WO2021049709A1 - Titanium electrode for water treatment electrolysis and method for manufacturing same - Google Patents

Abstract

A titanium electrode for water treatment electrolysis, according to the present invention, is for oxidizing or reducing an aqueous solution to be subjected to electrolysis by applying a positive or negative potential while immersed in the aqueous solution, and comprises: a base made of titanium or a titanium alloy; a titanium oxide layer formed by oxidizing at least a portion of the titanium on the surface of the base; and an active layer made of any transition metal and coating the titanium oxide layer.

Description

Titanium electrode for water treatment electrolysis and its manufacturing method

The present invention relates to a titanium electrode for water treatment electrolysis and a method of manufacturing the same, and more particularly, to a titanium electrode used for electrolysis for sterilizing an aqueous solution, and a method of manufacturing the titanium electrode.

In recent years, in order to remove pollutants contained in fresh water, wastewater, sewage, purified water, etc. obtained from seawater and to sterilize/disinfect them, an electrolysis method is used.

In the electrolysis method, by generating a strong oxidizing substance, it is possible to decompose, sterilize, and disinfect non-degradable organic substances without being affected by conditions such as biotoxicity, temperature, and dissolved oxygen. In addition, a large amount of processing can be performed within a short time, and the processing device can be downsized. In addition, there is an advantage of generating strong oxidizing substances without using chemical additives that can generate secondary waste.

In addition, the electrolysis method is used for sterilization/sterilization of ballast water in ships. When the ship's ballast water is injected or discharged, it passes through an electrolysis tank, and an electric current is applied to the electrode of the electrolysis tank to produce residual oxidizing agent from seawater to kill or sterilize marine life.

The basic operating principle of the electrolytic apparatus for such a use is to use an oxidation-reduction reaction occurring at the anode and cathode immersed in the aqueous solution to be treated. For example, when a substance containing Cl serving as an electrolyte in the aqueous solution is contained in the aqueous solution to be treated, Cl ⁻ is oxidized at the anode to generate chlorine gas and oxygen at the same time. In addition, water is reduced at the cathode to generate hydrogen. The reaction formula of this oxidation-reduction is as follows.

<Anode>

2Cl ^- → Cl ₂ + 2e ^-

_{H 2 O → 0.5O 2 + 2H} + + 2e -

<cathode>

^{_{2H 2 O + 2e - → H}} 2 + 2OH -

On the other hand, the chlorine generated by the oxidation reaction as the free chlorine (free chlorine), in pH 6.5 ~ 8 hypochlorous acid (HClO) and hypochlorous acid ions (ClO ^-) are present in the form of.

_{Cl 2 + H 2 O → H} + + Cl - + HClO (pH4.6, 25 ℃)

HClO ↔ H ⁺ + ClO (pH7.5, 25℃)

Among these compounds, HClO is an active chlorine and shows strong oxidizing power and disinfecting power.

On the other hand, the anode and/or cathode electrode used in such a general electrolysis device, as shown in FIG. 1, mainly uses a titanium substrate, and here, iridium (Ir), ruthenium (Ru ), platinum (Pt), palladium (Pd), and other platinum group metal oxides are coated to add a mixed metal coating layer (MMO coating).

In Korean Patent No. 10-1741401 (name: a coating solution for an electrochemically insoluble electrode and a method of manufacturing an electrode) (hereinafter referred to as "prior art"), a first oxide layer and a second oxide layer are coated on a titanium substrate, respectively. By doing so, a method of improving the performance and durability of an electrode is disclosed.

However, in the prior art, in order to form the first oxide layer, a process of applying a first coating solution containing tantalum chloride and hydrogen hexachloroiridate (IV) is required, and In addition, in order to form the second oxide layer, a process of applying an organic solvent including titanium dioxide, silicon dioxide, bismuth oxide, zirconium oxide, aluminum oxide, and mixtures thereof is additionally required.

Therefore, in the prior art, since the process of applying the oxide to the titanium substrate is performed twice, the manufacturing method is complicated and the material cost is doubled. In addition, a material different from the material constituting the substrate on the titanium substrate is used. Since it is coated, there is a disadvantage that the durability of the coating is low.

In addition, the conventional electrode in which the coating layer is formed in this way is in the area where the adhesion of the coating layer is deteriorated, the area where mud-crack occurs, the area where the current density is concentrated, etc. during the electrolysis reaction in the aqueous electrolyte solution. The coating layer can be easily peeled off. Where the coating layer is peeled off, titanium may be directly exposed to the aqueous solution. Then, the oxidation-reduction reaction may occur in the titanium itself on the electrode surface, resulting in damage to the electrode.

Particularly, on the surface of the anode electrode, a reaction for _{generating Cl 2 and} a reaction for generating H ⁺ occurs due to a water decomposition reaction, and these substances have very strong corrosive power to metals.

In addition, when these substances are generated on the surface of the electrode and concentrated in the aqueous electrolyte solution, they penetrate into the titanium substrate through the damaged or weak portions of the coating layer of the electrode.

When Cl ₂ or H ⁺ penetrates into the titanium substrate, titanium begins to corrode, the conductivity and adhesion of the coating layer covering the corroded area is further weakened, and damage may increase or a chain reaction may occur in which the coating layer is peeled off. .

In addition, when the titanium of the anode electrode is directly exposed to the aqueous electrolyte solution, an anodic oxidation reaction occurs on the surface of the exposed titanium, whereby a local insulating layer is generated on the titanium surface, and the insulating layer is continuously grown. As the insulating layer grows, the current density in the corresponding portion gradually increases, so that an overvoltage is applied, and thus the anode electrode may be more severely eroded or dissolved.

To prevent damage to the electrode during electrolysis by increasing the adhesion of the transition metal coating layer and preventing dry heat of the coating layer on the electrode of the general electrolysis device as described above, particularly on the surface of the titanium electrode.

The titanium electrode for water treatment electrolysis according to the present invention for achieving the above object is for oxidizing or reducing the aqueous solution by applying a positive or negative potential while immersed in an aqueous solution to be subjected to electrolysis, In particular, the electrode for electrolysis includes: a base made of titanium or a titanium alloy; A titanium oxide layer formed by oxidizing at least a portion of titanium on the surface of the base portion; It is prepared to include an active layer made of any transition metal coating the titanium oxide layer.

At this time, the titanium oxide layer: a first temperature included in the range of 400 to 800 ℃ by arranging the base portion of the electrode for electrolysis in a heating furnace, and supplying thermal energy to the base portion. A heating step of raising the temperature over time; A heat treatment step of maintaining the temperature of the base portion within the range for a second time; And cooling the base to room temperature by stopping the supply of thermal energy to the base.

In addition, in the heating step, the first temperature is selected in the range of 500 to 700 °C, and the first time is selected in the range of 90 to 150 minutes, and in the heat treatment step, the second time is 30 to The temperature of the base portion selected in the range of 90 minutes and heated may be kept constant at the first temperature during the second time period.

In addition, while performing at least one of the heating step, the heat treatment step, and the cooling step, oxygen may be injected into the heating furnace.

Here, the surface of the base may include irregularities formed by sand blasting or corrosion by corrosive substances.

Meanwhile, the transition metal forming the active layer may include at least one of iridium, ruthenium, palladium, platinum, tantalum, titanium, and tin.

A method of manufacturing a titanium electrode for water treatment electrolysis according to another embodiment of the present invention comprises: preparing a base portion made of titanium or a titanium alloy; Forming a titanium oxide layer by oxidizing at least a portion of titanium on the surface of the base portion; And forming an active layer made of an arbitrary transition metal coating an upper portion of the titanium oxide layer, wherein the forming of the titanium oxide layer comprises: placing the base in a heating furnace, and Supplying thermal energy to increase the temperature of the base portion from room temperature to a first temperature in the range of 400 to 800° C. over a first time period; Maintaining the temperature of the base within the range for a second time; And stopping the supply of thermal energy to the base part to cool the base part to room temperature.

In this case, the first temperature is selected in the range of 500 to 700 °C, and the first time is selected in the range of 90 to 150 minutes, and the second time is selected in the range of 30 to 90 minutes, and The temperature of the base portion heated to 1 temperature may be kept constant at the first temperature during the second time period.

In addition, during at least a portion of the period in the middle of performing the step of forming the titanium oxide layer, it may further include injecting oxygen into the interior of the heating furnace.

In addition, the step of preparing the base may further include forming irregularities by sandblasting the surface of the base or corroding it with a corrosive material.

In addition, the transition metal forming the active layer may include at least one of iridium, ruthenium, palladium, platinum, tantalum, titanium, and tin.

The titanium electrode for water treatment electrolysis according to the present invention having the configuration as described above has high adhesion of the transition metal coating layer and is difficult to generate dry heat. Accordingly, damage to the electrode during electrolysis is suppressed, thereby improving the life of the electrode.

Meanwhile, as described above, a titanium electrode for water treatment electrolysis having an improved life can be manufactured by a simple manufacturing method.

1 is a diagram illustrating a cross section of a part of a titanium electrode according to the prior art and a process in which the titanium electrode is damaged during electrolysis.

2 is a view showing a cross section of a portion of the titanium electrode for water treatment electrolysis according to the present invention.

3 is a flowchart illustrating a method of manufacturing a titanium electrode for water treatment electrolysis according to the present invention.

4 is a view showing the XRD analysis results of the titanium electrode for electrolysis manufactured according to various embodiments of the present invention.

FIG. 5 is a diagram showing the results of an electrokinetic positive polarization experiment of a titanium electrode for electrolysis manufactured according to various embodiments of the present invention.

Hereinafter, a preferred embodiment of a method of manufacturing a titanium electrode for water treatment electrolysis and a titanium electrode for water treatment electrolysis according to the present invention will be described with reference to the accompanying drawings. For reference, the terms referring to each component of the present invention are exemplarily named in consideration of their functions, and thus the technical content of the present invention should not be predicted and limited by the term itself.

2 is a cross-sectional view of a portion of the titanium electrode for water treatment electrolysis according to the present invention. The titanium electrode according to the present invention includes a base portion 110, a titanium oxide layer 120, and an active layer 130.

The titanium electrode for water treatment electrolysis disclosed in the present invention can be used as an electrode for oxidizing or reducing the aqueous solution by applying a positive or negative potential while immersed in an aqueous solution to be subjected to electrolysis. Is used.

The base portion 110 constitutes a basic shape of an electrode, and may be made of pure titanium or an alloy of titanium and other metals.

On the surface of the base portion 110, a titanium oxide layer 120, which is a characteristic configuration of the present invention, is formed. The titanium oxide layer 120 _{may be formed of titanium dioxide (TiO 2} ), and may be formed by oxidizing titanium on the surface of the base portion in the atmosphere or in an oxygen atmosphere. In particular, the base portion 110 is placed in a heating furnace (or a sintering furnace), and the inside of the heating furnace is set to an air presence condition under atmospheric pressure or an oxygen dominant atmosphere or a pure oxygen atmosphere or an inert gas atmosphere, and the heating furnace is closed to heat it. Make sure that the inside of the furnace is sealed. The configured system may be, for example, in a state in which the oxygen ratio is 15 to 30%.

In this state, the closed system in the heating furnace is heated (thermal energy is supplied) to raise the temperature of the base portion 110. For example, by heating at least a portion of the wall surface of the heating furnace, thermal energy is supplied to the internal system through the heated at least part of the wall surface to heat the internal system, and the base portion 110 is heated by the heated system.

On the other hand, the process of raising the temperature of the base 110 may be performed over 90 to 150 minutes, preferably over 120 minutes, and the temperature of the base 110 to a predetermined temperature in the range of 400 to 800 °C, preferably It includes raising the temperature to a temperature in the range of 500 to 700°C, more preferably to 600°C. Subsequently, the process of heat-treating the base portion 110, by controlling the heating operation of the heating furnace, to keep the temperature of the heated base portion 110 heated for 30 to 90 minutes, preferably for 60 minutes in the heating furnace. Includes maintaining. Subsequently, to cool the heat-treated base portion 110, the heating by the heating furnace is stopped (ie, the supply of thermal energy is stopped) and the heat-treated base portion 110 is left in the heating furnace at room temperature together with the heating furnace. It includes cooling to. A titanium oxide layer 120 may be formed on the surface of the base portion 110 made of titanium through a series of such processes.

Here, on the surface of the base portion 110, before forming the titanium oxide layer 120, a sandblast treatment or a corrosion treatment with a corrosive material may be performed, so that fine irregularities may be formed. Corrosive substances may include, for example, sulfuric acid, hydrochloric acid, oxalic acid.

On the other hand, in at least some of the processes of heating the base portion 110 to raise the temperature in a heating furnace, heat treatment by maintaining the temperature, and then allow cooling, oxygen or a gas containing oxygen may be injected into the heating furnace. In addition, the amount of oxygen injected into the heating furnace or the pressure inside the heating furnace may be set differently according to the temperature, shape, size, and material of the base portion 110 or according to the thickness of the titanium oxide layer 120 to be formed. have.

The active layer 130 is formed by coating an upper portion of the titanium oxide layer 120 formed on the surface of the base portion 110 with an arbitrary transition metal. The transition metal may be, for example, iridium, ruthenium, palladium, platinum, tantalum, titanium, or tin, and the active layer 130 may be formed by coating any one or two or more of them.

3 is a flowchart illustrating a method of manufacturing a titanium electrode for water treatment electrolysis according to the present invention. The method of manufacturing a titanium electrode according to the present invention includes the step of preparing a base portion 110 of a cathode electrode and/or an anode electrode made of titanium or a titanium alloy (S10), and by oxidizing titanium on the surface of the prepared base portion 110. And forming the titanium oxide layer 120 (S20), and forming the active layer 130 by coating the formed titanium oxide layer with an arbitrary transition metal (S30).

In particular, the step of preparing the base part 110 (S10) includes preparing the base part 110 (S11), forming fine irregularities by sand blasting the base part 110 or corrosion treatment with a corrosive substance. It may include a thing (S12).

On the other hand, as a method of forming fine irregularities in the base portion 110, other methods other than the above-described method may be applied. On the other hand, fine irregularities may not be formed on the base portion 110.

In the step of forming the titanium oxide layer 120 (S20), the prepared base portion 110 is placed in the heating furnace (S21), and the base portion ( 110) heating up to a first temperature over a first time period (S22), heat treatment by maintaining the heated temperature of the base portion 110 inside the heating furnace for a second time (S23), heat of the heating furnace It may include stopping the heating of the base part 110 by stopping the supply of energy and allowing the heating furnace and the base part 110 to be cooled to room temperature together with the base part 110 left inside the heating furnace (S24). have.

More specifically, in the process (S22), the first time may be selected from, for example, 90 minutes to 150 minutes, and preferably 120 minutes. Meanwhile, the first temperature may be selected in the range of 400 to 800°C, preferably 500 to 700°C, and more preferably 600°C.

In this process, the inside of the heating furnace may be at room temperature and atmospheric conditions as initial conditions. Alternatively, the initial conditions may be set to a specific temperature, and may be an inert gas atmosphere, an oxygen dominant atmosphere, or a pure oxygen atmosphere.

Subsequently, while the inside of the furnace is heated and/or the base portion 110 is heat treated, the inside of the furnace is sealed or exposed to the atmosphere, or the atmosphere or a gas containing oxygen or oxygen is heated (or not heated). It may not be in a state) and can be injected or circulated.

Meanwhile, in the process (S23) of heat-treating the heated base portion 110, the temperature of the heated base portion 110 may be varied in an arbitrary manner within the above-described temperature ranges that can be set as the first temperature. However, it is preferable to maintain the elevated first temperature as it is.

And, in the process of cooling the heat-treated base part 110 (S24), the heat-treated base part 110 is removed from the heating furnace and left to stand in the atmosphere at room temperature, or the sealing of the heating furnace is released and then left to free the outside air. It can be circulated, or it may be cooled by injecting or circulating an atmosphere of room temperature or an arbitrary temperature or a gas containing pure oxygen or oxygen into the inside of the heating furnace.

In the step of forming the active layer 130 made of the transition metal (S30), the transition metal is applied/sprayed on the upper portion of the titanium oxide layer 120 or the base portion 110 on which the titanium oxide layer 120 is formed is formed of a transition metal. Coating the titanium oxide layer 120 with a transition metal by immersing in a solution containing this or exposing the base portion 110 on which the titanium oxide layer 120 is formed to an atmosphere of a transition metal (S31), coated transition metal It may include drying (S32), and firing the dried transition metal (S33).

The characteristics of the titanium electrode for water treatment electrolysis according to the present invention manufactured in this way will be described with reference to FIGS. 4 and 5.

In the manufacturing method as described above, various electrode samples are prepared while varying the heat treatment temperature, that is, the first temperature (or the heat treatment temperature), and under the conditions used as an electrolysis electrode for each of the prepared samples. Several properties were tested.

4 is a view showing the XRD analysis results of the titanium electrode for electrolysis manufactured according to various embodiments of the present invention. In particular, it shows the XRD analysis results of the electrode in which the titanium oxide layer was formed by performing the heat treatment temperature at 500°C, 600°C, and 700°C, respectively.

_{Among the two TiO 2} phases of a rutile structure and an anatase structure, a rutile structure is known to be a structurally safer phase. In this analysis, a sample prepared by performing heat treatment at 500° C. known as the phase change temperature of the rutile structure was used. Through the XRD characteristic peak analysis result of the prepared sample, it can be confirmed that only the rutile structure exists under the above temperature conditions.

Only the titanium peak was observed in the titanium substrate (substrate that was not heat-treated) in which only the hydrochloric acid etching treatment was performed and no heat treatment was performed. On the other hand, in the substrate subjected to heat treatment at 500°C, a (110) plane peak of the rutile structure was observed at a position where the 2Θ value was 26.98°.

In the samples with higher heat treatment temperatures, the intensity of the (110) peak increased, and at positions where 2Θ values were 35.80°, 53.60°, 64.52°, and 69.33°, respectively (011), (121), (221), (112) ) Side peak was observed. Through this, it can be seen that the thickness _{of the rutile TiO 2} layer in the titanium substrate increases as the heat treatment temperature increases.

FIG. 5 shows the results of performing an electrokinetic bipolarization experiment in order to observe the effect of the thickness of the _{TiO 2 layer on the chlorine generation efficiency.} As the overvoltage increased, the positive polarization current density of each electrode increased.The electrode that did not undergo heat treatment showed the largest positive polarization current density at the same overvoltage, and the positive polarization current density decreased with the electrode with a higher heat treatment temperature. However, the onset potential of chlorine generation was similar to about 1.62V regardless of the heat treatment. This means that although the TiO ₂ layer produced through heat treatment has a kinetic effect on the positive polarization reaction, it does not have a thermodynamic effect.

On the other hand, when performing the polarization curve experiment, in addition to the chlorine generation reaction, a side reaction such as an oxygen generation reaction may be accompanied. Therefore, when comparing the performance of the heat-treated electrode, in order to eliminate the effect of this side reaction, an additional electrostatic potential polarization experiment was performed. In a further experiment, the chlorine generation performance was measured by comparing the measured value of the residual chlorine concentration with the theoretical value.

Experiment 1 is a sample formed by coating only the active layer of transition metal in the conventional method (i.e., _{not applying the TiO 2} layer) and a sample coated with the active layer of transition metal after forming _{the TiO 2 layer according to the present invention.} It was done using. A total of three experiments were conducted, and the initial voltage, effective operation time, and chlorine generation current efficiency were measured.

The titanium substrate was subjected to a sand blast treatment using an 80 mesh size diamond and pretreatment of etching for 15 minutes under 50% sulfuric acid conditions and a water temperature of 50°C.

The titanium substrate was heated to 600° C. for 2 hours in a heating furnace, heat-treated at 600° C. for about 1 hour, and then allowed to cool to room temperature in the heating furnace to form a _{TiO 2 layer.}

In the active layer coating the upper part of the electrode, RuCl ₃ and TiCl ₃ are mixed in a molar ratio of 7:3, and a solution dissolved in isopropyl alcohol at a concentration of 50 g/L of _{RuCl 3 is loaded onto a titanium substrate.} It was coated by 10 g/cm ² as a standard.

Each of the samples with or without the TiO ₂ layer applied was operated under severe life test conditions, that is, a sulfuric acid 0.5M condition and a water temperature of 2°C, with a current density of 1A/cm ^2. In addition, the effective operation time was determined when the voltage of the electrode increased by 5 to 10 V or more from the start voltage of the experiment or when the final 20 V was monitored.

The current efficiency of chlorine generation was tested under the conditions of a flow rate of 1m/sec, a Cl ^- concentration of 18000mg/L, and a current density of 0.05A/cm ² , and the current efficiency was calculated by the electrochemical equivalent of chlorine using the following equation. I did.

As can be seen from [Table 1], in three experiments, when the TiO ₂ layer was applied, the durability of the electrode was increased by about 15-50%. Here, since each of the samples used the same transition metal as the active layer, the current efficiency was similar.

<Experiment result under the condition of current density 1A/cm ^2>

	Sample	Initial voltage	Uptime	Current efficiency
1st experiment	Conventional coating method	15V	58.6 hours	96.3%
	TiO 2 layer applied	15.1V	67 hours	96.8%
2nd experiment	Conventional coating method	15V	46.9 hours	95.2%
	TiO 2 layer applied	15.2V	84.8 hours	96.4%
3rd experiment	Conventional coating method	15.9V	43.5 hours	96%
	TiO 2 layer applied	14.9V	66 hours	95.4%

In Experiment 2, the same samples as those used in Experiment 1 were used, but the current density was lowered. [Table 2] As can be seen through, the effective operating time (i.e., being associated with the electrode life) in the case of applying the TiO ₂ layer is confirmed that increase of about 2 times as compared with the case without applying the TiO ₂ layer have.

<Results of durability test under the condition of current density 0.05A/cm ^2>

	Sample	Initial voltage	Uptime	Uptime growth rate
1st experiment	Conventional coating method	8.8V	230 hours	172%
	TiO 2 layer applied	9.2V	397 hours
2nd experiment	Conventional coating method	9.8V	167 hours	226%
	TiO 2 layer applied	10V	379 hours
3rd experiment	Conventional coating method	9.2V	406 hours	200%
	TiO 2 layer applied	10.5V	812 hours

The embodiments of the present invention described above are merely illustrative of the technical idea of the present invention, and the protection scope of the present invention should be interpreted by the following claims. In addition, a person of ordinary skill in the technical field to which the present invention pertains will be able to make various modifications and variations without departing from the essential characteristics of the present invention, and all technical ideas within the scope equivalent to the present invention are the present invention. It should be construed as being included in the scope of rights of

Claims (11)

1. An electrode for electrolysis that oxidizes or reduces the aqueous solution by applying a positive or negative potential while immersed in an aqueous solution to be subjected to electrolysis,

   The electrode for electrolysis is:

   A base made of titanium or a titanium alloy;

   A titanium oxide layer formed by oxidizing at least a portion of titanium on the surface of the base portion; And

   A titanium electrode for water treatment electrolysis comprising an active layer made of any transition metal, which coats the titanium oxide layer.
2. The method of claim 1,

   The titanium oxide layer is:

   A heating step of disposing the base of the electrode for electrolysis in a heating furnace and supplying thermal energy to the base to raise the temperature of the base from room temperature to a first temperature in the range of 400 to 800°C over a first time period;

   A heat treatment step of maintaining the temperature of the base portion within the range for a second time; And

   A titanium electrode for water treatment electrolysis, characterized in that it is formed by a titanium oxidation process comprising a cooling step of cooling the base to room temperature by stopping supply of thermal energy to the base.
3. The method of claim 2,

   In the heating step, the first temperature is selected in the range of 500 to 700°C, and the first time is selected in the range of 90 to 150 minutes, and

   In the heat treatment step, the second time is selected in the range of 30 to 90 minutes, and the heated base portion temperature is maintained constant at the first temperature for the second time, for water treatment electrolysis Titanium electrode.
4. The method of claim 1,

   The surface of the base portion,

   A titanium electrode for water treatment electrolysis, characterized in that it contains irregularities formed by sand blasting or corrosion by corrosive substances.
5. The method of claim 1,

   The transition metal forming the active layer,

   Iridium, ruthenium, palladium, platinum, tantalum, titanium and titanium electrode for water treatment, characterized in that it comprises at least one of tin and tin.
6. As a method of manufacturing an electrode for electrolysis that oxidizes or reduces the aqueous solution by applying a positive or negative potential while immersed in an aqueous solution to be subjected to electrolysis:

   Preparing a base made of titanium or a titanium alloy;

   Forming a titanium oxide layer by oxidizing at least a portion of titanium on the surface of the base portion; And

   A method of manufacturing a titanium electrode for water treatment electrolysis, comprising the step of forming an active layer made of any transition metal, which coats an upper portion of the titanium oxide layer.
7. The method of claim 6,

   The step of forming the titanium oxide layer is:

   Disposing the base in a heating furnace, and supplying thermal energy to the base to increase the temperature of the base from room temperature to a first temperature in the range of 400 to 800°C over a first time period;

   Maintaining the temperature of the base within the range for a second time; And

   The method of manufacturing a titanium electrode for water treatment electrolysis, further comprising cooling the base part to room temperature by stopping supply of thermal energy to the base part.
8. The method of claim 7,

   The first temperature is selected in the range of 500 to 700 °C, and the first time is selected in the range of 90 to 150 minutes, and

   The second time is selected in the range of 30 to 90 minutes, and the temperature of the base portion heated to the first temperature is kept constant at the first temperature during the second time, for water treatment electrolysis Method of manufacturing a titanium electrode.
9. The method according to any one of claims 6 to 8,

   The method of manufacturing a titanium electrode for water treatment electrolysis, further comprising injecting oxygen into the heating furnace during at least a portion of the period in the middle of performing the step of forming the titanium oxide layer.
10. The method of claim 6,

    Preparing the base portion,

    A method of manufacturing a titanium electrode for water treatment electrolysis, further comprising forming irregularities by sandblasting the surface of the base portion or corroding by a corrosive substance.
11. The method of claim 6,

    The transition metal forming the active layer,

    Iridium, ruthenium, palladium, platinum, tantalum, titanium and tin, characterized in that it comprises at least one of, a method of manufacturing a titanium electrode for water treatment electrolysis.

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