KR20210060878A - Praseodymium doped metal oxide and method of manufacturing the same and solid oxide electrode using the same - Google Patents

Abstract

The present invention relates to a praseodymium-doped metal oxide having a perovskite structure, which realizes excellent performance even at high temperature by controlling oxygen-deficient and oxygen-excessive conditions through an oxidation and reduction process to obtain desired performance, and can substitute for a noble metal, such as platinum, a method for preparing the same, and a solid oxide electrode using the same. The method for preparing a praseodymium-doped metal oxide having a perovskite structure according to the present invention includes the steps of: (a) dissolving a praseodymium precursor, a strontium precursor and a titanium precursor in a solvent and heating them under irradiation of ultrasonic waves to form a mixture; (b) heat treating the mixture and pulverizing the resultant product to form pellets; (c) further heat treating the pellets to form a sintered body; and (d) carrying out reductive heat treatment of the sintered body under reductive atmosphere to form a praseodymium-doped metal oxide having a perovskite structure.

Description

Perovskite structure metal oxide substituted with praseodymium, and a method of manufacturing the same, and a solid oxide electrode using the same

The present invention relates to a perovskite structure metal oxide substituted with praseodymium and a method of manufacturing the same, and a solid oxide electrode using the same, and more particularly, to a desired performance by controlling oxygen deficiency and oxygen excess conditions through oxidation and reduction processes. A perovskite-structured metal oxide substituted with praseodymium that can replace noble metals such as platinum by controlling to exhibit excellent performance at high temperatures, and a method of manufacturing the same, and a solid oxide electrode using the same.

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 secondary charging and discharging concept is repeated through continuous forward and reversible reactions. Efforts to utilize it as a battery are in progress.

In order to be used in a 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. 10-2013-0075529 (published on May 5, 2013), and the document describes a solid oxide electrode, a solid oxide fuel cell including the same, and a method of manufacturing the same.

The object of the present invention is to control the oxygen deficiency and oxygen excess conditions through oxidation and reduction processes, thereby exhibiting excellent performance even at high temperatures, thereby replacing a praseodymium-substituted perovskite that can replace noble metals such as platinum. It is to provide a structured metal oxide, a method of manufacturing the same, and a solid oxide electrode using the same.

The method for producing a perovskite structure metal oxide substituted with praseodymium according to an embodiment of the present invention to achieve the above object is (a) a praseodymium precursor, a strontium precursor, and a titanium precursor are dissolved in a solvent and heated while irradiating with ultrasonic waves. Forming a mixture; (b) subjecting the mixture to primary heat treatment and grinding to form pellets; (c) forming a sintered body by secondary heat treatment of the pellets; And (d) forming a metal oxide having a perovskite structure in which praseodynium is substituted by reducing heat treatment in a reducing atmosphere.

The perovskite structure metal oxide substituted with praseodymium according to an embodiment of the present invention for achieving the above object is characterized by represented by the following formula (1) or the following formula (2).

[Formula 1]

Pr _x Sr _1-y TiO _3+z

(Where x is more than 0 ~ 0.4 or less, y is 0.1 ~ 0.4, z is an integer of 0 ~ 0.3.)

[Formula 2]

Pr _x Sr _1-1.5y TiO _3-z

(Where x is more than 0 ~ 0.4 or less, y is 0.1 ~ 0.4, z is an integer of 0 ~ 0.3.)

A perovskite structure metal oxide substituted with praseodymium according to the present invention and a method of manufacturing the same, and a solid oxide electrode using the same, by controlling oxygen deficiency and oxygen excess conditions through oxidation and reduction processes to control desired performance, It exhibits excellent performance even at high temperatures and can replace precious metals such as platinum.

Accordingly, the praseodymium-substituted perovskite structure metal oxide and the method of manufacturing the same, and the solid oxide electrode using the same can replace expensive precious metals, thereby reducing manufacturing cost and improving excellent performance such as electrical conductivity. I can plan an effect.

In addition, the praseodymium-substituted perovskite structure metal oxide and its manufacturing method according to the present invention, and the solid oxide electrode using the same, reduce the resistance by improving the performance of the electrode based on excellent electrical conductivity and high temperature stability. It is suitable for use as an electrode for solid oxide fuel cells and gas sensors, as it can maintain high efficiency even in the region.

1 is a process flow chart showing a method of manufacturing a perovskite structure metal oxide substituted with praseodynium according to an embodiment of the present invention.
2 is a cross-sectional view showing a limited current type gas sensor.
3 is a perspective view showing the upper portion of the limited current type gas sensor.
4 is a graph showing the results of X-ray diffraction analysis of samples prepared according to Examples 1 to 4.
5 is a graph showing the results of X-ray diffraction analysis of samples prepared according to Examples 5 to 8.
6 is a graph showing electrical conductivity measurement results for samples 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 intended 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 the possessor, 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 praseodymium-substituted 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 substituted with praseodymium

The perovskite structure metal oxide substituted with praseodymium according to an embodiment of the present invention is represented by the following Formula 1 or Formula 2.

[Formula 1]

Pr _x Sr _1-y TiO _3+z

(Where x is more than 0 ~ 0.4 or less, y is 0.1 ~ 0.4, z is an integer of 0 ~ 0.3.)

[Formula 2]

Pr _x Sr _1-1.5y TiO _3-z

(Where x is more than 0 ~ 0.4 or less, y is 0.1 ~ 0.4, z is an integer of 0 ~ 0.3.)

The metal oxide represented by Formula 1 above corresponds to an oxygen-excessive structure, and the metal oxide represented by Formula 2 corresponds to an oxygen-deficient structure.

As described above, in the present invention, it is possible to control desired performance by controlling oxygen deficiency and oxygen excess conditions through oxidation and reduction processes.

Accordingly, it is possible to produce a perovskite-structured metal oxide substituted with praseodymium, which can replace noble metals such as platinum by exhibiting excellent performance even at high temperatures.

As a result, since the present invention provides a perovskite structure metal oxide substituted with praseodymium, it is possible to replace expensive precious metals, thereby reducing manufacturing costs and achieving excellent performance improvement effects such as electrical conductivity.

Method for producing a perovskite structure metal oxide substituted with praseodymium

1 is a process flow chart showing a method of manufacturing a perovskite structure metal oxide substituted with praseodynium according to an embodiment of the present invention.

As shown in FIG. 1, the method for producing a perovskite structure metal oxide substituted with praseodynium according to an embodiment of the present invention includes a mixture formation step (S110), a first heat treatment step (S120), and a second heat treatment. It includes a step (S130) and a reduction heat treatment step (S140).

Mixture formation

In the mixture forming step (S110), a praseodymium precursor, a strontium precursor, and a titanium precursor are dissolved in a solvent and then heated while irradiating 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 addition, as a solvent, acetone, 2-methoxyethanol, DMF (dimethylformamide), octanol, ethoxy ethanol, tetradecane, pentanol ), dipropylene glycol monomethyl ether, ethylene glycol, benzene, distilled water (H ₂ O), and the like may be used, but is not limited thereto.

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, and the titanium precursor may not be uniformly mixed in a 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.

1st heat treatment

In the first heat treatment step (S120), the mixture is first heat treated and pulverized to form pellets.

The primary heat treatment is preferably performed at 1,000 to 1,200°C for 6 to 12 hours. If the first heat treatment temperature is less than 1,000°C or the first heat treatment time is less than 6 hours, there is a concern that the surface of the mixture may not melt well. Conversely, when the first heat treatment temperature exceeds 1,200°C or the first heat treatment time exceeds 12 hours, the mixtures may react with each other to form a different composition locally, and the size of the crystal grains may be excessively large. It is not desirable.

Secondary heat treatment

In the second heat treatment step (S130), the pellet is subjected to a second heat treatment to form a sintered body.

The secondary heat treatment is preferably performed at 1,500 to 1,700°C for 5 to 10 hours. If the secondary heat treatment temperature is less than 1,500° C. or the second heat treatment time is less than 5 hours, there is a high concern that the relative density may be lowered due to poor crystallization. Conversely, if the secondary heat treatment temperature exceeds 1,700°C or the second heat treatment time exceeds 10 hours, the average particle diameter of the oxide increases and the strength decreases due to the growth of pores, and only increases the manufacturing cost without any further effect. It can act as a factor, so it is not desirable.

Reduction heat treatment

In the reduction heat treatment step (S140), the sintered body is subjected to reduction heat treatment in a reducing atmosphere to form a metal oxide having a perovskite structure in which praseodynium is substituted.

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 praseodymium cannot be substituted because the reduction process is not performed smoothly. 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, and thus 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 praseodymium is not smoothly substituted. Conversely, when the reduction heat treatment temperature exceeds 1,800°C or the reduction heat treatment time exceeds 10 hours, it is not economical because it acts as a factor that increases only the manufacturing cost without any further effect.

After this step, the metal oxide of the perovskite structure in which praseodynium is substituted has a structure represented by the following Formula 1 or Formula 2.

[Formula 1]

Pr _x Sr _1-y TiO _3+z

(Where x is more than 0 ~ 0.4 or less, y is 0.1 ~ 0.4, z is an integer of 0 ~ 0.3.)

[Formula 2]

Pr _x Sr _1-1.5y TiO _3-z

(Where x is more than 0 ~ 0.4 or less, y is 0.1 ~ 0.4, z is an integer of 0 ~ 0.3.)

The metal oxide represented by Formula 1 above corresponds to an oxygen-excessive structure, and the metal oxide represented by Formula 2 corresponds to an oxygen-deficient structure.

As described above, in the present invention, it is possible to control desired performance by controlling oxygen deficiency and oxygen excess conditions through oxidation and reduction processes.

Accordingly, it is possible to produce a perovskite-structured metal oxide substituted with praseodymium, which can replace noble metals such as platinum by exhibiting excellent performance even at high temperatures.

As a result, since the present invention provides a perovskite structure metal oxide substituted with praseodymium, it is possible to replace expensive precious metals, thereby reducing manufacturing costs and achieving excellent performance improvement effects such as electrical conductivity.

As described so far, the solid oxide electrode using the perovskite structure metal oxide substituted with praseodymium prepared by the method according to the embodiment of the present invention can be used as any one of a solid oxide fuel cell and a gas sensor. .

Hereinafter, a gas sensor to which a solid oxide electrode using a perovskite structure metal oxide substituted with praseodymium is applied will be described as an example.

2 is a cross-sectional view showing a limited current type gas sensor, and FIG. 3 is a perspective view showing an upper portion of the limited current type gas sensor.

2 and 3, 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. A gas diffusion barrier 140 having) may be further included.

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 limiting 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 limiting 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, a Pr-Sr-Ti-based metal oxide having a perovskite structure in which praseodymium is substituted with the first and second electrodes 120 and 130 of the limited current type gas sensor 100 When used as an electrode, sensor sensing performance can be improved and manufacturing cost can be reduced.

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.

In this 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, in the limited current type gas sensor 100, a solid electrolyte 110 is provided under the gas diffusion barrier 140, a second electrode 130 is provided under the solid electrolyte 110, and a second electrode 130 is connected to the second lead wire 131.

As described so far, the praseodymium-substituted perovskite structure metal oxide and its manufacturing method, and the solid oxide electrode using the same according to an embodiment of the present invention control oxygen deficiency and oxygen excess conditions through oxidation and reduction processes. Thus, by controlling the desired performance, excellent performance can be exhibited even at high temperatures, and noble metals such as platinum can be replaced.

Accordingly, since the praseodymium-substituted perovskite structure metal oxide and the method of manufacturing the same, and the solid oxide electrode using the same can replace expensive precious metals, the manufacturing cost can be reduced while reducing the manufacturing cost. Excellent performance improvement effect can be achieved.

In addition, the praseodymium-substituted 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, reduce resistance by improving electrode performance based on excellent electrical conductivity and high temperature stability. Therefore, it is suitable for use as an electrode such as a solid oxide fuel cell and gas sensor because it can maintain high efficiency even in the middle and low temperature range.

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 has been 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 this technical field, and thus description thereof will be omitted.

1. Sample preparation

Example 1

After _{weighing Pr 6} O ₁₁ , SrN ₂ O ₆ , Cu(NO ₃ ) ₂ and TiO ₂ according to the stoichiometric ratio, dissolving in acetone and heating to 150℃ while irradiating ultrasonic waves for 30 minutes under 40kHz condition to acetone A mixture was prepared by evaporation.

Next, the mixture was subjected to primary heat treatment at 1,100° C. for 8 hours and then pulverized to prepare a pellet.

Next, the pellet was subjected to secondary heat treatment at 1,600° C. for 7 hours to prepare a sintered body.

Next, the sintered body was subjected to reduction heat treatment at 1,600°C for 9 hours _{in a 5wt% H 2} atmosphere to prepare a metal oxide substituted with praseodymium composed of _{Pr 0.4} Sr _0.4 TiO _3.1.

Example 2

In Chemical Formula 1, a metal oxide substituted with praseodymium was prepared in the same manner as in Example 1, except that the stoichiometric ratio was adjusted so that x and y each had 0.3, _{and the composition was controlled to be composed of Pr 0.3} Sr _0.3 TiO _3.1.

Example 3

In Chemical Formula 1, a metal oxide substituted with praseodymium 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 _3.1.

Example 4

In Chemical Formula 1, a metal oxide substituted with praseodymium 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 _3.1.

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 170°C while irradiating ultrasonic waves for 40 minutes at 40 kHz. A mixture was prepared by evaporation.

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

Next, the pellet was subjected to secondary heat treatment at 1,650° C. for 9 hours to prepare a sintered body.

Next, the sintered body was subjected to reduction heat treatment at 1,600°C for 8 hours _{in a 5wt% H 2} atmosphere to prepare a metal oxide substituted with praseodymium composed of _{Pr 0.4} Sr _0.4 TiO _2.9.

Example 6

In Chemical Formula 2, a metal oxide substituted with praseodymium 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 _2.9.

Example 7

In Chemical Formula 2, a metal oxide substituted with praseodymium 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 _2.9.

Example 8

In Chemical Formula 2, a metal oxide substituted with praseodymium 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 _2.9.

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 subjected to primary heat treatment at 1,100° C. for 7 hours and then pulverized to prepare a pellet.

Next, the pellet was subjected to secondary heat treatment at 1,500° C. for 10 hours to prepare a metal oxide composed of _{Pr 0.3} Sr _0.3 TiO _3.

Comparative Example 2

A metal oxide substituted with praseodymium was prepared in the same manner as in Comparative Example 1, except that the stoichiometric ratio was controlled to _{be composed of Pr 0.2} Sr _0.2 TiO _3.

Comparative Example 3

A metal oxide substituted with praseodymium was prepared in the same manner as in Comparative Example 1, except that the stoichiometric ratio was controlled to _{be composed of Pr 0.1} Sr _0.1 TiO _3.

2. Observation of crystal structure

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

5 and 6, as can be seen through the XRD measurement results, it can be seen that the samples prepared according to Examples 1 to 8 exhibit a perovskite structure.

3. Property evaluation

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

As shown in FIG. 6, in the case of samples prepared according to Examples 1 to 2, 4, and 6 to 8, it can be seen that electrical conductivity is significantly improved compared to the samples prepared according to Comparative Examples 1 to 3.

In particular, it was confirmed that the samples prepared according to Examples 1 to 2 and 4 exhibited superior results in terms of electrical conductivity characteristics compared to Examples 6 to 8.

Although the above has been described with reference to the embodiments of the present invention, various changes or modifications can be made at the level of those of ordinary skill in the art to which the present invention pertains. Such changes and modifications may be said to belong to the present invention as long as they do not depart from the scope of the technical idea provided by the present invention. Therefore, the scope of the present invention should be determined by the claims set forth below.

S110: mixture formation step
S120: 1st heat treatment step
S130: 2nd heat treatment step
S140: reduction heat treatment step

Claims (13)

(a) dissolving a praseodymium precursor, a strontium precursor, and a titanium precursor in a solvent and heating while irradiating ultrasonic waves to form a mixture;
(b) subjecting the mixture to primary heat treatment and grinding to form pellets;
(c) forming a sintered body by secondary heat treatment of the pellets; And
(d) forming a metal oxide having a perovskite structure in which praseodynium is substituted by reducing heat treatment in a reducing atmosphere;
Praseodynium-substituted perovskite structure metal oxide manufacturing method comprising a.
The method of claim 1,
After step (d),
The metal oxide is
A method for producing a perovskite structure metal oxide substituted with praseodymium, which is represented by the following Chemical Formula 1 or Chemical Formula 2.

[Formula 1]
Pr _x Sr _1-y TiO _3+z
(Where x is more than 0 ~ 0.4 or less, y is 0.1 ~ 0.4, z is an integer of 0 ~ 0.3.)

[Formula 2]
Pr _x Sr _1-1.5y TiO _3-z
(Where x is more than 0 ~ 0.4 or less, y is 0.1 ~ 0.4, z is an integer of 0 ~ 0.3.)
The method of claim 1,
In step (a),
The praseodymium precursor is
Pr ₆ O ₁₁ and Pr ₂ O ₃ Praseodynium-substituted perovskite structure metal oxide manufacturing method comprising at least one selected from the group consisting of.
The method of claim 1,
In step (a),
The strontium precursor is
_{SrN 2} O ₆ , SrCO ₃ and SrSO ₄ Praseodynium-substituted perovskite structure metal oxide production method comprising at least one selected from the group consisting of.
The method of claim 1,
In step (a),
The titanium precursor is
TiO ₂ , TiCl ₄ and TiOCl ₂ Praseodynium-substituted perovskite structure metal oxide manufacturing method comprising at least one selected from the group consisting of.
The method of claim 1,
In step (a),
The ultrasonic irradiation is
Praseodynium-substituted perovskite structure metal oxide manufacturing method, characterized in that carried out for 1 to 60 minutes under the conditions of 10 to 60 kHz.
The method of claim 1,
In step (b),
The primary heat treatment is
A method for producing a perovskite structure metal oxide substituted with praseodynium, characterized in that carried out at 1,000 to 1,200°C for 6 to 12 hours.
The method of claim 1,
In step (c),
The secondary heat treatment is
Praseodynium-substituted perovskite structure metal oxide production method, characterized in that carried out for 5 to 10 hours at 1,500 ~ 1,700 ℃.
The method of claim 1,
In step (d),
The reduction heat treatment is
A method for producing a perovskite structure metal oxide substituted with praseodynium, characterized in that it is 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% by weight.
Praseodymium-substituted perovskite structure metal oxide, characterized in that represented by the following Chemical Formula 1 or the following Chemical Formula 2.

[Formula 1]
Pr _x Sr _1-y TiO _3+z
(Where x is more than 0 ~ 0.4 or less, y is 0.1 ~ 0.4, z is an integer of 0 ~ 0.3.)

[Formula 2]
Pr _x Sr _1-1.5y TiO _3-z
(Where x is more than 0 ~ 0.4 or less, y is 0.1 ~ 0.4, z is an integer of 0 ~ 0.3.)
The method of claim 10,
The metal oxide is
A perovskite structure metal oxide substituted with praseodymium, characterized in that performance control is possible by selectively controlling oxygen deficiency represented by Formula 1 or excess oxygen represented by Formula 2.
A solid oxide electrode using the perovskite structure metal oxide substituted with praseodymium according to claim 10.
The method of claim 12,
The solid oxide electrode is
A solid oxide electrode using a perovskite structure metal oxide substituted with praseodymium, which is used as an electrode of any one of a solid oxide fuel cell and a gas sensor.

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