JP2000290789A - Production of electrode for electrolysis and device therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To stably and easily form an electrolysis catalytic layer having tight adhesion on the wide surface of an electrode substrate by holding an electrode substrate and a coating material at a prescribed interval and relatively moving the coating material along the surface of the electrode substrate while generating a spark discharge under CNC control. SOLUTION: An electrode substrate of titanium or the like and a coating material of platinum or the like are held at a interval capable of discharging on the space therebetween. While spark discharge is generated on the space therebetween, the coating material is relatively moved along the surface of the electrode substrate while it is vibrated or rotated at need. At this time, it is possible that plural coating materials are used, and they are respectively moved by servo-operation. In this way, a sufficient liq. phase condition is formed on the surfaces of both, and thermal diffusing treatment is executed to form a coating layer composed of the coating material on the surface of the electrode substrate. At this time, it is possible that powder having a desired compsn. is fed to the discharge part, and the compsn. of this powder is incorporated into the coating layer. All these operations are executed under CNC control, thereby, this coating working can stably be executed with high controllability.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and an apparatus for producing an electrode for electrolysis, and more particularly to an electrode for electrolysis formed by forming an intermediate coating layer and an electrocatalyst coating layer on an electrode substrate. It should be noted that the coating layer referred to in the present specification includes, in addition to the surface coating layer formed by the electrolytic catalyst, all intermediate coating layers that are applied as a base treatment thereof. It shall include all of the electrocatalyst layer and intermediate layer formed on the surface of the substrate, and their composite layers.

[0002]

2. Description of the Related Art Electrolytic electrodes formed by coating an electrode substrate with an electrolytic catalyst are widely used mainly in anodes. For example, a coating layer of an electrode in which a surface of an electrode substrate made of a valve metal such as titanium is coated with an electrocatalyst containing a platinum group metal or oxide as a main component is mainly formed by a plating method or a thermal decomposition method. ing. When the electrode substrate is made of a titanium material, an intermediate layer of a valve metal containing tantalum or niobium may be provided in order to enhance corrosion resistance and adhesion at the boundary between the titanium material and the electrode catalyst layer. As a forming method of the PVD, use of a PVD method or a thermal spraying method has been attempted. Furthermore,
Recently, JP-A-6-200391 or JP-A-8-199384
Disclosed a technique for forming an intermediate layer using a discharge method.

[0003] However, in the PVD method and the thermal spraying method, the valve metal used as the material of the electrode substrate has a high melting point, and metal diffusion between the electrode substrate and the intermediate coating layer is not sufficiently performed. However, the durability of the electrode was limited.
In addition, the thermal spraying method has a problem that the intermediate coating layer becomes too thick or a dense intermediate coating layer cannot be obtained, so that a significant improvement in electrode durability cannot be expected. Furthermore, in the PVD method and the thermal spraying method, the loss of the coating material when forming the coating layer is large, the material is wasteful, and there are also economic problems.

In general, various devices using electric discharge often use relatively stable electric discharge, and arc discharge and glow discharge for welding fall into the category of stable electric discharge. Used industrially. However, even with such stable electric discharges, machining by hand requires extremely high skill.
Or automatic control machining by CNC control, but it uses a discharge mainly composed of spark discharge, which is particularly unstable among discharges, to stably cover the entire electrode substrate with a large electrode area. It has been very difficult to apply a coating and to provide a large amount of electrodes at a low cost. Another problem is that the coating efficiency is poor when the discharge treatment is used.

Further, when a coating material containing tantalum or niobium is coated on an electrode substrate made of titanium by a conventional discharge method, it is difficult to sufficiently alloy titanium of the electrode substrate with tantalum or niobium as a coating material. In addition, there is also a problem that the composition of the intermediate layer remains substantially the same as that of the coating material. For example,
In the method of obtaining an alloy intermediate layer of titanium and tantalum disclosed in Japanese Patent Application Laid-Open No. 8-199384, the allowable range of discharge conditions required for diffusing the tantalum of the coating material into the titanium component of the electrode substrate and alloying the same is extremely narrow. However, it is difficult to stably maintain the discharge state, and there is a problem to be solved. In particular, since tantalum and niobium have an extremely high melting point and are easily oxidized, it has been extremely difficult to control discharge for obtaining an alloy having a desirable composition distribution.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems, and to control the range and discharge conditions over a wide electrode substrate surface by CNC control or the like. Method and apparatus for forming an intermediate layer of an electrode for electrolysis having strong adhesiveness that does not peel off during the reaction, a coating layer,
In particular, it is an object of the present invention to provide a method and an apparatus capable of performing stable processing and easily controlling a coating state.

[0007]

Means for Solving the Problems Between the coating material and the electrode substrate
A uniform spark discharge is generated by CNC control, etc., a sufficient liquid phase state is formed on the surface of the coating material and the electrode substrate, a heat diffusion process is performed, and an electric field diffusion is caused. A high pressure and a high electric field are concentrated on the discharge point, and the desired discharge position is controlled in the X, Y and Z directions to form a coating layer for the electrode for electrolysis.

Before describing the embodiments, the formation of a coating on the electrode substrate will be described. As means for reacting the coating material and the electrode base material in a sufficiently high temperature state,
Controlling the gap (Z), relative position (X, Y), and relative moving speed between the coating material and the electrode substrate by CNC control, and controlling the supply of discharge energy to generate spark discharge, By controlling the amount of supply, an attempt is made to obtain a strong bonding coating or an alloyed state on a necessary portion of the electrode substrate. In general, if the temperature generated during discharge is T,

(Equation 1) Here, K: constant determined by discharge conditions κ: thermal conductivity ρ: specific resistance E: discharge voltage

[0009] Even if the calculation is made with a normally used discharge voltage of about 50 V, the discharge point is a sufficiently high temperature which is about the evaporation temperature of the coating material and the electrode substrate. As a result, the constituent material is melted between the coating material and the electrode substrate, and the lower viscosity material in the molten metal at that temperature is transferred to the higher viscosity side to form an electrode for electrolysis. Can be done.
Its transfer characteristics are:

(Equation 2) Here, α: the moving weight of the coating material, K ₁ : a constant depending on the material, I: the discharge current time integration amount, and shows a moving amount characteristic proportional to the square root of the discharge current. If the discharge current changes with time, it is necessary to control the discharge current time characteristic according to the required coating formation.

[0010] Immediately after the discharge, the voltage between the two electrodes of the coating material and the electrode substrate does not become zero instantaneously, and this voltage causes a metal ion diffusion action until the ion equilibrium is reached between the two electrodes. If the ion concentration in the depth direction at that time is C,

(Equation 3) Here, C ₀ : surface ion concentration (coating material) D: diffusion coefficient U: ion mobility E: electric field strength η: diffusion speed This represents diffusion at the point of discharge. Generally, when the ion mobility in the molten state is 10 ⁻⁷ m ² / v · s, the diffusion coefficient is about 10 ⁻⁸ m ² / s. This means that when an electric field is applied, the diffusion speed is calculated to be 150 to 1000 times higher than in the case of only thermal diffusion.

At the discharge point, a magnetic field is generated due to the discharge current, so that a magnetic field of about H = 130 to 150 kA / m acts on the coating material and the molten portion of the electrode substrate generated by the discharge heat. In this case, the viscosity of the molten metal increases due to the magnetic field at this time. Assuming now that the viscosity of the molten metal is σ _m ,

(Equation 4) Becomes Here, H: magnetic field ρ: specific resistance μ: magnetic permeability ν: diffusion rate of the molten metal.

Accordingly, the viscosity of the molten metal at the discharge point is high irrespective of the high temperature in the discharge melting portion, and therefore, a coating is formed on the surface of the electrode substrate by repeated pulse discharge. Due to the cooling effect when the discharge is stopped, the viscosity of the molten metal further increases, and it is 10 ³ to 1 in comparison with the viscosity at the time of melting.
Since the viscosity is about ⁴ times higher, the coating material at the discharge point is
Even if the internal pressure acts on the melt, the melt of the coating material does not scatter so much, but is deposited around the crater formed by the discharge column to form a diffusion coating. Generally, the temperature is higher on the side of the coating material having a lower heat capacity than on the side of the electrode substrate having a higher heat capacity, so that the coating material is easily diffused and joined to the surface layer of the electrode substrate.

[0013] By appropriately controlling the discharge conditions, the diffusion depth of the coating material can be controlled, and an alloy layer of the coating material and the electrode substrate can be formed on the surface of the electrode substrate.

However, in order to increase the diffusion, for example, when the peak value of the discharge current is higher than the normal deposition condition at the discharge point, the internal pressure of the molten metal increases at the discharge point,
Explosive scattering occurs, which hinders the deposition and formation of the alloy layer. In addition, when forming a coating while supplying an inert gas or liquid to the discharge part, it is necessary to control the supply amount and pressure so that the molten metal is not scattered by the pressure. There is also. Now, if this discharge pressure is P, and the gas constant is R,

(Equation 5) M: molecular weight of metal x _i : degree of ionization T: medium temperature v: gas volume at the end of discharge

[0015] Therefore, when extra energy is injected into the discharge portion beyond the amount necessary for forming the coating, explosive vaporization occurs at the discharge point, and the molten metal is scattered to reduce the discharge coating amount. For example, with a discharge time on the order of 100 μs
Assuming that a discharge energy pulse of about 0.3 Joule is used, the calculation for the Ti electrode shows that the internal pressure of the melting point is
It will be about 0.1GPa. This is a pressure sufficient to scatter the molten metal at the discharge point.

Since the melting generally starts at about 350 A / mm ² or more, the current density at the discharge point of the discharge used for coating is generally maintained at about 1000 A / mm ² . This level is sufficient for the dimple formation pressure, and the coating material can be deposited on the surface layer of the electrode substrate at the same time as the dimples are formed. Desirable surface roughness of the electrode surface for electrolysis or the intermediate layer in which dimple formation is performed in the pretreatment before the discharge coating of the electrode substrate is 150 μm or less, more preferably 120 μm or less.
μm or less. In the case of the intermediate layer of the electrode for electrolysis, it is desirable that the surface roughness is large, but if the surface roughness exceeds 150 μm, the uniformity of the thickness of the electrode catalyst layer is lost or uniform discharge coating cannot be obtained. And the like. When dimple formation is performed, it is difficult to reduce the surface roughness to 10 μm or less. When viewed from the application of the electrode for electrolysis, various surface roughness is required depending on the application, but if it can be freely controlled in a range of usually 150 μm or less,
It is possible to respond in a wide range.

When a discharge is caused to be superposed on one coating layer (deposited layer), the first deposited layer has an anchoring effect with respect to the next discharge coated layer, and the superposed coating has a strong effect on the electrode substrate. Multilayer coating can be applied with adhesive strength. Since the coating is formed on the electrode substrate while repeating the discharge, the discharge portion repeats rapid heating, rapid diffusion, and rapid cooling according to the respective discharge conditions, thereby providing a desired composition distribution,
A coating having a thickness and properties is formed. By keeping the heating characteristics, diffusion characteristics, and cooling characteristics stable under the desired conditions,
In order to form a desired coating, it is important to precisely control each condition by CNC control or the like.

In order to stably form the electrode for electrolysis or its intermediate layer, the following items are controlled. a) Discharge gap (Z) at the start of discharge b) Relative moving speed (dX / dt, dY / dt) between coating material and electrode substrate c) Time from start of discharge to maximum discharge current d) Energy released during discharge time (energy density of discharge surface) e) Discharge medium conditions for generating discharge (gas, liquid, solid,
F) cycle of repetitive discharge g) temperature before discharge at discharge point h) electrode temperature at which discharge occurs i) thickness and composition of discharge deposition layer j) between coating material and electrode substrate In the present invention, "a) discharge gap at the time of starting discharge
(Z) "is an essential item for CNC control. Usually, in order to form an electrode for electrolysis according to the present invention or an intermediate layer thereof,
It is sufficient to perform the CNC control only on the control item a), and other control methods such as NC can be used for other control target items. However, the controlled items b), c) and d)
In the case of, CNC control is effective, and if it is adopted, more stable machining is possible. Other simple controls are sufficient for the control items e) to j).

When the electrode for electrolysis is manufactured by such a method, all problems when using spark discharge are eliminated. That is, according to the present invention, as described above, a particularly unstable spark discharge is mainly used in the discharge,
It is very difficult to form a uniform and stable coating layer over a large surface area of the electrode substrate, and it is very difficult to provide it inexpensively and in large quantities, and the problem that the coating efficiency by the discharge treatment is poor is solved. I do. In addition, the effect of controlling the dimple shape or the state of the electrode for electrolysis according to the use or condition of electrolysis was obtained. Further, according to the present invention, it becomes possible to form a discharge coating layer having various characteristics according to the electrolysis conditions when the electrode is used by the CNC control, and the following operational effects are also brought about. 1) The production of minute electrolysis electrodes having a partial discharge coating and electrolysis electrodes having a complicated partial coating can be easily performed. 2) Various high performance cathodes can be manufactured easily and at low cost. Examples of these are a low-hydrogen overvoltage cathode in which nickel is used as an electrode substrate and an alloy of ruthenium and nickel is coated. When producing effective chlorine by electrolyzing seawater or salt with a diaphragm, a stainless steel electrode substrate and a silver-coated electrode for electrolysis are used as a cathode that does not easily reduce effective chlorine. Can be mentioned.

Embodiment 1 The position of the coating material is servo-controlled in the direction of the normal line (Z-axis) with respect to the surface of the electrode substrate by CNC control so that the gap between the coating material and the electrode substrate is within a range in which discharge can be generated. While maintaining, the NC of the movement of the table on which the electrode substrate is placed in the X-Y axis direction and the movement speed are further controlled. An electrode for electrolysis was manufactured according to the method of the present invention by controlling the number of revolutions of the material using an apparatus capable of setting control conditions arbitrarily. The electrode substrate is prepared by degreased a titanium plate equivalent to JIS type 2 with an alcohol solution, treated with a 5% by weight HF aqueous solution at 25 ° C. for 1 minute, and then with a 50% by weight H ₂ S
Use a material treated for 1 minute in an O ₄ solution.
Using a platinum rod of mm, the average voltage between the platinum electrode and the electrode substrate during discharge is 45 V, the moving speed of the electrode substrate is 60 mm / min, the peak current _Ip is 100 A, τ _ON is 100 μs, and the repetition frequency is 200 H.
z, platinum-coated titanium electrodes for electrolysis having various shapes were manufactured under the conditions that the maximum current density was 10 ⁵ A / cm ² and the platinum electrode was rotated at 240 rpm. As a result, platinum electrodes having various covering surface shapes were obtained. The platinum coating amount of those electrodes was stable irrespective of the coating shape, and the platinum film thickness was uniform. Among the various electrolysis electrodes manufactured in this manner, the catalyst electrode surface has an L-shape, and the main portion has a width of 20 mm.
× length 50 mm, arm width 2 mm × length 50 mm, the thickness of the platinum coating layer is 0.5 μm was selected, and was used as an example electrode-1, and an electrolytic test was performed for comparison with a comparative example electrode-1 described later. Was done.

Comparative Example-1 The same titanium substrate as in Example-1 was used as an electrode substrate, degreased with an alcohol or the like, and then treated in a 50% by weight H ₂ SO ₄ solution at 120 ° C. for 1 minute. It was immersed in 1% by weight hydrofluoric acid for 1 minute to perform pretreatment of platinum plating. The pre-treated titanium plate was subjected to electroplating in a sulfuric acid acidic platinum plating solution to prepare Comparative Example Electrode-1. The thickness of the platinum plating layer was measured with a fluorescent X-ray film thickness meter to obtain a value of 0.5 μm.

Electrolysis tests were performed on the electrode of Example 1 and the electrode of Comparative Example 1 under the following conditions, and the consumption rates of platinum were compared. Electrolysis test conditions Electrolyte: 1 mol H ₂ SO ₄ +1 mol Na ₂ SO ₄ aqueous solution Temperature: 40 ° C. Current density: 18 A / dm ² Counter electrode: Ni Distance between electrodes: 10 mm Electrode-1 is 4 μg /
Compared to AH, Comparative Example Electrode-1 was 5 μg / AH, and it was confirmed that according to the present invention, the life was extended by 25%.

Embodiment 2 Eight vertical (Z-axis) servo drives for performing the CNC control operation are mounted on the XY drive axis table, and the mutual intervals between the servo drives can be adjusted arbitrarily. , Except that the position movement by the XY axis drive and the movement speed were controlled by NC, the same apparatus of the present invention as in Example-1 was used, and the electrode base was the same as in Example-1. Using a block made of titanium having a width of 400 mm, a length of 500 mm and a thickness of 3 mm, acid treatment was performed in the same manner as in Example 1, and attached to the above apparatus. The coating material is a Ta bar with a diameter of 3 mm.
Each one was attached to the base. The pitch between the Ta coating materials is 50 mm, the average discharge voltage is 45 V, the moving speed of the Ta coating material is 60 mm / min, the peak current _Ip is 100 A, τ _ON is 100 μs,
The pulse repetition frequency was 200 Hz, the maximum current density was 10 ⁵ A / cm ² , Ar gas was injected at a rate of 1 cc / min, and Ta was rotated at 240 rpm to form a Ta intermediate layer. The resulting interlayer is EP
As a result of elemental analysis by MA and roughness measurement by a surface roughness meter, it contains an alloy layer of Ti and Ta, and the roughness is 45μ.
It was found to be mRmax. Further, as a result of obtaining the Ta coverage of the intermediate layer formed by the eight servo drives, the values shown in Table 1 were obtained. According to this, it is understood that the coating of Ta is extremely uniform and stable.

[Table 1] The Ta coverage S is a value measured by a fluorescent X-ray film thickness meter and calculated by the following equation.

(Equation 6) Here, N: the total number of measurement points Np: the number of measurement points showing a predetermined coating film thickness In addition, a butanol solution of iridic acid chloride and an ethanol solution of tantalum chloride are mixed, and Ir 5.0 g / l and Ta 50.0 g are mixed. /
After adjusting the coating solution containing a l, on the intermediate layer of the electrode for electrolysis obtained in the above, 1 cm ² per 3 with a micropipette.
It was weighed out at a rate of 0 μl, applied to the above Ta coating, dried at room temperature for 30 minutes, baked in air at 500 ° C. for 10 minutes, and this process was repeated three times. Then, in order to obtain a catalyst layer, a butanol solution of iridium chloride and an ethanol solution of tantalum chloride were mixed, and Ir50.0 g / l and Ta2
After preparing a coating solution containing 0.2 g / l, the same steps as described above are repeated eight times using this coating solution to evaluate the intermediate layer of the electrode for electrolysis formed by the method of the present invention. Example 2 was manufactured.

Example 3 As in Example 1, titanium was used as an electrode substrate, blasting was performed with cast iron grit # 80, aqua regia treatment was performed, and then an aqueous solution of 5% by weight HF at 25 ° C. for 1 minute. Then, it was immersed in a 50% by weight H ₂ SO ₄ solution at 120 ° C. for 1 minute to perform a roughening treatment. Next, Ta and T having a powder particle size of 325 mesh or less
The mixed powder having a powder ratio of 1: 1 was sprinkled on the roughened surface to obtain an electrode substrate in which the powder was fixed in the concave portions. This electrode substrate was mounted on the same apparatus of the present invention as in Example 1, a Ti rod having a diameter of 3 mm was used as a coating material, and the average voltage was 40 V and T
i The moving speed of the coating material is 90 mm / min, the peak current _Ip is 100 A,
The tau _ON 100 [mu] s, 200 Hz pulse repetition frequency, the maximum current density and 10 ⁵ A / cm ^2, injecting Ar gas at a flow rate of 1 cc / min, under conditions of rotating the Ti electrode at 120 rpm, to obtain a Ti intermediate layer Was. The obtained intermediate layer was subjected to elemental analysis by EPMA,
It turned out to be an alloy layer of Ti and Ta. As a result of the roughness measurement, a value of 85 μm Rmax was obtained. Next, on the intermediate layer, an Ir-Ta oxide coating layer was formed on the Ta-Ti alloy layer in the same manner as in Example electrode-2,
Example electrode-3 for evaluating this intermediate layer was produced.

Example 4 After the electrode substrate made of Ni was degreased with an alcohol solution, it was attached to the apparatus of the present invention used in Example 1, and a 90 mm Ru-10Ni alloy having a diameter of 2.0 mm was used as a coating material. The average voltage between the electrode substrates is 45 V, and the moving speed of the coating material is 120 mm /
Min, 120A peak current I _p, 100 [mu] s to tau _ON, pulse 200Hz repetition frequency of the maximum current density and 10 ⁵ A / cm ^2, while injecting an Ar gas at a rate of 1 cc / min, 240 rpm the coating material The electrode was discharged under the conditions of rotating at a speed of, thereby obtaining Example electrode-4 having a Ru-Ni alloy coating layer on a Ni plate. With respect to the obtained Example-4 electrode, the hydrogen overvoltage was measured under the following conditions.
The overvoltage was lower by about 200 mV than the hydrogen overvoltage, and it was confirmed that the overvoltage was usable as a cathode electrode. Electrolysis test conditions Electrolyte solution: 3 mol NaOH Solution temperature: 80 ° C Current density: 12.5 A / dm ² (conditions with reference to hydrogen overvoltage)

Comparative Example 2 The same electrode base made of titanium as in Example 1 was used.
After the acid treatment in the same manner as described above, a 3.0 mm diameter Ta rod is used as a coating material and attached to a commercially available discharge coating device (Spark Depot), and the coating material is manually moved while being in contact with the electrode substrate surface to perform the discharge treatment. Then, a discharge treatment was performed at a rate of 0.1 dm ^{2 /} min to form an intermediate coating layer on the surface of the electrode substrate. The thickness of the obtained intermediate coating layer was measured with a fluorescent X-ray film thickness meter, and the coverage of Ta was determined by the above formula 6, and as a result, the obtained coverage was 70%.
%. Also, the variation in the amount of Ta coating was large and uneven. In addition, an Ir-Ta oxide coating layer was formed on the intermediate coating layer in the same manner as in Example electrode-2, to produce Comparative example electrode-2.

Comparative Example 3 Example 1 was applied to the same electrode substrate made of titanium as in Example 1.
Acid treatment was performed in the same manner as described above to remove oxides. next,
An Ir-Ta oxide coating layer was formed on the surface of the electrode substrate from which the oxide had been removed in the same manner as in Example electrode-2, to produce comparative example electrode-3.

The electrodes of Example electrode-2, Example electrode-3, Comparative example electrode-2 and Comparative example electrode-3 were subjected to an electrolytic test under the following conditions, and the durability of the intermediate coating layer was compared. . Table 2 shows the results. From Table 2, it can be seen that the intermediate coating layer produced by the method of the present invention has higher durability than those produced by a conventionally known method. <Electrolysis conditions> _{electrolyte: 1 mol H 2 SO 4 +1} mol Na 2 SO 4 aqueous Current Density: 4A / cm ² counter: Pt distance between target were tested at 10 mm or more electrolysis conditions, the initial electrolytic voltage for
The life of the electrode was determined by a 10% voltage rise, and the durability of the intermediate layer was evaluated by the electrolysis time until the life was reached.

[Table 2]

As is apparent from the above, according to the present invention, the gap between the coating material and the electrode substrate is controlled by CNC, and a fully automatic and stable spark discharge is generated, whereby the surface of the electrode substrate is uniformly formed. In addition, a coating layer suitable for the purpose can be formed, and an electrode for electrolysis having various characteristics and excellent durability can be provided inexpensively and in large quantities.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C25C 7/02 307 C25C 7/02 307 C25D 17/10 101 C25D 17/10 101A 17/12 17/12 B

Claims (7)

[Claims] 1. A coating material is held by a CNC control with a distance capable of generating a discharge between the electrode material to be processed and a discharge material between the two, and the coating material is formed along the surface of the electrode substrate while generating a discharge between the two. A method for producing an electrode for electrolysis, comprising a step of forming a coating layer made of a coating material on a surface of an electrode substrate by relatively moving the electrode layer. 2. The method for producing an electrode for electrolysis according to claim 1, wherein a plurality of coating materials are used, and each of them is servo-driven to form a coating layer. 3. The method for producing an electrode for electrolysis according to claim 1, wherein dimple formation is performed simultaneously with formation of the surface coating layer so that the surface roughness is not less than 10 μm and not more than 150 μm Rmax. 4. The apparatus for producing an electrode for electrolysis according to claim 1, wherein the coating layer is formed while vibrating the coating material. 5. The apparatus for producing an electrode for electrolysis according to claim 1, wherein the coating layer is formed while rotating the coating material. 6. The coating layer according to claim 1, wherein a coating layer containing at least a part of the composition of the powder is formed while supplying a powder having a desired composition to a discharge portion between the coating material and the electrode substrate. A method for producing an electrode for electrolysis of 7. An apparatus for detachably holding an electrode base,
A device that holds the coating material through a distance capable of generating a discharge between the electrode substrate and the electrode substrate held by the above device, and relatively moves along the surface of the electrode substrate, and generates a discharge between the electrode substrate and the coating material. Device to control and CN controlling all of the above devices
2. An apparatus for producing an electrode for electrolysis by the method according to claim 1, comprising C control.