KR20220114366A - Manufacturing method for complex of positive electrode active materials with improved durability and complex of positive electrode active materials therefrom - Google Patents

Abstract

The present invention relates to a preparation method for a composite cathode active material (100) which can improve durability of a cathode essential in an electric chemical reaction device and a composite cathode active material (100) prepared thereby and, more specifically, to a preparation method for a composite cathode active material (100) and a composite cathode active material (100) prepared thereby, which forms a double layer (25) consisting of a metal plating layer (20) and a metal oxide layer (30) between the cathode base material (10) and a catalyst layer (40) to prevent the cathode base material (10) and the catalyst layer (40) from being peeled, thereby drastically enhancing durability.

Description

Method for manufacturing a positive electrode active material composite with improved durability and a positive electrode active material composite prepared therefrom { Manufacturing method for complex of positive electrode active materials with improved durability and complex of positive electrode active materials therefrom }

The present invention relates to a method for manufacturing a positive electrode active material composite in which a double layer composed of a metal plating layer and a metal oxide layer is formed between a positive electrode base material and a catalyst layer in order to improve the durability of a positive electrode, which is a core component of various reaction devices such as an electrochemical process, and a method for manufacturing the same To provide a positive electrode active material composite.

A mixed metal oxide (MMO) electrode is also called a dimensionally stable anode (DSA), and refers to an electrode that is recently widely used as an anode corresponding to a cathode in an electrolysis reaction. MMO is composed of oxides mixed with two or more platinum group metals such as iridium, ruthenium, platinum, and rhodium, which have excellent corrosion resistance to chemicals. It acts as a catalyst to accelerate the reaction. MMO electrode is a material component widely used in industries such as chlor-alkali process, sterilizing water production, metal electrolysis extraction, metal electrolytic refining, cathodic corrosion protection and plating. In particular, the supply current density is very high, and the It is widely used in electrolysis reactions in which a large amount of oxygen is generated.

The MMO electrode can be broadly classified into a bulk MMO electrode and a supported MMO electrode depending on whether the metal oxide forms a single layer or the metal oxides of different components form a multi-layer structure.

Methods of manufacturing the anode as described above include chemical methods such as thermal decomposition, electroplating, anodization, sol-gel, plasma enhanced chemical vapor deposition (PECVD), and sputtering or physical vapor deposition. , PVD) and the like).

For example, the thermal decomposition method is the most advantageous method for manufacturing a bulk MMO positive electrode that forms a uniform film on the positive electrode base material, and the sol-gel method is an advantageous method for manufacturing a supported MMO positive electrode.

The biggest advantage of the thermal decomposition method, which is most widely used in electrode coating, is that it is easy to process, and the biggest disadvantage is a low lifespan due to crack generation due to high internal stress. In addition, the sol-gel method was developed to improve the lack of durability due to crack generation, which is a disadvantage of the thermal decomposition method.

In general, anodizing (anodizing) is a compound word of anode and oxidation. Connect the anode power to the metal and apply direct current to the diluted acidic electrolyte. It refers to a method of forming an oxide film with strong adhesion to Representative materials of the anodization process are aluminum (Al), magnesium (Mg), zinc (Zn), titanium (Ti), tantalum (Ta), hafnium (Hf), niobium (Nb), etc. Materials that increase resistance to corrosion by forming a metal oxide layer on the surface are being sold under pressure.

As the characteristics of the metal oxide layer formed by the anodization, it has excellent corrosion resistance, excellent abrasion resistance because it is quite hard, improves adhesion to paint, and has excellent bonding performance.

Looking at the prior art related to the formation of a metal oxide layer through such anodizing, Korean Patent Registration No. 10-1608862 and many others mention anodizing apparatus and method, but most of the mentioned products are products for increasing corrosion resistance to chemicals of specific parts There is no mention of the contents applied to the improvement of the anode performance. In addition, Korean Patent Registration No. 10-1419276, etc. discloses that the anodizing technology uses a low voltage of around 15V to form an oxide film on the metal surface, thereby improving the disadvantage of lowering productivity. Plasma that can use a high voltage Aluminum (Al), magnesium (Mg), titanium (Ti), zirconium (Zr), zinc (Zn), tantalum (Ta), niobium (Nb) using an electrolytic oxidation method (PEO: Plasma Electronic Oxidation, hereinafter PEO) process ) to form an oxide film on the surface of the alloy.

However, the metal oxide layer formed by the conventional PEO process is known to have excellent adhesion and corrosion resistance, but due to the effect of plasma generated on the surface, the surface roughness is large, the metal oxide layer is thickly formed, and the oxide layer has many pores on the upper surface of the oxide layer. There is a disadvantage in that the layer is generated and the bondability is rather deteriorated. In addition, as the surface roughness becomes excessively rough, it is difficult to obtain a smooth surface.

In addition, micropores are formed on the surface of the produced anode, and the cathode base material is damaged by the electrolyte introduced through the micropores.

Therefore, in order to secure more economic feasibility when forming a metal oxide layer, a method for manufacturing a positive electrode active material composite having sufficiently satisfactory durability in a process using a high current density and a process in which a large amount of oxygen is generated, and development of a positive electrode active material composite manufactured therefrom this is being requested

The present invention has been devised to solve this problem, and has improved durability, which is used in an electrochemical reaction device that generates a high current density and a large amount of oxygen, in particular, an Invar thin film film production and a copper thin film production plating apparatus. An object of the present invention is to provide a method for manufacturing a composite and a positive active material composite prepared therefrom.

The positive electrode active material composite 100 of the present invention for solving the above problems, the positive electrode base material 10; a metal plating layer 20 provided on the upper surface of the anode base material 10; a metal oxide layer 30 formed by oxidizing an upper portion of the metal plating layer 20 to a predetermined thickness; and a catalyst layer 40 provided on the metal oxide layer 30, wherein the anode base material 10 is titanium (Ti), tantalum (Ta), hafnium (Hf), niobium (Nb), and zirconium. (Zr), wherein the metal plating layer 20 is a platinum group metal or a valve metal, and the platinum group metal is iridium (Ir), ruthenium (Ru), palladium (Pd), platinum (Pt). ) and rhodium (Rh), and the valve metal is preferably any one of tantalum (Ta), titanium (Ti), zirconium (Zr), hafnium (Hf), and niobium (Nb).

In addition, the metal plating layer 20 has a thickness of 2 mm or less, the metal oxide layer 20 has a thickness of 3 μm or less, and the catalyst layer 40 may be composed of a main catalyst and a cocatalyst, The main catalyst is a chloride or nitrate of a platinum group metal, and the promoter is a chloride or nitrate of a valve metal,

The positive electrode active material composite 100 can manufacture a positive electrode, and also a plating apparatus for manufacturing an Invar thin film, a plating apparatus for manufacturing copper foil, an electrolysis apparatus for generating oxygen, an electrolysis apparatus for salt water electrolysis, or wastewater using the positive electrode It is possible to manufacture an electrochemical reaction device, which is any one of the electrolysis devices for treatment.

And the manufacturing method of the positive electrode active material composite 100 with improved durability according to the present invention, a first step of preparing the positive electrode base material (10); a second step of forming a metal plating layer 20 plated with a metal on the surface of the anode base material 10; a third step of forming a metal oxide layer 30 by oxidizing a predetermined thickness of the surface of the metal plating layer 20 formed in the second step; and a fourth step of coating the catalyst layer 40 on the surface of the metal oxide layer 30, wherein the metal is a platinum group metal or a valve metal, and the third step is a pretreatment step, an anodizing step and a post-treatment step The anodizing step is performed at an electrolyte solution that is a sulfuric acid solution of 1 molar concentration or less, a current of 5 to 15 ± 2A, and a voltage of 10 to 20 ± 2V, and the temperature of the electrolyte is preferably 10 ° C. or less .

The positive electrode active material composite 100 according to the present invention forms a double layer 25 composed of a metal plating layer 20 and a metal oxide layer 30 between the positive electrode base material 10 and the catalyst layer 40 through micropores. By preventing the penetration of the electrolyte into the anode base material 10, it has an effect of preventing damage to the cathode base material 10 by the electrolyte. That is, it has the effect of remarkably increasing durability by preventing damage by the electrolyte and oxygen generated from the anode base material 10 .

1 is a cross-sectional schematic view of a positive electrode active material composite 100 according to the present invention,
2 is a photomicrograph of the positive electrode active material composite 100 according to the present invention.

In the present application, terms such as “comprises”, “have” or “include” are intended to designate that the features, numbers, steps, components, parts, or combinations thereof described in the specification exist, but one or more other It should be understood that this does not preclude the possibility of addition or presence of features or numbers, steps, operations, components, parts, or combinations thereof.

In addition, unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention pertains. Terms such as those defined in commonly used dictionaries should be interpreted as having a meaning consistent with the meaning in the context of the related art, and should not be interpreted in an ideal or excessively formal meaning unless explicitly defined in the present application. does not

Hereinafter, preferred embodiments of the present invention will be described in more detail with reference to the accompanying drawings. In describing the present invention, in order to facilitate the overall understanding, the same reference numerals are used for the same components in the drawings, and duplicate descriptions of the same components are omitted.

Hereinafter, according to the present invention, a method for manufacturing a positive electrode active material composite 100 having improved durability by forming a double layer 25 comprising a metal plating layer 20 and a metal oxide layer 30 and a positive electrode active material composite 100 manufactured therefrom ) will be described in detail with reference to the accompanying drawings. 1 is a cross-sectional schematic view of the positive electrode active material composite 100 according to the present invention, and FIG. 2 is a micrograph of the positive electrode active material composite 100 according to the present invention.

The present invention relates to an electrochemical reaction device operating at high current density, in particular, an anode, which is a main component of a plating device, such as an Invar thin film manufacturing device, a copper thin film manufacturing device, and an electrochemical wastewater treatment device, using a high current density. It relates to a method of manufacturing a positive electrode active material composite 100 with improved durability to prevent a decrease in durability due to the influence of oxygen generated in a large amount during reaction in a reaction apparatus, and a positive electrode active material composite 100 manufactured therefrom.

According to the present invention, the positive electrode active material composite 100 with improved durability includes a positive electrode base material 10, a metal plating layer 20 provided on the positive electrode base material 10, and the a metal oxide layer 30 formed by oxidizing a predetermined thickness on the metal plating layer 20; and a catalyst layer 40 provided on the metal oxide layer 30 .

Hereinafter, examples will be given to describe the present invention in detail. However, the embodiments of the present invention are provided to more completely explain the present invention to those of ordinary skill in the art. Also, the embodiment according to the present invention may be modified in various other forms, and the scope of the present invention should not be construed as being limited to the embodiment described in detail below.

In the present invention, as shown in FIG. 1 as a method to improve durability, a metal plating layer 20 is formed on the upper portion of the positive electrode base material 10 constituting the positive electrode active material composite 100, and the surface of the metal plating layer 20 is formed. By oxidizing a predetermined thickness to form a metal oxide layer 30 , a double layer 25 composed of a metal plating layer 20 and a metal oxide layer 30 is formed. By coating the catalyst layer 40 necessary for the electrochemical reaction on the surface of the double layer 25 formed as described above, the anode showing excellent durability against oxygen generation and improving adhesion between the cathode base material 10 and the catalyst layer 40 It relates to an active material composite 100 and a method for manufacturing the same.

According to the present invention, the positive electrode base material 10 constituting the positive electrode active material composite 100 is selected from the group consisting of titanium (Ti), tantalum (Ta), hafnium (Hf), niobium (Nb) and zirconium (Zr). It may consist of one or more selected.

A metal plating layer 20 is formed on the upper surface of the anode base material 10 as shown in FIG. 1 . The metal plating layer 20 may be manufactured through a known surface coating method capable of uniformly coating a metal on the surface of the positive electrode base material 10 , and is not limited to a specific method.

According to the present invention, the metal plating layer 20 may be formed of a platinum group metal or a valve metal. The platinum group metal is preferably any one of iridium (Ir), ruthenium (Ru), palladium (Pd), platinum (Pt), and rhodium (Rh), and the valve metal is tantalum (Ta), titanium (Ti), It is preferable to use any one of zirconium (Zr), hafnium (Hf), and niobium (Nb).

The platinum group is an element belonging to the tenth group of the periodic table, and the valve metal is called a valve metal because it has a valve action in which current flows from solution to metal, but hardly current flows from metal to solution.

The metal plating layer 20 preferably has a thickness of 2 mm or less. When the thickness of the metal coating layer 20 exceeds 2 mm, the manufacturing cost according to the increase in the plating thickness rises sharply, and thus economic efficiency is deteriorated.

As described above, the metal plating layer 20 formed on the surface of the anode base material 10 is oxidized to a predetermined thickness to form the metal oxide layer 30 .

The metal oxide layer 30 may be formed by immersing the anode base material 10 on which the metal plating layer 20 is formed in an aqueous electrolyte solution and applying a predetermined voltage.

According to the present invention, the metal oxide layer 30 preferably has a thickness of 3 μm or less. That is, when the thickness of the metal oxide layer 30 exceeds 3 μm, the manufacturing cost greatly increases, and the formation time of the metal oxide layer 30 takes a long time, resulting in poor economic feasibility. In addition, the resistance according to the increase of the metal oxide layer 30 on the electrode surface is gradually increased, and accordingly the operating voltage of the electrolysis device increases, and as a result, the operating cost of the electrolysis device also increases.

According to the present invention, by forming the catalyst layer 40 on the metal oxide layer 20, the positive electrode active material composite 100 can be manufactured.

The catalyst layer 40 may be composed of one or more main catalysts and one type of promoter, the main catalyst may be an oxide of a platinum group metal, and the promoter may be an oxide of a valve metal.

According to the present invention, the platinum group metal is any one of iridium (Ir), ruthenium (Ru), palladium (Pd), platinum (Pt), and rhodium (Rh), and the valve metal is tantalum (Ta), titanium (Ti) , it is preferably any one of zirconium (Zr), hafnium (Hf), and niobium (Nb).

At this time, it is particularly preferable that the amount of the catalyst layer 40 according to the present invention is 2 to 5 mg/cm 2 . That is, when the amount of the catalyst layer 40 is formed to be less than 2 mg/cm 2 , the required catalyst activity is insufficient, and the durability of the catalyst is reduced, so that a sufficient operating time of the anode cannot be guaranteed. In addition, when the amount of the catalyst layer 40 exceeds 5 mg/cm 2 , the amount of the catalyst layer 40 that is not coated on the anode and is lost is sharply increased compared to the amount of the catalyst coated on the anode in the process of forming the catalyst layer 40 . Therefore, the amount of the catalyst layer 40 is most preferably formed in a range of 2 to 5 mg/cm 2 .

The positive electrode active material composite 100 of the present invention configured as described above can manufacture a positive electrode, which is a main component of an electrochemical reaction device operating at a high current density, in particular a plating device, an electrochemical reaction device, and an electrochemical wastewater treatment device. there will be

The anode manufactured as described above is formed with a double layer 25 composed of a metal plating layer 20 and a metal oxide layer 30, so that durability is reduced due to the influence of oxygen generated in a large amount in an electrochemical reaction device using a high current density. It is characterized in that it has the effect of preventing

The positive electrode active material composite 100 of the present invention configured as described above can manufacture a positive electrode that can be used in an electrochemical reaction device, and the positive electrode manufactured as described above is an electrochemical reaction device, that is, plating for producing an Invar thin film. It can be applied to any one of an apparatus, a plating apparatus for manufacturing copper foil, an electrolysis apparatus for generating oxygen, an electrolysis apparatus for salt water electrolysis, or an electrolysis apparatus for wastewater treatment.

Hereinafter, a method of manufacturing the positive electrode active material composite 100 according to the present invention will be described in detail.

The method of manufacturing the positive electrode active material composite 100 according to the present invention includes a first step of preparing the positive electrode base material 10; and forming a metal plating layer 20 plated with a metal on the surface of the positive electrode base material 10 a second step; and a third step of forming a metal oxide layer 30 by oxidizing a predetermined thickness of the surface of the metal plating layer 20 formed in the second step; and a fourth step of coating the catalyst layer 40 on the surface of the metal oxide layer 30 .

Looking at this in detail, the first step is a step of preparing the anode base material 10, and the cathode base material 10 can be used without limitation as long as it is made of a metal, preferably titanium (Ti), tantalum (Ta), hafnium. At least one selected from the group consisting of (Hf), niobium (Nb) and zirconium (Zr) is particularly preferable.

As described above, the anode base material 10 prepared through the first step is subjected to a step of forming a metal plating layer 20 plated with a metal on the surface of the cathode base material 10 as a second step. The second step of forming the metal plating layer 20 may be performed through a general physical vapor deposition (PVD) method or an electrolytic plating method.

The physical vapor deposition method is a technique for depositing a thin film material to be deposited on a metal substrate by evaporating or sputtering in a vacuum, and has an advantage in that the process is simple and a high-purity plating layer can be obtained.

In addition, the electrolytic plating method is a plating method using electrolysis, has the advantage of forming a uniform plating layer regardless of the type of substrate, and has high reliability and low process cost, so it is easy to mass-produce and is commonly used.

In the present invention, the second step of forming the metal plating layer 20 on the surface of the anode base material 10 may be appropriately performed through physical vapor deposition (PVD) or electrolytic plating.

After the metal plating layer 20 is formed as described above, a third step of oxidizing a predetermined thickness of the surface of the metal plating layer 20 to form the metal oxide layer 30 is performed.

According to the present invention, the metal oxide layer 30 may be formed by an anodizing process. The anodizing is a compound word of anode and oxidation, and refers to anodizing. The anodizing refers to a process of forming an oxide film having great adhesion to the metal by oxygen generated from the anode when a metal or the like is placed on an anode and electrolyzed in an electrolyte solution.

According to the present invention, the third step for forming the metal oxide layer 30 on the surface of the metal plating layer 20 may be composed of a pre-treatment step, an anodizing step, and a post-treatment step.

The pretreatment step is a process for removing impurities and improving roughness in order to form a uniform metal oxide layer 30 on the surface of the metal plating layer 20 through an anodizing step.

The pretreatment step of the third step is a step for increasing the anodizing efficiency for the surface of the metal plated on the anode base material 10. In order to remove impurities and oil attached to the surface of the metal plating layer 20, the following sequence can proceed with

That is, the cathode base material 10 on which the metal plating layer 20 is formed is immersed in a 5 wt% aqueous hydrochloric acid solution, and impurities and oil components are removed by ultrasonic cleaning at room temperature for 60 minutes. Thereafter, the ultrasonically cleaned anode base material 10 on which the metal plating layer 20 is formed is ultrasonically washed for 10 minutes in distilled water at room temperature to remove an aqueous hydrochloric acid solution, and then dried by supplying air at 60° C. for 1 hour or more.

The anode base material 10 that has undergone the pretreatment step as described above is subjected to an anodizing step to form the metal oxide layer 30 .

In the anodizing step, an anodizing process is performed on the surface of the metal plating layer 20 to form the metal oxide layer 30 . To this end, the anode base material 10 on which the metal plating layer 20 is formed is used as a positive electrode, immersed in an electrolyte solution, and then a voltage is applied to apply a negative electrode (-) to the counter electrode to anodize. occurs At this time, the anode base material 10 is electrically oxidized from the surface by the applied voltage, and the surface of the cathode base material 10 is converted into the metal oxide layer 30 .

According to the present invention, the anodizing step can be performed through an anodizing processing apparatus. The anodizing treatment apparatus includes an electrolytic cell filled with an electrolyte, an anode (+) power supply provided in the electrolytic space of the electrolytic cell to which anode power is input, and a cathode (-) power supply to one side of the electrolytic space filled with the electrolyte. A negative terminal may be provided.

At this time, the electrolytic cell stores the electrolyte of a certain capacity, and power is supplied through the rectifier. The power supplied from the rectifier may be appropriately set within a range of 10 to 50V to supply a DC voltage. The metal oxide layer 30 of various thicknesses can be formed through the supply of various power sources as described above. In addition, the thickness of the metal oxide layer 30 is determined in proportion to the voltage and current values supplied to the electrolytic cell and the anodizing treatment time.

According to the present invention, when performing the anodizing step, the electrolyte is preferably a sulfuric acid solution of 1 molar concentration or less, the current is set to 5 ~ 15 ± 2A, and the voltage is set to 10 ~ 20 ± 2V.

When the concentration of the electrolyte exceeds 1 molar copper, the possibility of generation of sulfurous acid gas (SO ₂ ) or hydrochloric acid gas (Cl ₂ ) is increased along with the generation of oxygen in the acid solution used as the electrolyte in proportion to the concentration of the electrolyte, so unnecessary reaction in the coating layer may cause

In addition, it is preferable that the temperature of the electrolyte solution is a low temperature state of 10° C. or less. That is, when oxidation is performed under the above conditions, it is possible to form the metal oxide layer 30 having a thickness of 2 μm or less.

In particular, the temperature of the electrolyte has the advantage that the metal oxide layer 30 formed at 10° C. or less does not change color and has excellent mechanical strength.

After performing the anodizing step, a post-treatment step is performed to resolve impurities attached to the surface of the metal oxide layer 30 formed through the anodizing step and the non-uniformity of the plating surface.

As described above, impurities attached to the surface in the anodizing step and the non-uniformity of the plating surface may cause a local deviation in the thickness of the metal oxide layer 30, and in order to remove this thickness deviation, the surface of the metal plating layer 20 Heat treatment is performed in an electric furnace at 450 ~ 550 °C. Through this, it is possible to obtain the metal oxide layer 30 having a uniform thickness, and also to obtain the effect of removing foreign substances together.

That is, the cathode base material 10 that has undergone the anodizing step as described above is a post-treatment step. First, process impurities such as plating solution are removed by ultrasonic washing in distilled water at 60° C. for 30 minutes, and then dried at 100° C. for 1 hour or more to retain moisture. to remove Thereafter, heat treatment is performed at 450 to 550° C. while supplying air to uniformize and stabilize the metal oxide layer 30 .

According to the present invention, the thickness of the metal oxide layer 30 formed through the third step is preferably 2 ㎛ or less. That is, when the thickness of the metal oxide layer 30 exceeds 2 μm, the manufacturing cost of the manufactured anode increases, thereby lowering economic efficiency.

After the third step is completed as described above, a fourth step of forming the catalyst layer 40 for the electrochemical reaction on the surface of the metal oxide layer 30 generated through the third step is performed.

A method of forming the catalyst layer 40 on the surface of the metal oxide layer 30 through the fourth step is as follows.

That is, according to the present invention, the catalyst forming the catalyst layer 40 may be composed of a main catalyst and a cocatalyst, and the main catalyst may be a chloride or nitrate of a platinum group metal. In addition, the co-catalyst may be a chloride or nitrate of the valve metal.

The catalyst layer 40 may be composed of one or more main catalysts and one kind of promoter, and one or more kinds of the main catalyst and one kind of the promoter are mixed with alcohol to which a small amount of hydrochloric acid is added, that is, isopropyl alcohol, ethanol. Alternatively, after preparing a catalyst solution by dissolving it in butanol, it is coated on the surface of the metal oxide layer 30 . The catalyst solution coated as described above is dried to form a pre-catalyst layer composed of a main catalyst and a co-catalyst.

When the precatalyst layer is heat-treated at 450 to 500° C. for 15 to 20 minutes, the metal chloride or metal nitrate is converted into a metal oxide form.

The catalyst layer 40 can be formed by heat-treating the metal oxide formed as described above at 520 to 550° C. for 30 minutes or more to stabilize the crystal structure of the metal oxide.

The thickness of the catalyst layer 40 formed as described above is preferably 3.5 to 4 μm. That is, when the thickness of the catalyst layer 40 is out of the above range, economic efficiency is reduced due to an increase in manufacturing cost due to excessive coating, and the electrolysis device caused by an increase in resistance by the catalyst layer 40 made of metal oxide As the voltage increases, the operating cost increases.

When the formation of the catalyst layer 40 is completed as described above, a double layer 25 composed of the metal plating layer 20 and the metal oxide layer 30 is formed from the anode base material 10 according to the present invention, and through this, a large amount The production of the positive electrode active material composite 100 as shown in FIG. 2 is completed, which has the effect of remarkably increasing durability by preventing the catalyst layer 40 from being peeled off by oxygen generated by the .

The positive electrode active material composite 100 prepared as described above can produce a positive electrode with improved durability, and also uses the same for Invar thin film production plating apparatus, copper foil production plating apparatus, oxygen generation electrolysis apparatus, salt water electrolysis electricity It becomes possible to manufacture an electrochemical reaction device of either the decomposition device or the electrolysis device for wastewater treatment.

Although the present invention has been described with reference to the experimental examples shown in the drawings, which are merely exemplary, those of ordinary skill in the art will understand that various modifications and equivalent other experimental examples are possible therefrom. In addition, those of ordinary skill in the art to which the present invention pertains will understand that it can be easily modified into other specific forms without changing the technical spirit or essential features of the present invention. Therefore, it should be understood that the embodiments described above are illustrative in all respects and not restrictive, and the true technical protection scope of the present invention should be defined by the technical spirit of the appended claims.

10: anode base material
20: metal plating layer
30: metal oxide layer
40: catalyst layer

Claims (8)

Anode Base (10)
A metal plating layer (20) provided on the upper surface of the anode base material (10)
a metal oxide layer 30 formed by oxidizing an upper portion of the metal plating layer 20 to a predetermined thickness; and
Catalyst layer 40 provided on the metal oxide layer 30; cathode active material composite 100 comprising a
The method according to claim 1,
The positive electrode base material 10 is a positive electrode active material composite 100, characterized in that at least one selected from the group consisting of titanium (Ti), tantalum (Ta), hafnium (Hf), niobium (Nb), and zirconium (Zr)
The method according to claim 1,
The metal plating layer 20 is a positive electrode active material composite 100, characterized in that the platinum group metal or valve metal.
4. The method of claim 3,
The platinum group metal is any one of iridium (Ir), ruthenium (Ru), palladium (Pd), platinum (Pt), and rhodium (Rh), and the valve metal is tantalum (Ta), titanium (Ti), or zirconium (Zr). , hafnium (Hf), positive active material composite 100, characterized in that any one of niobium (Nb)
A positive electrode manufactured using the positive electrode active material composite 100 of any one of claims 1 to 4.
An electrochemical reaction device manufactured using the anode of claim 5 .
7. The method of claim 6,
The electrochemical reaction device is an electrochemical device, characterized in that any one of a plating device for producing an Invar thin film, a plating device for producing copper foil, an electrolysis device for generating oxygen, an electrolysis device for salt water electrolysis, or an electrolysis device for wastewater treatment reaction device
As a manufacturing method of the positive electrode active material composite 100 with improved durability,
A first step of preparing the positive electrode base material (10);
a second step of forming a metal plating layer 20 plated with a metal on the surface of the anode base material 10;
a third step of forming a metal oxide layer 30 by oxidizing a predetermined thickness of the surface of the metal plating layer 20 formed in the second step; and
A fourth step of coating the catalyst layer 40 on the surface of the metal oxide layer 30; a method of manufacturing a positive electrode active material composite 100 with improved durability, including a

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