KR102201668B1 - Copper doped metal oxide of perovskite structure and method of manufacturing the same and solid oxide electrode using the same - Google Patents

Abstract

Copper-doped prase that can reduce manufacturing cost and improve performance through the replacement of precious metals through the application of metallic copper, as metallic copper is eluted at high temperature to increase catalytic performance and excellent performance at high temperatures. Disclosed is a method for preparing audinium strontium titanium oxide and a solid oxide electrode using the same.
The copper-doped perovskite-structured metal oxide according to the present invention includes a perovskite-structured metal oxide; And copper eluted to the surface of the metal oxide and doped so as to partially fill the surface of the metal oxide, wherein the metal oxide includes praseodymium (Pr), strontium (Sr), and titanium (Ti). It is characterized.

Description

Preparation of copper-doped praseodynium strontium titanium oxide and production of a solid oxide electrode using the same {COPPER DOPED METAL OXIDE OF PEROVSKITE STRUCTURE AND METHOD OF MANUFACTURING THE SAME AND SOLID OXIDE ELECTRODE USING THE SAME}

The present invention relates to a copper-doped perovskite structure metal oxide and a method of manufacturing the same, and a solid oxide electrode using the same, and more particularly, metal copper is eluted in the metal oxide at a high temperature, thereby increasing catalytic performance, A copper-doped perovskite structure metal oxide that has excellent performance even at high temperatures and can reduce manufacturing cost and improve performance through the replacement of precious metals by applying metallic copper, and a solid oxide electrode using the same. About.

A solid oxide battery is a battery that uses a solid oxide having oxygen or hydrogen ion conductivity as an electrolyte membrane.Oxygen ions generated by the reduction reaction of oxygen from the positive electrode pass through the solid electrolyte membrane to the negative electrode and react with the hydrogen supplied to the negative electrode. It generates water and uses an external current generated when the generated electrons are transferred to the anode.

To this end, the solid oxide battery has a basic configuration of a unit cell composed of a cathode electrode, a solid electrolyte, and an anode electrode. At this time, in order to collect electricity generated in the solid oxide battery, the cathode electrode and the anode electrode are electrically connected using a current collector.

Recently, at least one type of fuel among CO ₂ and CO is sealed in a single injection into SOFC (solid oxide fuel cell) and SOEC (solid oxide electrolyzer cell) system, and then the second charge/discharge concept is repeated through continuous forward and reversible reactions. Efforts to use as batteries are in progress.

In order to be used in the membrane reactor of such a solid oxide fuel cell (SOFC) and a solid oxide electrolyzer cell (SOEC) system, a metal oxide having excellent catalytic performance and excellent thermal stability is required.

As a related prior document, there is Korean Laid-Open Patent Publication No. 10-2006-0046533 (published on May 17, 2006), and the document describes a perovskite-type composite oxide and catalyst.

It is an object of the present invention to elute metallic copper in a metal oxide at a high temperature, thereby increasing catalytic capacity, and having excellent performance even at high temperatures, and copper that can reduce manufacturing costs and improve performance through the replacement of precious metals by applying metallic copper. It is to provide a doped perovskite structure metal oxide, a method of manufacturing the same, and a solid oxide electrode using the same.

The copper-doped perovskite-structured metal oxide according to an embodiment of the present invention for achieving the above object may include a perovskite-structured metal oxide; And copper eluted to the surface of the metal oxide and doped so as to partially fill the surface of the metal oxide, wherein the metal oxide includes praseodymium (Pr), strontium (Sr), and titanium (Ti). It is characterized.

The method for producing a copper-doped perovskite-structured metal oxide according to an embodiment of the present invention for achieving the above object is (a) a praseodymium precursor, a strontium precursor, a titanium precursor, and a copper precursor are dissolved in a solvent and then ultrasonic waves are applied. Heating while irradiating to form a mixture; (b) calcining the mixture and then pulverizing to form a pellet; (c) sintering the pellets to form a sintered body; And (d) subjecting the sintered body to reduction heat treatment in a reducing atmosphere to elute copper contained in the sintered body to the surface of the sintered body to form a copper-doped metal oxide.

The copper-doped perovskite structure metal oxide according to the present invention and the method of manufacturing the same and the solid oxide electrode using the same increase the catalytic performance by eluting and depositing metallic copper in the Pr-Sr-Ti metal oxide at a high temperature. In addition, it has excellent performance even at high temperatures, and it is possible to reduce manufacturing cost and improve performance through the replacement of precious metals by the application of metallic copper.

As a result, the copper-doped perovskite structure metal oxide according to the present invention and the method of manufacturing the same, and the solid oxide electrode using the same have excellent catalytic performance and high-temperature stability, thereby improving the performance of the solid oxide fuel cell and gas sensor. It can be used as an electrode such as.

In addition, the copper-doped perovskite structure metal oxide according to the present invention and the method of manufacturing the same, and the solid oxide electrode using the same, are part of the surface of the metal oxide by eluting metallic copper in the Pr-Sr-Ti metal oxide at a high temperature. The electrical conductivity is improved by doping metallic copper so that is buried. Accordingly, when used as an electrode such as a solid oxide fuel cell and a gas sensor, the resistance can be reduced, so that high efficiency can be maintained even in a medium-low temperature region.

1 is a process flow chart showing a method of manufacturing a copper-doped perovskite structure metal oxide according to an embodiment of the present invention.
2 is a schematic diagram showing a limited current type gas sensor.
Figure 3 is a schematic diagram showing the upper portion of the limited current type gas sensor.
Figure 4 is a schematic diagram showing a lower portion of the limited current type gas sensor.
5 is a graph showing the results of X-ray diffraction analysis on specimens prepared according to Examples 1 to 4.
6 is a graph showing the results of X-ray diffraction analysis of specimens prepared according to Examples 5 to 8.
7 is a graph showing electrical conductivity measurement results for specimens prepared according to Examples 1 to 2, 4, 6 to 8 and Comparative Examples 1 to 3;

Advantages and features of the present invention, and a method of achieving them will become apparent with reference to the embodiments described below in detail together with the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, but will be implemented in a variety of different forms, only this embodiment is to complete the disclosure of the present invention, and the general knowledge in the technical field to which the present invention pertains. It is provided to completely inform the scope of the invention to those who have it, and the invention is only defined by the scope of the claims. The same reference numerals refer to the same elements throughout the specification.

Hereinafter, a copper-doped perovskite structure metal oxide according to a preferred embodiment of the present invention, a method of manufacturing the same, and a solid oxide electrode using the same will be described in detail below with reference to the accompanying drawings.

Perovskite structure metal oxide doped with copper

The perovskite-structured metal oxide doped with copper according to an exemplary embodiment of the present invention comprises a perovskite-structured metal oxide and copper doped so that a part of the metal oxide is eluted to the surface of the metal oxide. Include.

In this case, the metal oxide includes praseodymium (Pr), strontium (Sr), and titanium (Ti).

Here, the metal oxide may be represented by the following formula (1).

[Formula 1]

Pr _x Sr _y TiO ₃

Here, x is 0.1 to 0.5, and y is an integer of 0.1 to 0.5.

In addition, the metal oxide may be represented by the following formula (2).

[Formula 2]

Pr _x Sr _1-1.5y TiO ₃

Here, x is 0.1 to 0.5, and y is an integer of 0.1 to 0.5.

In addition, the copper-doped perovskite structure metal oxide according to an embodiment of the present invention is more preferably doped with copper in an amount of 0.04 to 0.08 mol%. At this time, when copper is doped to less than 0.04 mol%, it may be difficult to properly exhibit the effect of improving catalytic performance. Conversely, when copper is doped in excess of 0.08 mol%, it may cause a problem in which copper is not eluted into the metal oxide having a perovskite structure but is volatilized.

Method for producing copper-doped perovskite structure metal oxide

1 is a process flow chart showing a method of manufacturing a copper-doped perovskite structure metal oxide according to an embodiment of the present invention.

Referring to FIG. 1, a method of manufacturing a copper-doped perovskite structure metal oxide according to an embodiment of the present invention includes a melting step (S110), a calcination step (S120), a sintering step (S130), and a reduction heat treatment step ( S140).

Dissolution

In the dissolution step (S110), a praseodymium precursor, a strontium precursor, a titanium precursor, and a copper precursor are dissolved in a solvent and then heated while irradiating with ultrasonic waves to form a mixture.

Here, the praseodymium precursor includes at least one selected from the group consisting of Pr ₆ O ₁₁ and Pr ₂ O ₃ . The strontium precursor includes at least one selected from the group consisting of SrN ₂ O ₆ , SrCO ₃ and SrSO ₄ .

In addition, the titanium precursor includes at least one selected from the group consisting of TiO ₂ , TiCl ₄ and TiOCl ₂ . The copper precursor includes at least one selected from the group consisting of Cu(NO ₃ ) ₂ , CuCl ₂ , CuCO ₃ and Cu ₂ SO ₄ .

In particular, it is preferable that the copper precursor is mixed so that the amount of copper eluting to the surface of the metal oxide is 0.04 to 0.08 mol%.

In this step, the solvents include acetone, 2-methoxyethanol, DMF (dimethylformamide), octanol, ethoxy ethanol, tetradecane, pentanol. One or more selected from (pentanol), dipropylene glycol monomethyl ether, ethylene glycol, benzene, distilled water (H ₂ O), etc. may be used, but is not limited thereto.

In addition, in this step, the ultrasonic irradiation is preferably performed for 1 to 60 minutes under the conditions of 10 to 60 kHz. When the ultrasonic irradiation is less than 10 kHz or less than 1 minute, the praseodymium precursor, the strontium precursor, the titanium precursor, and the copper precursor may not be uniformly mixed with the solvent. Conversely, when the ultrasonic irradiation exceeds 60 kHz or exceeds 60 minutes, there is a problem in that excessive energy is consumed from the viewpoint of process efficiency, which is not preferable.

calcination

In the calcination step (S120), the mixture is calcined and then pulverized to form a pellet.

In this step, calcination is preferably carried out at 1,000 to 1,200°C for 6 to 12 hours. When the calcination temperature is less than 1,000°C or the calcination time is less than 6 hours, there is a concern that the surface of the mixture may not melt well. Conversely, when the calcination temperature exceeds 1,200°C or the calcination time exceeds 12 hours, the mixture may react with each other to form a different composition locally, and the size of the crystal grains may be excessively large, which is not preferable.

Sintering

In the sintering step (S130), the pellets are sintered to form a sintered body.

In this step, sintering is preferably performed at 1,400 to 1,500° C. for 5 to 10 hours. If the sintering temperature is less than 1,400°C or the sintering time is less than 5 hours, there is a high concern that the relative density may be lowered because crystallization is not properly performed. Conversely, when the sintering temperature exceeds 1,500°C or the sintering time exceeds 10 hours, the average particle diameter of the oxide increases and the strength decreases due to the growth of pores, and it can act as a factor that increases the manufacturing cost without any further effect. So, I can't cheat.

Reduction heat treatment

In the reduction heat treatment step (S140), the sintered body is subjected to reduction heat treatment in a reducing atmosphere to elute copper contained in the sintered body to the surface of the sintered body to form a copper-doped metal oxide.

In this step, the reduction heat treatment is preferably carried out for 5 to 10 hours under conditions of 1,500 to 1,800° C. in an H ₂ atmosphere of 5 to 10 wt %. In this case, when H ₂ is less than 5% by weight, there is a problem in that the reduction process is not performed smoothly, so that copper cannot be eluted. Conversely, when H ₂ exceeds 10% by weight, there is a problem in that an excess of hydrogen is used in terms of energy efficiency, so it is not economical.

In addition, when the reduction heat treatment temperature is less than 1,500° C. or the reduction heat treatment time is less than 5 hours, there is a problem in that copper is not smoothly eluted. Conversely, when the reduction heat treatment temperature exceeds 1,800°C, or the reduction heat treatment time exceeds 10 hours, there is a problem in that copper is volatilized.

In addition, the reduction process may be performed 2 to 3 times to elute more copper on the surface of the particles.

At this time, it is preferable to repeat the reduction heat treatment for 2 to 3 times. In this way, when the reduction heat treatment is repeatedly performed for 2 to 3 times, more copper is eluted on the surface of the sintered body, thereby improving electrical conductivity.

By the above-described process, a copper-doped perovskite-structured metal oxide may be prepared.

The solid oxide electrode using the copper-doped perovskite structure metal oxide manufactured by the method according to the embodiment of the present invention described above may be used as an electrode of any one of a solid oxide fuel cell and a gas sensor. The sensor will be described as an example.

2 is a schematic diagram showing a limited current type gas sensor, FIG. 3 is a schematic diagram showing an upper portion of a limited current type gas sensor, and FIG. 4 is a schematic diagram showing a lower portion of the limited current type gas sensor.

2 to 4, the limited current type gas sensor 100 includes a solid electrolyte 110 serving as an ion conductor, and a first electrode 120 disposed on the upper and lower surfaces of the solid electrolyte 110, respectively. ) And a second electrode 130.

In addition, the limited current type gas sensor 100 is provided on the upper surface of the solid electrolyte 110, a diffusion hole 141 through which an external gas flows into the solid electrolyte 110, and an internal space 142 through which the external gas is diffused. It may further include a gas diffusion barrier 140 having ).

The limiting current type gas sensor 100 may use yttria stabilized zirconia (YSZ) containing yttrium oxide (Y2O ₃ ) as an additive as the solid electrolyte 110. Additionally, a heater (not shown) may be provided outside the gas diffusion barrier 140 to set the solid electrolyte 110 to a predetermined temperature.

The limited current type gas sensor 100 has a structure in which an output current flows through the solid electrolyte 110 in proportion to the voltage due to the application of a voltage between the first and second electrodes 120 and 130.

Further, in the limited current type gas sensor 100, when the voltage increases, the output current is saturated, and the output current in the saturation region is referred to as a limit current. The magnitude of the output current is related to the oxygen concentration. Accordingly, the limiting current type gas sensor 100 makes it possible to detect and measure the oxygen concentration from the limit current value obtained according to the voltage.

The current flow in the solid electrolyte 110 of the limited current type gas sensor 100 is based on the movement of oxygen ions and has a current value that is dependent on voltage and temperature. Therefore, the limited current type gas sensor 100 is set to a temperature of approximately 650 to 800°C and applies a voltage.

As described above, the first and second electrodes 120 and 130 are conventionally made of porous platinum (Pt) or silver (Ag), and there is a limit to improving the sensor sensing performance, and the process cost for manufacturing the sensor I had this a lot of trouble. However, as in the present invention, the Pr-Sr-Ti-based metal oxide of a perovskite structure doped with copper as the first and second electrodes 120 and 130 of the limited current type gas sensor 100 is used as an electrode. If used, it is possible to improve the sensor detection performance and reduce the manufacturing cost.

The first and second electrodes 120 and 130 are connected to the first and second lead wires 121 and 131, respectively. The first and second lead wires 121 and 131 are connected to the power supply unit 150 to apply a voltage. The power supply unit 150 is connected in series with the ammeter and in parallel with the voltmeter.

As shown in FIG. 3, in the limited current type gas sensor 100, a diffusion hole 141 is formed in the upper center of the gas diffusion barrier 140, and a solid electrolyte 110 is provided at the lower portion.

In addition, as shown in FIG. 4, in the limited current type gas sensor 100, a solid electrolyte 110 is provided under the gas diffusion barrier 140, and a second electrode 130 is provided under the solid electrolyte 110. ) Is provided, and the second electrode 130 is connected to the second lead wire 131.

As described so far, the copper-doped perovskite structure metal oxide according to an embodiment of the present invention and the method of manufacturing the same, and the solid oxide electrode using the same, the metal copper is eluted in the Pr-Sr-Ti metal oxide at high temperature. By being stuck, the catalytic capacity increases, and not only has excellent performance at high temperatures, but also it is possible to reduce manufacturing cost and improve performance through the replacement of precious metals by applying metallic copper.

As a result, the copper-doped perovskite structure metal oxide according to the embodiment of the present invention and the method of manufacturing the same, and the solid oxide electrode using the same have excellent catalytic performance and high-temperature stability, thereby improving the performance of the solid oxide fuel cell. And it can be used as an electrode such as a gas sensor.

In addition, the copper-doped perovskite structure metal oxide according to an embodiment of the present invention and a method of manufacturing the same, and a solid oxide electrode using the same, are obtained by dissolving metal copper to Pr-Sr-Ti metal oxide at a high temperature. Electrical conductivity is improved by doping metallic copper so that a part of the surface is buried. Accordingly, when used as an electrode such as a solid oxide fuel cell and a gas sensor, the resistance can be reduced, so that high efficiency can be maintained even in a medium-low temperature region.

Example

Hereinafter, the configuration and operation of the present invention will be described in more detail through preferred embodiments of the present invention. However, this is presented as a preferred example of the present invention and cannot be construed as limiting the present invention in any sense.

Contents not described herein can be sufficiently technically inferred by those skilled in the art, and thus description thereof will be omitted.

1. Sample preparation

Example 1

Pr ₆ O ₁₁ , SrN ₂ O ₆ , Cu(NO ₃ ) ₂ and TiO ₂ were weighed according to the stoichiometric ratio, dissolved in acetone, and heated to 150°C while irradiating ultrasonic waves for 40 minutes at 30 kHz. Was evaporated to prepare a mixture.

Next, the mixture was calcined at 1,100° C. for 7 hours and then pulverized to prepare a pellet.

Next, the pellets were sintered at 1,400° C. for 10 hours to prepare a sintered body.

Next, the sintered body is subjected to reduction heat treatment at 1,600°C for 8 hours in a 5wt% H ₂ atmosphere, and the copper contained in the sintered body is eluted to the surface of the sintered body, and the copper-doped metal composed of Pr _0.4 Sr _0.4 TiO ₃ The oxide was prepared.

Example 2

In Chemical Formula 1, a copper-doped metal oxide was prepared in the same manner as in Example 1, except that the stoichiometric ratio was adjusted so that x and y were respectively 0.3, and the composition was controlled to be composed of Pr _0.3 Sr _0.3 TiO ₃ .

Example 3

In Chemical Formula 1, a copper-doped metal oxide was prepared in the same manner as in Example 1, except that the stoichiometric ratio was adjusted so that x and y each had 0.2, and the composition was controlled to be composed of Pr _0.2 Sr _0.2 TiO ₃ .

Example 4

In Chemical Formula 1, a copper-doped metal oxide was prepared in the same manner as in Example 1, except that the stoichiometric ratio was adjusted so that x and y each had 0.1, and the composition was controlled to be composed of Pr _0.1 Sr _0.1 TiO ₃ .

Example 5

Pr ₆ O ₁₁ , SrN ₂ O ₆ , Cu(NO ₃ ) ₂ and TiO ₂ were weighed according to the stoichiometric ratio, dissolved in acetone, and heated to 160°C while irradiating ultrasonic waves for 30 minutes at 40 kHz. Was evaporated to prepare a mixture.

Next, the mixture was calcined at 1,100° C. for 7 hours and then pulverized to prepare a pellet.

Next, the pellets were sintered at 1,400° C. for 10 hours to prepare a sintered body.

Next, the sintered body was repeatedly subjected to reduction heat treatment twice for 8 hours under conditions of 1,600°C in a 5 wt% H ₂ atmosphere, and the copper contained in the sintered body was eluted to the surface of the sintered body, which was composed of Pr _0.4 Sr _0.4 TiO ₃ . A copper-doped metal oxide was prepared.

Example 6

In Chemical Formula 2, a copper-doped metal oxide was prepared in the same manner as in Example 5, except that the stoichiometric ratio was adjusted so that x and y were respectively 0.3, and the composition was controlled to be composed of Pr _0.3 Sr _0.55 TiO ₃ .

Example 7

In Chemical Formula 2, a copper-doped metal oxide was prepared in the same manner as in Example 5, except that the stoichiometric ratio was adjusted so that x and y each had 0.2, and the composition was controlled to be composed of Pr _0.2 Sr _0.7 TiO ₃ .

Example 8

In Chemical Formula 2, a copper-doped metal oxide was prepared in the same manner as in Example 5, except that the stoichiometric ratio was adjusted so that x and y each had 0.1, and the composition was controlled to be composed of Pr _0.1 Sr _0.85 TiO ₃ .

Comparative Example 1

Pr ₆ O ₁₁ , SrN ₂ O ₆ and TiO ₂ were weighed according to the stoichiometric ratio, dissolved in acetone, and heated to 150° C. while irradiating ultrasonic waves for 40 minutes at 30 kHz to evaporate acetone to prepare a mixture. .

Next, the mixture was calcined at 1,100° C. for 7 hours and then pulverized to prepare a pellet.

Next, the pellets were sintered at 1,400° C. for 10 hours to prepare a metal oxide composed of Pr _0.3 Sr _0.3 TiO ₃ .

Comparative Example 2

A copper-doped metal oxide was prepared in the same manner as in Comparative Example 1, except that the stoichiometric ratio was adjusted so that x and y were respectively 0.2, and the composition was controlled to be composed of Pr _0.2 Sr _0.2 TiO ₃ .

Comparative Example 3

A copper-doped metal oxide was prepared in the same manner as in Comparative Example 1, except that the stoichiometric ratio was adjusted so that x and y were respectively 0.1, and the composition was controlled to be composed of Pr _0.1 Sr _0.1 TiO ₃ .

2. Observation of crystal structure

5 is a graph showing the results of X-ray diffraction analysis of specimens prepared according to Examples 1 to 4, and FIG. 6 is a graph showing the results of X-ray diffraction analysis of specimens prepared according to Examples 5 to 8. This is the graph shown.

As shown in FIGS. 5 and 6, as can be seen through the XRD measurement results, the specimens prepared according to Examples 1 to 8 exhibit a perovskite structure, and after reduction heat treatment, they elute to the surface of the metal oxide. It was confirmed that the crystal plane 111 of copper, which is a nano metal, appeared.

3. Property evaluation

7 is a graph showing electrical conductivity measurement results for specimens manufactured according to Examples 1 to 2, 4, 6 to 8 and Comparative Examples 1 to 3.

As shown in FIG. 7, in the case of the specimens manufactured according to Examples 1 to 2, 4, and 6 to 8, it can be seen that the electrical conductivity is significantly improved compared to the specimens manufactured according to Comparative Examples 1 to 3. At this time, it can be seen that the specimens manufactured according to Examples 1 to 2 and 4 have better electrical conductivity characteristics than those of Examples 6 to 8.

Although the above has been described based on the embodiments of the present invention, various changes or modifications can be made at the level of a person skilled in the art to which the present invention pertains. Such changes and modifications can be said to belong to the present invention as long as it does not depart from the scope of the technical idea provided by the present invention. Accordingly, the scope of the present invention should be determined by the claims set forth below.

S110: dissolution step
S120: calcining step
S130: Sintering step
S140: reducing heat treatment step

Claims (17)

Metal oxide of perovskite structure; And
Includes; copper eluted to the surface of the metal oxide and doped so that a part of the metal oxide is embedded in the surface of the metal oxide,
The copper is eluted in a high temperature condition of 1,500 to 1,800° C. in an H ₂ atmosphere of 5 to 10% by weight, and a part is buried in the surface of the metal oxide to increase electrical conductivity,
The metal oxide includes praseodymium (Pr), strontium (Sr) and titanium (Ti),
The metal oxide is a copper-doped perovskite structure metal oxide, characterized in that represented by the following Formula 1 or Formula 2.
[Formula 1]
Pr _x Sr _y TiO ₃
(Where x is 0.1 ~ 0.4, y is an integer of 0.1 ~ 0.4.)
[Formula 2]
Pr _x Sr _1-1.5y TiO ₃
(Where x is 0.1 ~ 0.3, y is an integer of 0.1 ~ 0.3.)
delete delete The method of claim 1,
The copper is
Copper-doped perovskite structure metal oxide, characterized in that doped with 0.04 ~ 0.08 mol%.
(a) dissolving a praseodymium precursor, a strontium precursor, a titanium precursor, and a copper precursor in a solvent and heating while irradiating ultrasonic waves to form a mixture;
(b) calcining the mixture and then pulverizing to form a pellet;
(c) sintering the pellets to form a sintered body; And
(d) forming a copper-doped metal oxide by eluting copper contained in the sintered body to the surface of the sintered body by reducing heat treatment in a reducing atmosphere; and
In the step (d), the reduction heat treatment is performed for 5 to 10 hours under conditions of 1,500 to 1,800°C in an H ₂ atmosphere of 5 to 10% by weight, and the reduction heat treatment is repeated for 2 to 3 times. , Copper is partially embedded in the surface of the metal oxide to increase electrical conductivity,
The metal oxide includes praseodymium (Pr), strontium (Sr) and titanium (Ti),
The metal oxide is a method for producing a copper-doped perovskite structure metal oxide, characterized in that represented by the following formula (1) or (2).
[Formula 1]
Pr _x Sr _y TiO ₃
(Where x is 0.1 ~ 0.4, y is an integer of 0.1 ~ 0.4.)
[Formula 2]
Pr _x Sr _1-1.5y TiO ₃
(Where x is 0.1 ~ 0.3, y is an integer of 0.1 ~ 0.3.)
The method of claim 5,
In step (a),
The praseodymium precursor is
Pr ₆ O ₁₁ and Pr ₂ O ₃ Method for producing a copper-doped perovskite structure metal oxide comprising at least one member selected from the group consisting of.
The method of claim 5,
In step (a),
The strontium precursor is
SrN ₂ O ₆ , SrCO ₃ and SrSO ₄ Method for producing a copper-doped perovskite structure metal oxide comprising at least one selected from the group consisting of.
The method of claim 5,
In step (a),
The titanium precursor is
TiO ₂ , TiCl ₄ and TiOCl ₂ Method for producing a copper-doped perovskite structure metal oxide comprising at least one selected from the group consisting of.
The method of claim 5,
In step (a),
The copper precursor is
Cu(NO ₃ ) ₂ , CuCl ₂ , CuCO ₃ and Cu ₂ SO _{4 A} method of producing a copper-doped perovskite structure metal oxide comprising at least one selected from the group consisting of.
The method of claim 5,
The copper precursor is
A method for producing a copper-doped perovskite structure metal oxide, characterized in that the copper eluted to the surface of the metal oxide is mixed to be 0.04 to 0.08 mol%.
The method of claim 5,
In step (a),
The ultrasonic irradiation is
Method for producing a copper-doped perovskite structure metal oxide, characterized in that carried out for 1 to 60 minutes under the conditions of 10 to 60 kHz.
The method of claim 5,
In step (b),
The calcination is
Method for producing a copper-doped perovskite structure metal oxide, characterized in that carried out for 6 to 12 hours at 1,000 ~ 1,200 ℃.
The method of claim 5,
The sintering is
Copper-doped perovskite structure metal oxide, characterized in that carried out at 1,400 ~ 1,500 ℃ for 5 ~ 10 hours.
delete delete A solid oxide electrode using a copper-doped perovskite structure metal oxide prepared using a metal oxide including praseodymium, strontium, and titanium prepared by the manufacturing method according to any one of claims 5 to 13.
The method of claim 16,
The solid oxide electrode is
A solid oxide electrode using a copper-doped perovskite structure metal oxide, which is used as an electrode of any one of a solid oxide fuel cell and a gas sensor.

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