 of the present embodiment, the surface of the porous membrane 6 in contact with the bubbles 4 is made lyophobic with respect to the electrolytic solution 18. For this reason, the surface of the conductive substrate 2 becomes easily compatible with the bubbles 4, and separation of the bubbles 4 due to buoyancy is difficult. Therefore, a large amount of the generated bubbles 4 can be attached to the conductive substrate 2 and efficiently separated to the gas chamber 16 side.

  Further, according to the gas-liquid separation electrodes 1 </ b> A and 1 </ b> B of the present embodiment, the backing substrate that supports the porous membrane 6 is provided. Thereby, the gas-liquid separation electrode 1 can be comprised firmly and it becomes possible to perform gas-liquid separation stably.

  In addition, according to the electrolysis apparatus of the present embodiment, the gas-liquid separation electrode 1 is provided with the porous film 6 facing the liquid contact surface of the conductive substrate 2 made of a conductive member via the gap 7. . Furthermore, a through hole 2 a is provided as an electrolyte flow path for introducing the electrolyte solution 18 into the gap 7 to impregnate the gap 7 with the electrolyte solution 18. Such a gas-liquid separation electrode 1 is used as a cathode. A molten salt containing a fluorine compound is used as the electrolytic solution 18. As a result, the hydrogen gas generated at the cathode can be quickly moved to the gas flow path side, and there is no need to provide a separate space for avoiding mixing with the fluorine gas generated at the anode. Contribute. In addition, since the electrolyte solution and the gas flow path are completely separated by the porous membrane, the molten salt does not enter the gas flow path due to the hydraulic pressure, and a stable interface can be formed.

  Further, according to the electrolysis apparatus of the present embodiment, the gas-liquid separation electrode 1 is provided with the porous film 6 facing the liquid contact surface of the conductive substrate 2 made of an electrically conductive member via the gap 7. . Furthermore, a through hole 2 a is provided as an electrolyte flow path for introducing the electrolyte solution 18 into the gap 7 to impregnate the gap 7 with the electrolyte solution 18. Such a gas-liquid separation electrode 1 is used as an anode. A molten salt containing a fluorine compound is used as the electrolytic solution 18. As a result, the fluorine gas generated at the anode can be quickly moved to the gas flow path side, and there is no need to provide a separate space for avoiding mixing with the hydrogen gas generated at the cathode. Contribute. In addition, since the electrolyte solution and the gas flow path are completely separated by the porous membrane, the molten salt does not enter the gas flow path due to the hydraulic pressure, and a stable interface can be formed.

  The scope of application of the present invention is not limited to the above embodiment. In the present embodiment, the electrode unit 10 and the electrolytic cell 19 are independent, but may be configured as a single unit in which the electrode unit 10 and the electrolytic cell 19 are combined.

1, 1A, 1B Gas-liquid separation electrode 2, 2B, 2C, 2D Conductive substrate 2a, 2b, 2c, 2d Through-hole 3, 3B, 3C, 3D Insulating coating 4 Bubble 5 Spacer 6 Porous membrane 7 Gap 8 8B, 8C Backing substrate 8a, 8b, 8c Through hole 10, 10A, 10B Electrode unit 11 Electrode cover 12 Electrode holder 13 Gas channel 14, 14A, 14B, 14C Conductor 15 Fastening screw 16 Gas chamber 18 Electrolytic solution 19 Electrolyzer 20 Electrolysis Power supply 21 Counter electrode

Claims (10)

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 porous membrane that is disposed opposite to the liquid contact surface with a gap therebetween, and selectively transmits the generated gas to the gas flow path side without allowing the electrolyte solution to pass therethrough;
An electrolyte channel for impregnating the electrolyte in the gap by introducing the electrolyte into the gap;
With
The electrolysis electrode characterized in that the gap is formed so that the generated gas generated in the liquid contact surface in the form of bubbles comes into contact with the porous membrane.   The electrolytic electrode according to claim 1, wherein a pore diameter of the porous membrane is smaller than a width or a pore diameter of the electrolyte channel.   The electrolytic electrode according to claim 1 or 2, wherein a wall surface of the electrolyte channel is made of an insulating material.   The electrolysis electrode according to any one of claims 1 to 3, wherein at least a part of a region other than the liquid contact surface is made of an insulating material among the surface of the electrolysis electrode.   The electrolysis electrode according to claim 3, wherein the insulating material is lyophilic with respect to the electrolytic solution.   The electrolysis electrode according to claim 3, wherein the insulating material is a passive film of fluoride.   The electrolysis electrode according to any one of claims 1 to 6, wherein the surface of the porous membrane in contact with the generated gas is lyophobic with respect to the electrolytic solution.   The electrolysis electrode according to claim 1, further comprising a backing substrate that supports the porous film.   An electrolysis apparatus using a molten salt containing a fluorine compound as the electrolytic solution, and generating hydrogen gas using the electrolysis electrode according to claim 1 as a cathode.   An electrolysis apparatus using a molten salt containing a fluorine compound as the electrolytic solution, and generating fluorine gas using the electrolysis electrode according to claim 1 as an anode.