JP2011038144A - Electrolytic electrode, electrolytic apparatus and electrolytic method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To improve the decomposition efficiency of electrolysis compared to a conventional one. <P>SOLUTION: The electrolytic electrode A1 applied for the electrolysis of a predetermined electrolyte is provided with a liquid contact surface 1b immersed in the electrolyte, a gas contact surface for forming a gas chamber 3a and a plurality of through holes communicating the liquid contact surface 1b and the gas contact surface with each other, each having a liquid repellent film provided on the wall surface and each having a hole diameter having a size set to selectively pass fluorine gas to the electrolyte. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an electrolysis electrode, an electrolysis apparatus, and an electrolysis method.

  The following Patent Document 1 (International Publication) is provided with a number of through-holes that lead from an arbitrary surface to the contralateral surface, and is subjected to a surface treatment to make it lyophilic on the one surface immersed in the electrolytic solution. There is disclosed an electrolysis apparatus characterized in that an electrode that has been subjected to a surface treatment that makes the opposite surface not immersed is lyophobic is used for at least one of an anode and a cathode. According to such an electrolysis apparatus, the gas generated on the surface of the one surface is lyophilic on one surface and lyophobic on the other surface. Therefore, the efficiency of electrolysis can be improved. Such an electrolysis apparatus uses a solution containing a KF-HF mixed molten salt in which potassium fluoride (KF) and hydrogen fluoride (HF) are mixed as an electrolytic solution, and electrolyzes the electrolytic solution to form an anode. And used as a fluorine gas generator for generating fluorine gas.

International Publication No. 2008/132818 Pamphlet

By the way, the conventional electrolyzer described above does not necessarily have a sufficient capability of removing generated gas. That is, by making one surface lyophilic and the opposite surface lyophobic, there is a problem that the fluorine gas generated on one surface of the anode cannot be effectively removed to the opposite surface of the anode through the through hole. .
In addition, when a metal material such as nickel is used as the electrode material for the anode, when the surface of the through hole is not lyophobic, the electrolyte enters the through hole, and the through hole wall is used. Electrolysis causes metal elution from the wall surface and changes the shape of the through hole, so that there is a problem that the effective area of the electrode changes and stable electrolysis cannot be performed.

The present invention has been made in view of the above-described circumstances, and has the following objects.
(1) The generated gas is removed from the generation surface more quickly than in the past.
(2) The generation efficiency of generated gas is improved as compared with the conventional case.
(3) The decomposition efficiency of electrolysis is stabilized more than before.

  In order to achieve the above object, according to the present invention, as a first solution for an electrolysis electrode, an electrolysis electrode used for electrolysis of a predetermined electrolyte solution, which is immersed in the electrolyte solution The surface, the air contact surface that forms the gas flow path, and the liquid contact surface and the air contact surface communicate with each other, the wall surface is lyophobic with respect to the electrolyte, and the pore size is selected with respect to the electrolyte. And a plurality of through-holes set to a size that allows them to pass through.

  As a second solving means relating to the electrolysis electrode, a means is adopted in which the liquid contact surface is lyophilic in the first means.

  As a third solution for the electrolysis electrode, a foam having a plurality of through-holes connected to each other, a single pore monolith structure, a double pore monolith structure, a powder in the first or second means A means is adopted in which one surface of the sintered body or fiber sintered body is a wetted surface.

  As a fourth means for solving the electrolysis electrode, the electrolysis electrode is subjected to electrolysis, and has a first surface that is lyophilic with respect to the electrolytic solution and lyophobic with respect to the electrolytic solution. A means is adopted in which the second surface, the first surface, and the second surface are communicated with each other, and the wall surface includes a plurality of through holes that are lyophobic with respect to the electrolytic solution.

  Further, in the present invention, as the first solving means related to the electrolysis apparatus, either one or both of the anode electrode and the cathode electrode is composed of the electrolysis electrode according to any one of the first to fourth solving means, Adopt the means.

  As a second solving means related to the electrolysis apparatus, a means is adopted in which, in the first means, the electrolytic solution uses a fluorine compound as a molten salt, and the electrolytic solution generates fluorine gas at the anode electrode. .

  The present invention also provides an electrolysis method for electrolyzing a predetermined electrolyte by supplying a predetermined potential to an anode electrode and a cathode electrode as a first means for solving the electrolysis method, the anode electrode Alternatively, the liquid contact surface immersed in the electrolytic solution, the air contact surface forming the gas flow path, the liquid contact surface and the air contact surface are communicated with one or both of the cathode electrodes, and the wall surface is in contact with the electrolyte solution. On the other hand, a means is used in which a material having a plurality of through-holes that are lyophobic and has a pore size set to a size that allows the generated gas to selectively pass through the electrolytic solution is used.

  As a second solving means relating to the electrolysis method, a means is adopted in which the contacting surface is made lyophilic in the first means.

  As a third solving means related to the electrolysis method, in the first or second means, a means is adopted in which the through holes are connected to each other so that the liquid contact surface and the air contact surface communicate with each other.

  As a fourth means for solving the electrolysis method, an electrolysis method for electrolyzing a predetermined electrolyte by supplying a predetermined potential to an anode electrode and a cathode electrode, which is either an anode electrode or a cathode electrode One or both of the first surface that is lyophilic with respect to the electrolytic solution, the second surface that is lyophobic with respect to the electrolytic solution, and the first surface and the second surface are communicated, and the wall surface is electrolyzed. A means of using a plurality of through holes that are lyophobic with respect to the liquid is employed.

According to the present invention, the electrolytic electrode communicates the wetted surface immersed in the electrolytic solution, the wetted surface forming the gas flow path, the wetted surface and the wetted surface, and the wall surface is in contact with the electrolytic solution. On the other hand, since it has a plurality of through-holes that are lyophobic and have a pore size that allows the generated gas to selectively pass through, the generated gas generated on the wetted surface is effectively removed from the wetted surface. It is eliminated and moves to the inside of the through hole, and selectively enters the inside of the through hole from the liquid contact surface and moves to the air contact surface.
According to the present invention, the electrolysis electrode has a first surface that is lyophilic with respect to the electrolytic solution, a second surface that is lyophobic with respect to the electrolytic solution, a first surface, and a second surface. And the wall surface includes a plurality of through holes that are lyophobic with respect to the electrolytic solution, so that generated gas is generated exclusively on the first surface that is lyophilic, and this generated gas is From the first surface to the inside of the through hole, and selectively penetrates into the through hole from the first surface and moves to the second surface.

Therefore, according to the present invention as described above, the generated gas is removed from the generation surface (the wetted surface or the first surface) more quickly than before, thereby improving the generation efficiency of the generated gas as compared with the conventional case. Can do.
In addition, according to the present invention, since the generated gas is eliminated from the generation surface (the wetted surface or the first surface) more quickly than in the past, the decomposition efficiency of electrolysis can be stabilized more than in the past. Can do.

BRIEF DESCRIPTION OF THE DRAWINGS The structure of electrode unit A1 which concerns on 1st Embodiment of this invention is shown, (a) is a front view, (b) is an arrow line view of the X1-X1 line in a front view, (c) is a side view. is there. The structure of the porous electrode plate 1 of electrode unit A1 which concerns on 1st Embodiment of this invention is shown, (a) is a front view, (b) is an arrow line view of the Y1-Y1 line | wire in a front view. It is an arrow view which shows the modification of the through-hole in the porous electrode plate 1 of electrode unit A1 which concerns on 1st Embodiment of this invention, (a) is a 1st modification, (b) is a 2nd modification. Indicates. The structure of electrolysis apparatus B1 which concerns on 1st Embodiment of this invention is shown, (a) is a front view, (b) is an arrow line view of the Z1-Z1 line in a front view. It shows the configuration of an electrode unit A2 according to a second embodiment of the present invention, (a) is a front view, (b) is an arrow view of line X2-X2 in the front view, and (c) is a side view. is there. The structure of the electrolyzer B2 which concerns on 2nd Embodiment of this invention is shown, (a) is a front view, (b) is an arrow line view of the Z2-Z2 line in a front view. It is an arrow line view which shows the structure of the electrolyzer B3 which concerns on 3rd Embodiment of this invention.

Embodiments of the present invention will be described below with reference to the drawings.
[First Embodiment]
First, the first embodiment will be described. As shown in FIG. 1, the electrode unit A 1 according to the first embodiment includes a porous electrode plate 1, a conducting wire 2, an electrode holder 3, a gas conduit 4, an electrode cover 5, and a fastening screw 6. Although details will be described later, the electrode unit A1 is used as an anode electrode or a cathode electrode of the electrolyzer B1.

  As shown in FIG. 2, the porous electrode plate 1 includes a liquid contact surface 1b, a contact surface 1c, and a contact surface 1c between the contact surface 1b and the contact surface 1c of the square and constant thickness conductor plate 1a. A large number of through holes 1d are formed to communicate with each other. The conductor plate 1a is a flat plate made of a predetermined metal, for example, nickel (Ni).

  As shown in the figure, the through-hole 1d is formed by forming a lyophobic coating 1e (a lyophobic film) on the wall surface, and a liquid contact surface 1b and an air contact surface 1c whose cross-sectional shapes are parallel to each other. They are formed so as to be orthogonal and have a constant cross-sectional area. The diameter of 1 d of through-holes is 500 micrometers or less, for example, More preferably, they are 10 micrometers-500 micrometers. The diameter of the through-hole 1d is optimized so that the electrolyte does not enter the through-hole 1d as described in detail below.

The arrangement pitch of the through holes 1d is not particularly limited, but is preferably about 10 μm to 500 μm. That is, the arrangement pitch of the through holes 1d is preferably about the same as the diameter of the through holes 1d.
2 is formed in a state in which the through holes 1d are arranged like a grid, but the arrangement of the through holes 1d is not limited to this, for example, a staggered pattern It may be in a lattice form or an array state without regularity.

  Further, regarding the through hole 1d, a modified example having a cross-sectional shape as shown in FIG. 3 is conceivable. In the first modification shown in FIG. 3 (a), although the central axis of the through hole 1f is orthogonal to the liquid contact surface 1b and the air contact surface 1c, the cross-sectional area becomes farther from the liquid contact surface 1b and the air contact surface 1c. The shape gradually decreases and becomes the smallest on the liquid contact surface 1b and the air contact surface 1c. A lyophobic film 1g is entirely provided on the wall surface of the through hole 1f having such a cross-sectional shape.

  In the second modification shown in FIG. 3B, the central axis of the through hole 1h is orthogonal to the liquid contact surface 1b and the air contact surface 1c, but the cross-sectional area is from the liquid contact surface 1b toward the air contact surface 1c. The shape gradually increases. A lyophobic film 1i is provided on the entire wall surface of the through hole 1h. Such through holes 1f and 1h according to the first and second modifications can be easily formed by, for example, laser processing the conductor plate 1a.

  The liquid contact surface 1b of the porous electrode plate 1 is surface-treated so as to be lyophilic with respect to the electrolytic solution. The porous electrode plate 1 is formed using the conductor plate 1a as a base material. The wall surface of each through-hole 1d has a lyophobic film 1e which is a lyophobic film against the electrolyte on the surface of the conductive material. It is formed entirely. Each such film is formed by applying a lyophobic material by various coating methods such as spray coating, flow coating, spin coating, dip coating, roll coating, and pressure coating.

Here, “lyophilic” means a state in which the angle (contact angle) between the gas-liquid interface and the solid-liquid interface of the droplet is smaller than 90 ° when a certain amount of the droplet is placed on the solid surface. In addition, “liquidphobic” means that the contact angle is greater than 90 °. When the liquid contact surface 1b (lyophilic surface) and the lyophobic film 1e (liquid lyophobic surface) of each through-hole 1d are viewed as the contact angle, the contact angle α of the liquid contact surface 1b (lyophilic surface) with respect to the electrolytic solution (Α <90 °) and the contact angle β (90 ° <β) of the lyophobic film 1e (lyophobic surface) with respect to the electrolyte satisfy the following relational expression (1). That is, the contact angle α of the liquid contact surface 1b is set smaller than the contact angle β of the lyophobic film 1e of each through hole 1d.
α <90 ° <β (1)

  That is, in the porous electrode plate 1, the diameter of the through-hole 1 d is set to 500 μm or less, and the contact angles of the liquid contact surface 1 b (lyophilic surface) and the liquid-phobic film 1 e (liquid-phobic surface) of each through-hole 1 d α and β are configured to satisfy the relational expression (1). For each contact angle α, β, it is more preferable to satisfy the condition of α + 10 ° <90 ° <β or α + 25 ° <90 ° <β instead of the relational expression (1). The contact angle of the air contact surface 1c is not particularly limited, but is preferably set to be larger than 90 ° (that is, lyophobic).

  The conducting wire 2 is an electric wire having one end connected to the air contact surface 1c of the porous electrode plate 1 and the other end connected to the output end of an external power source (not shown). This is for supplying a potential for decomposition to the porous electrode plate 1. The electrode holder 3 is a cubic non-conductive member having a recess formed therein. As shown in the figure, the above-mentioned flat porous electrode plate 1 is attached to the electrode holder 3 in such a state that the hollow portion is closed from one side. Note that the cavity surrounded by the hollow portion of the electrode holder 3 and the porous electrode plate 1 is a gas chamber 3a. Such a gas chamber 3a is a gas flow path formed by the air contact surface 1c and the recessed portion of the electrode holder 3 as shown in the figure, and communicates with the liquid contact surface 1b through a plurality of through holes 1d.

  The gas conduit 4 is a hollow cylindrical non-conductive member whose one end is fixed to the upper part of the electrode holder 3, and the internal cavity is a gas channel 4a communicating with the gas chamber 3a. Although not shown, the other end of the gas conduit 4 is connected to a gas recovery device. The electrode cover 5 is a square non-conductive member having a square opening 5a formed in the center. The electrode cover 5 is for holding the porous electrode plate 1 on a part of the electrode holder 3 so that the liquid contact surface 1b is exposed to the outside through the opening 5a. The fastening screws 6 are used to fasten and fix the electrode cover 5 to the electrode holder 3 and are provided in the vicinity of the respective portions of the electrode cover 5.

  As shown in FIG. 4, the electrode unit A1 configured in this way constitutes an electrolysis apparatus B1 together with the electrolytic cell 7, the electrolytic solution 8, and the power source 9. That is, the electrode unit A1 is immersed as a pair in the electrolytic solution 8 stored in the electrolytic cell 7 and connected to the power source 9 for electrolysis. The electrode unit A1 connected to the positive terminal of the power supply 9 is an anode electrode unit A1p, and the electrode unit A1 connected to the negative terminal of the power supply 9 is a cathode electrode unit A1m. As shown in the figure, the anode electrode unit A1p and the cathode electrode unit A1m are immersed in the electrolytic solution 8 so that the liquid contact surfaces 1b of the porous electrode plates 1 face each other in parallel.

The electrolytic cell 7 is a box-shaped container in which the upper end is released and the electrolytic solution 8 is stored inside. The electrolytic solution 8 is a molten salt containing a predetermined compound (electrolysis object). Various electrolytic solutions 8 are selected depending on the purpose of the electrolysis apparatus B1, that is, what kind of gas (gas) is generated and recovered by electrolysis. For example, when the purpose is to generate and recover fluorine gas (F ₂ ), a mixture of potassium fluoride (KF) and hydrogen fluoride (HF) is used as the electrolyte 8 as a molten salt (KF · nHF). (1 ≦ n ≦ 3)) is selected. The power source 9 is a direct current power source including a positive terminal for outputting a positive potential and a negative terminal for outputting a negative potential.

  Next, the operation of the electrode unit A1 (anode electrode unit A1p, cathode electrode unit A1m) and the electrolysis apparatus B1 configured in this manner will be described in detail.

In the following description, in order to generate and recover fluorine gas (F ₂ ), a fluorine compound, for example, a mixture of potassium fluoride (KF) and hydrogen fluoride (HF) is used as a molten salt (KF · nHF). A case where the electrolytic solution 8 (1 ≦ n ≦ 3) is electrolyzed will be described. In this case, nickel (Ni) is preferably selected as the material of the porous electrode plate 1 (conductor plate 1a) of the anode electrode unit A1p. In addition, although there is no restriction | limiting in particular about the material of the porous electrode plate 1 (conductor plate 1a) of cathode electrode unit A1m, nickel (Ni) is selected similarly to anode electrode unit A1p in this embodiment.

When the electrolytic solution 8 of the molten salt is electrolyzed using the electrolysis apparatus B1, the following reaction formula (2) is applied to the liquid contact surface 1b of the porous electrode plate 1 of the anode electrode unit A1p in contact with the electrolytic solution 8. The chemical reaction shown occurs and fluorine gas (F ₂ ) is generated as bubbles. On the liquid contact surface 1b of the porous electrode plate 1 of the cathode electrode unit A1m, a chemical reaction shown in the following reaction formula (3) occurs, and hydrogen gas (H ₂ ) is generated as bubbles.
Anode: 2F ⁻ → F ₂ + 2e ⁻ (2)
Cathode: 2H ⁺ + 2e ⁻ → H ₂ (3)

Here, since the liquid contact surface 1b of the anode electrode unit A1p is lyophilic, it is familiar with the electrolyte solution 8, and thus fluorine gas (F ₂ ) is efficiently generated. Further, such a wetted surface 1b is not well-suited with fluorine gas (F ₂ ) which is a bubble (gas). On the other hand, since the lyophobic film 1e of the through-hole 1d formed in large numbers on the liquid contact surface 1b is covered with a lyophobic film, the familiarity with the electrolyte 8 is poor, but bubbles (gas) Familiarity with fluorine gas (F ₂ ) is good.

That is, in the porous electrode plate 1 of the anode electrode unit A1p, the relational expression (1) is established between the contact angle α of the liquid contact surface 1b and the contact angle β of the lyophobic film 1e of the through hole 1d. The bubbles of fluorine gas (F ₂ ) generated in the vicinity of the through hole 1d on the liquid contact surface 1b of the anode electrode unit A1p are excluded from the liquid contact surface 1b (lyophilic surface), and the lyophobic film 1e (sparse) in the through hole 1d. Move to liquid level. The bubbles of fluorine gas (F ₂ ) generated in the vicinity of the through hole 1d on the liquid contact surface 1b move from the liquid contact surface 1b to the through hole 1d by the action of this force.

When the surface tension γ [N / m] of the electrolytic solution 8, the contact angle α [deg] of the liquid contact surface 1 b with respect to the electrolytic solution 8, and the radius r [m] of the through hole 1 d, the electrolytic solution 8 is in the through hole 1 d. The pressure (Young-Laplace pressure) ΔP required to enter the interior is expressed by the following equation (4).
ΔP = −2γ (cos α) / r (4)
Therefore, the pressure of the electrolyte 8 at the inlet of the through hole 1d (depending on the depth of the through hole 1d with respect to the electrolyte 8 and the pressure inside the electrolytic cell 7 containing the electrolyte 8) must not exceed the Young Laplace pressure ΔP. In this case, the electrolytic solution 8 cannot enter the through hole 1d.

Thus, in the porous electrode plate 1 of the anode electrode unit A1p, the electrolyte solution 8 has a size that cannot enter the inside, that is, a size that allows the fluorine gas (F ₂ ), which is a generated gas (gas), to pass selectively (described above). And the lyophobic film 1e having a contact angle β larger than the contact angle α of the liquid contact surface 1b is provided on the wall surface of the through hole 1d. Therefore, the fluorine gas (F ₂ ) bubbles generated on the liquid contact surface 1b are effectively excluded from the liquid contact surface 1b and move to the inside of the through hole 1d, and from the liquid contact surface 1b to the through hole 1d. Selectively enters the electrolyte 8 and moves to the air contact surface 1c.

That is, in the anode electrode unit A1p of the present electrolysis apparatus B1, the fluorine gas (F ₂ ) which is a bubble (gas) is effectively separated from the liquid electrolyte 8 and the electrolyte 8 passes through the through hole 1d. Without such, the electrolyte 8 is selectively collected through the through hole 1d and collected in the gas chamber 3a. The fluorine gas (F ₂ ) in the gas chamber 3 a is recovered to the outside through the gas channel 4 a formed by the gas conduit 4.

The operation of the anode electrode unit A1p is the same for the cathode electrode unit A1m paired with the anode electrode unit A1p. That is, in the porous electrode plate 1 of the cathode electrode unit A1m, hydrogen gas (H ₂ ) generated as bubbles on the liquid contact surface 1b selectively passes through the through hole 1d with respect to the electrolyte solution 8 and enters the gas chamber 3a. To be collected. The fluorine gas (F ₂ ) in the gas chamber 3 a is recovered to the outside through the gas channel 4 a formed by the gas conduit 4.

According to such a first embodiment, fluorine gas (F ₂ ) generated on the liquid contact surface 1b of the porous electrode plate 1 of the anode electrode unit A1p and the liquid contact surface 1b of the porous electrode plate 1 of the cathode electrode unit A1m. The generated hydrogen gas (H ₂ ) is effectively excluded from the liquid contact surface 1b into the through hole 1d and selectively penetrates into the through hole 1d with respect to the electrolyte 8 and enters the gas chamber 3a. Collected.

Therefore, according to the first embodiment, the time during which fluorine gas (F ₂ ) or hydrogen gas (H ₂ ) stays on the liquid contact surface 1b can be shortened as compared with the prior art. It is possible to increase the current density of the power supplied to the cathode electrode unit A1m as compared with the conventional case, so that the decomposition efficiency of electrolysis, that is, generation of fluorine gas (F ₂ ) and hydrogen gas (H ₂ ) as generated gases. Efficiency can be improved as compared with the conventional case.

Further, according to the first embodiment, the decomposition efficiency of electrolysis in the anode electrode unit A1p, that is, the generation efficiency of fluorine gas (F ₂ ) can be stabilized more than before.

[Second Embodiment]
Next, a second embodiment will be described. In FIG. 5, the same components as those in FIG. In the following, the same components as those in FIG.

  As shown in FIG. 5, the electrode unit A2 according to the second embodiment is composed of a porous electrode plate 1C, a conducting wire 2, an electrode holder 3A, a gas conduit 4, an electrode cover 5A, and a fastening screw 6. The porous electrode plate 1C is not a plurality of through-holes 1d independent of each other like the porous electrode plate 1 of the first embodiment described above, but a flat plate-like conductive material having a plurality of through-holes 1j connected to each other. It is a sex member. Such a porous electrode plate 1C is made 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.

  As shown in the drawing, the upper portion of the porous electrode plate 1C is sandwiched between the electrode holder 3A and the electrode holder 3A while being accommodated in the recess of the electrode holder 3A. A cavity surrounded by the upper surface of the porous electrode plate 1C, the electrode holder 3A, and the electrode cover 5A forms a gas chamber 3b. In the porous electrode plate 1C, the surface that is not surrounded by the electrode holder 3A and the electrode holder 3A, that is, the lower surface and the side surface is the liquid contact surface 1k. The liquid contact surface 1k of such a porous electrode plate 1C communicates with the gas chamber 3b through a plurality of through holes 1j.

  Further, the liquid contact surface 1k of the porous electrode plate 1C is lyophilically treated, and the wall of each through hole 1j is provided with a lyophobic film 1m which is a lyophobic film. That is, in the porous electrode plate 1C, the relational expression (1) described above with respect to the contact angle with respect to the electrolytic solution 8 is established between the liquid contact surface 1k and the lyophobic film 1m. Also, the hole diameter (diameter) of the through hole 1j is the same as the porous electrode plate 1 of the first embodiment described above, that is, the hole diameter at which the pressure of the electrolyte 8 at the inlet of the through hole 1j does not exceed the Young Laplace pressure ΔP, that is, The hole diameter (for example, 500 μm or less) is set so that the electrolytic solution 8 cannot enter the inside.

  The electrode holder 3A is a box-shaped non-conductive member in which a hollow portion is formed. The electrode cover 5A is a flat plate (with window) non-conductive member as shown in the figure. The electrode cover 5A is provided with fastening screws 6 provided in the vicinity of both ends. The electrode holder 3A and the electrode cover 5A sandwich the upper portion of the porous electrode plate 1C when the electrode cover 5A is fixed to the electrode holder 3A by the fastening screw 6.

  As shown in FIG. 6, the electrode unit A <b> 2 configured in this way is immersed as a pair in an electrolytic solution 8 stored in the electrolytic cell 7 and connected to a power source 9 for electrolysis. The electrode unit A2 connected to the positive terminal of the power source 9 is an anode electrode unit A2p, and the electrode unit A2 connected to the negative terminal of the power source 9 is a cathode electrode unit A2m. Are immersed in the electrolytic solution 8 so as to face each other in a parallel state.

When the molten salt electrolyte solution 8 is electrolyzed using such an electrolyzer B2, the liquid contact surface 1k of the porous electrode plate 1C of the anode electrode unit A2p in contact with the electrolyte solution 8 is based on the reaction (2). Then, bubbles of fluorine gas (F ₂ ) are generated, while bubbles of hydrogen gas (H ₂ ) are generated on the liquid contact surface 1k of the porous electrode plate 1C of the cathode electrode unit A2m based on the reaction formula (3).

In the porous electrode plate 1C of the anode electrode unit A2p, the liquid contact surface 1k is lyophilic, the lyophobic film 1m of the through hole 1j is lyophobic, and the hole diameter of the through hole 1j cannot enter the electrolyte 8 inside. Since the hole diameter is set, the bubbles of fluorine gas (F ₂ ) generated on the liquid contact surface 1k are effectively excluded from the liquid contact surface 1k to the through hole 1j and selectively enter the inside of the through hole 1j. And collected in the gas chamber 3b of the anode electrode unit A2p.

On the other hand, in the porous electrode plate 1C of the cathode electrode unit A2m, the liquid contact surface 1k is lyophilic, the lyophobic film 1m of the through hole 1j is lyophobic, and the hole diameter of the through hole 1j cannot enter the electrolyte 8 inside. Since the hole diameter is set, bubbles of hydrogen gas (H ₂ ) generated on the liquid contact surface 1k are effectively excluded from the liquid contact surface 1k into the through hole 1j and selectively enter the inside of the through hole 1j. And collected in the gas chamber 3b of the cathode electrode unit A2m. Therefore, according to the second embodiment, it is possible to obtain the same effect as that of the first embodiment described above.

  In addition, according to the second embodiment, it is easier to increase the area of the liquid contact surface 1k than in the first embodiment described above, and therefore, it is possible to improve the electrolysis decomposition efficiency as compared with the first embodiment. As a result, the generation efficiency of the generated gas can be improved as compared with the first embodiment.

[Third Embodiment]
Next, a third embodiment will be described with reference to FIG. In FIG. 7, the same components as those shown in FIGS. 2 and 4 are denoted by the same reference numerals. In the following, the same components as those in FIGS. 2 and 4 are duplicated, and the description thereof is omitted.

  The electrolysis apparatus B3 according to the third embodiment uses an anode electrode A3p and a cathode electrode A3m in place of the anode electrode unit A1p and the cathode electrode unit A1m shown in FIG. These anode electrode A3p and cathode electrode A3m are porous electrode plates in which the air contact surface 1c of the porous electrode plate 1 shown in FIG. 2 is a lyophobic air contact surface 1c '. That is, the anode electrode A3p and the cathode electrode A3m in the present electrolysis apparatus B3 are lyophilic on the liquid contact surface 1b (first surface), and the lyophobic film 1e in the through hole 1d and the air contact surface 1c '( The second surface) is set to be lyophobic.

In such an electrolysis apparatus B3, the potential of the positive voltage is applied to the anode electrode A3p by the power source 9, and the potential of the negative voltage is similarly applied to the cathode electrode A3m by the power source 9. As a result, the strongest electric field is generated in which the relative distance is the shortest and the solution resistance between the liquid contact surface 1b of the anode electrode A3p and the liquid contact surface 1b of the cathode electrode A3m is uniform at any point on the liquid contact surface. . Further, regarding the anode electrode A3p, since the liquid contact surface 1b is lyophilic and the air contact surface 1c is lyophobic, the reaction formula (2) described above is applied to the lyophobic air contact surface 1c. The exchange of electrons shown in the reaction formula (2) is performed exclusively between the lyophilic liquid contact surface 1b and the fluorine ions (F ⁻ ), and fluorine gas (F ₂ ) Are generated as bubbles.

The fluorine gas (F ₂ ) bubbles generated on the liquid contact surface 1b of the anode electrode A3p in this way are lyophilic on the liquid contact surface 1b and the through-hole 1d, like the electrolysis devices B1 and B2 described above. The lyophobic film 1e is lyophobic and the hole diameter of the through hole 1d is set to a hole diameter in which the electrolytic solution 8 cannot enter, so that it passes through the through hole 1d and moves to the air contact surface 1c ', and buoyancy. Thus, the electrolyte solution 8 is raised and collected.

Here, in place of the anode electrode A3p and the cathode electrode A3m described above, the inner diameter from the liquid contact surface 1b toward the air contact surface 1c ′ as in the through hole 1h of the porous electrode plate 1B shown in FIG. 3B. Is gradually increased, the bubble of fluorine gas (F ₂ ) or the bubble of hydrogen gas (H ₂ ) generated on the liquid contact surface 1 b moves to the larger inner diameter due to the surface tension of the electrolyte 8. Therefore, the removal of fluorine gas (F ₂ ) from the liquid contact surface 1b is further promoted.

On the other hand, regarding the cathode electrode A3m, since the liquid contact surface 1b is lyophilic and the air contact surface 1c is lyophobic, the lyophobic air contact surface 1c is shown in the above reaction formula (3). Reaction does not occur, and the exchange of electrons shown in the reaction formula (3) is performed exclusively between the lyophilic liquid contact surface 1b and hydrogen ions (H ⁺ ), and hydrogen gas (H ₂ ) is converted into bubbles. appear. The bubbles of hydrogen gas (H ₂ ) are lyophilic on the liquid contact surface 1b, the lyophobic film 1e of the through hole 1d is lyophobic, and the hole diameter of the through hole 1d cannot enter the electrolyte 8 inside. Since it is set to the hole diameter, it passes through the through-hole 1d and moves to the air contact surface 1c ′, and rises in the electrolyte solution 8 by buoyancy and is collected.

  According to the third embodiment as described above, the same effects as those of the first and second embodiments described above can be obtained. Further, according to the third embodiment, the configuration of the anode electrode A3p and the cathode electrode A3m is very simple, so that the cost of the apparatus can be reduced.

In addition, this invention is not limited to said each embodiment, For example, the following modifications can be considered.
(1) In the first embodiment, the liquid contact surface 1b is made lyophilic, but the present invention is not limited to this. The object of the present invention can also be achieved by making the wall surface of the through-hole 1d lyophobic without making the liquid contact surface 1b lyophilic, that is, not lyophilic or lyophobic. It is.
(2) In each of the above embodiments, the electrode unit A1 or the electrode unit A2 is employed for both the anode and the cathode, but the present invention is not limited to this. A conventional electrode may be adopted for the cathode.

(3) In each of the above embodiments, nickel (Ni) is selected as the material of the porous electrode plate 1 (metal plate 1a) of the first electrode unit A1p. However, the present invention is not limited to this. The following materials may be used instead of nickel (Ni). That is, as a metal electrode, platinum (Pt), gold (Au), silver (Ag), palladium (Pb), rhodium (Rh), iridium (Ir), tungsten (W) alone, or these as a main component Alloy or nickel (Ni) -copper (Cu) alloy, nickel (Ni) -chromium (Cr) -iron (Fe) alloy, nickel (Ni) -molybdenum (Mo) alloy, nickel (Ni) -chromium (Cr) -Molybdenum (Mo) alloy, etc. may be used.

Also, as the carbon electrode, glassy carbon, pyrolytic graphite, basal plain pyrolytic graphite, carbon paste, HOPG (Highly Oriented Pyrolytic Graphite), carbon fiber, conductive diamond, BDD (Boron Doped Diamond), conductive DLC (Diamond) Like Carbon) electrodes may be used. Further, Nesa (tin oxide doped with antimony (Sb) (SnO ₂ )), Nesatoron (indium oxide doped with tin (Sn) (In ₂ O ₃ )), or the like may be used as the transparent electrode. As the oxide electrode, titanium oxide (TiO ₂ ), manganese oxide (MnO ₂ ), lead dioxide (PbO ₂ ), perovskite oxide, bronze oxide, or the like may be used.

As the semiconductor electrode, silicon (Si), germanium (Ge), zinc oxide (ZnO), cadmium sulfide (CdS), gallium arsenide (GaAs), titanium oxide (TiO ₂ ), or the like may be used. Further, a polymer solid electrolyte electrode may be used. Furthermore, as the combination of the anode electrode and the cathode electrode, each of the above materials may be used alone or a combination of two or more materials may be employed.

(3) In the third embodiment, the anode electrode A3p or the cathode is formed by changing the air contact surface 1c of the porous electrode plate 1 or 1B shown in FIG. 2 or 3B to the lyophobic air contact surface 1c ′. Although the electrode is A3m, the present invention is not limited to this. The one in which the air contact surface 1c of the porous electrode plate 1B shown in FIG. 3 (a) is a liquidphobic air contact surface, or one surface of the porous electrode plate 1C shown in FIG. 5 is a liquidphobic surface. it may also be used.

  A1, A2 ... Electrode unit, A1p, A2p ... Anode electrode unit, A1m, A2m ... Cathode electrode unit, A3p ... Anode electrode, A3m ... Cathode electrode, B1-B3 ... Electrolyzer, 1 ... Porous electrode plate, 1a ... Conductor Plate, 1b ... liquid contact surface, 1c ... air contact surface, 1d ... through hole, 1e ... lyophobic film, 2 ... conducting wire, 3 ... electrode holder, 4 ... gas conduit, 5 ... electrode cover, 6 ... fastening screw, 7 ... electrolyzer, 8 ... electrolyte

Claims (10)

An electrolysis electrode for electrolysis of a predetermined electrolyte solution,
A wetted surface immersed in the electrolyte;
An air contact surface forming a gas flow path;
A plurality of through holes in which the liquid contact surface and the air contact surface are communicated, the wall surface is lyophobic with respect to the electrolyte solution, and the hole diameter is set to a size that allows the generated gas to selectively pass through the electrolyte solution. An electrolysis electrode comprising:   2. The electrolysis electrode according to claim 1, wherein the liquid contact surface is lyophilic.   A surface of a foam having a plurality of through-holes connected to each other, a single pore monolith structure, a double pore monolith structure, a powder sintered body, or a fiber sintered body is a wetted surface. Item 3. The electrolytic electrode according to Item 1 or 2. An electrolysis electrode for electrolysis,
A first surface that is lyophilic with respect to the electrolyte;
A second surface that is lyophobic to the electrolyte;
An electrolysis electrode comprising: a plurality of through-holes, wherein the first surface and the second surface are communicated, and the wall surface is lyophobic with respect to the electrolytic solution.   Either one or both of an anode electrode and a cathode electrode consists of the electrolysis electrode as described in any one of the said Claims 1-4, The electrolysis apparatus characterized by the above-mentioned.   6. The electrolyzer according to claim 5, wherein the electrolytic solution uses a fluorine compound as a molten salt, and fluorine gas is generated at the anode electrode. An electrolysis method for electrolyzing a predetermined electrolyte by supplying a predetermined potential to an anode electrode and a cathode electrode,
Either one or both of the anode electrode and the cathode electrode is in communication with the liquid contact surface immersed in the electrolyte, the air contact surface forming the gas flow path, and the liquid contact surface and the air contact surface. An electrolysis method comprising using a plurality of through-holes that are lyophobic with respect to a liquid and have a hole diameter set to a size that allows the generated gas to selectively pass through the electrolyte .   The electrolysis method according to claim 7, wherein the air contact surface is lyophilic.   9. The electrolysis method according to claim 7, wherein the through holes are connected to each other so as to communicate the liquid contact surface and the air contact surface. An electrolysis method for electrolyzing a predetermined electrolyte by supplying a predetermined potential to an anode electrode and a cathode electrode,
Either one or both of the anode electrode and the cathode electrode has a first surface that is lyophilic with respect to the electrolytic solution, a second surface that is lyophobic with respect to the electrolytic solution, a first surface, and a second surface. And a plurality of through holes whose wall surfaces are lyophobic with respect to the electrolyte solution.

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