KR20200119953A - Catalyst for solid oxide electrolyzer cell having double perovskite structure, solid oxide electrolyzer cell having the same, method of manufacturing solid oxide electrolyzer cell - Google Patents

Abstract

The present invention provides a solid oxide electrolysis cell excellent in oxygen generation reaction. The solid oxide electrolysis cell comprises: a cathode which discharges hydrogen gas formed by decomposing water; an anode disposed facing the cathode and discharging oxygen gas formed by decomposing the water; and an electrolyte disposed between the anode and the cathode, wherein the solid oxide electrolysis cell generates hydrogen and oxygen, and at least one of the anode and the cathode includes a catalyst body.

Description

Catalyst for solid oxide electrolyzer cell having double perovskite structure, solid oxide electrolyzer cell having the same, method of manufacturing solid oxide electrolyzer cell}

The present invention relates to a catalyst body for a solid oxide electrolytic cell composed of a double layer perovskite material, a solid oxide electrolytic cell including the same, and a method of manufacturing the same.

In recent years, research on a technology for obtaining energy using hydrogen gas has been attracting attention. While conventional energy sources such as coal or petroleum contain carbon, hydrogen gas does not contain carbon at all and is mostly converted to water, so there is no generation of unnecessary by-products after being used as an energy source, and large energy is saved when converting to water. Can occur. Therefore, hydrogen gas is considered the most environmentally friendly and ideal energy source. In order to use hydrogen as an energy source, it is necessary to obtain hydrogen gas from water or hydrocarbons. In order to obtain hydrogen gas, hydrogen gas may be generated through a steam reforming pyrolysis gasification process using hydrocarbon-based substances such as natural gas, coal, and petroleum. However, since these hydrocarbon-based materials generate unwanted by-products together, there is a concern of polluting the environment.

Another way to obtain hydrogen gas is to generate hydrogen by electrolysis, which applies energy to water. Water is a clean resource that exists anywhere, and since water is decomposed into hydrogen gas and oxygen gas or can react in reverse, it has an advantage of high regeneration potential, and thus water can be treated as an ideal source of hydrogen gas. In addition, since the hydrogen production technology by electrolysis of water can recycle waste heat, it is in the spotlight as a hydrogen gas production technology.

Since the electrolysis of water according to the current technology uses heat of 800° C. or higher, it is limited to the temperature level of waste heat discharged from nuclear power generation. In addition, in such a high-temperature environment, there is a concern that nickel, which is an electrode material in contact with hydrogen, coarsens and deteriorates at high temperatures. In addition, during water decomposition, oxygen ions are oxidized to generate oxygen gas, while hydrogen ions are reduced to generate hydrogen gas. A commonly used catalyst for water decomposition has a problem in that the other performance is deteriorated when one of the hydrogen generation reaction (HER) performance and the oxygen generation reaction (OER) performance is good. Therefore, it is required to develop a water electrolytic cell with excellent oxygen generation reaction.

Korean Patent Publication No. 10-2018-00886545A

An object of the present invention is to provide a catalyst body for a solid oxide water electrolysis cell composed of a double layer perovskite material having excellent oxygen evolution reaction.

The technical object of the present invention is to provide a solid oxide electrolytic cell including the catalyst body.

The technical object of the present invention is to provide a method of manufacturing a solid oxide hydroelectrolyte cell including the catalyst body.

However, these problems are exemplary, and the technical idea of the present invention is not limited thereto.

The solid oxide electrolytic cell according to the technical idea of the present invention for achieving the above technical problem comprises: a cathode for discharging hydrogen gas formed by decomposing water; An anode disposed facing the cathode and discharging oxygen gas formed by decomposing the water; And an electrolyte disposed between the anode and the cathode, wherein at least one of the anode and the cathode includes a catalyst body, and the catalyst body is the following formula It includes the compound of 1.

<Formula 1>

PrBa _{0 . 5} Sr _{0 . 5} Co _{2 - x} Fe _x O _{5 +δ}

In Formula 1, x is a number in the range of more than 0 to 1.0 or less, and δ is a positive number of 1 or less, which is a value that makes the compound of Formula 1 electrically neutral.

In one embodiment of the present invention, in the catalyst body, x may be a number in the range of 0.25 or more to 1 or less.

In one embodiment of the present invention, in the catalyst body, x may be a number in the range of more than 0.4 to less than 0.8.

In one embodiment of the present invention, the catalyst body is PrBa _{0 . 5} Sr _{0 . 5} Co _{1 . 75} Fe _{0 . 25} O _{5 +δ} compound, PrBa _{0 . 5} Sr _{0 . 5} Co _{1 . 6} Fe _{0 . 4} O _{5 +δ} compound, PrBa _{0 . 5} Sr _{0 . 5} Co _{1 . 5} Fe _{0 . 5} O _{5 +δ} compound, PrBa _0.5 Sr _0.5 Co _1.25 Fe _0.75 O _5+δ compound, PrBa _{0 . 5} Sr _{0 . 5} Co _{1 . 2} Fe _{0 . 8} O _{5 +δ} compound, or PrBa _0.5 Sr _0.5 Co ₁ Fe ₁ O _{5 +δ} compound may be included.

In one embodiment of the present invention, the oxygen generating activity of the catalyst body may represent a voltage of 1.52 V to 1.570 V at a current density of 10 mA cm ^-1 .

The solid oxide electrolytic cell according to the technical idea of the present invention for achieving the above technical problem comprises: a cathode for discharging hydrogen gas formed by decomposing water; An anode disposed facing the cathode and discharging oxygen gas formed by decomposing the water; And an electrolyte disposed between the anode and the cathode, wherein at least one of the anode and the cathode includes a catalyst body, and the catalyst body is the following formula It includes the compound of 2.

<Formula 2>

LnBa _a Sr _b Co _{2 - x} Fe _x O _{5 +δ}

In Formula 2, Ln is neodymium (Nd), praseodymium (Pr), samarium (Sm), gadolinium (Gd), europium (Eu), terbium (Tb), erbium (Er), or a mixture thereof, and a and b is a number greater than 0 and less than 1, satisfies a+b=1, x is a number greater than 0 and less than 1.0, and δ is a positive number less than or equal to 1, which is a value that makes the compound of Formula 1 electrically neutral.

In one embodiment of the present invention, in the catalyst body, x may be a number in the range of 0.25 or more to 1 or less.

In one embodiment of the present invention, in the catalyst body, x may be a number in the range of more than 0.4 to less than 0.8.

A method of manufacturing a solid oxide aqueous electrolytic cell according to the present invention for achieving the above technical problem comprises: forming a mixture by mixing a plurality of metal precursors; Calcining the mixture; Reducing the calcined mixture; And annealing the reduced mixture to form a catalyst body including the compound of Formula 1 below.

<Formula 1>

PrBa _{0 . 5} Sr _{0 . 5} Co _{2 - x} Fe _x O _{5 +δ}

In Formula 1, x is a number in the range of more than 0 to 1.0 or less, and δ is a positive number of 1 or less, which is a value that makes the compound of Formula 1 electrically neutral.

In one embodiment of the present invention, in the catalyst body, x may be a number in the range of 0.25 or more to 1 or less.

In one embodiment of the present invention, in the catalyst body, x may be a number in the range of more than 0.4 to less than 0.8.

In one embodiment of the present invention, the catalyst body is PrBa _{0 . 5} Sr _{0 . 5} Co _{1 . 75} Fe _{0 . 25} O _{5 +δ} compound, PrBa _{0 . 5} Sr _{0 . 5} Co _{1 . 6} Fe _{0 . 4} O _{5 +δ} compound, PrBa _{0 . 5} Sr _{0 . 5} Co _{1 . 5} Fe _{0 . 5} O _{5 +δ} compound, PrBa _0.5 Sr _0.5 Co _1.25 Fe _0.75 O _5+δ compound, PrBa _{0 . 5} Sr _{0 . 5} Co _{1 . 2} Fe _{0 . 8} O _{5 +δ} compound, or PrBa _0.5 Sr _0.5 Co ₁ Fe ₁ O _{5 +δ} compound may be included.

The catalyst body for a solid oxide water electrolysis cell according to the technical idea of the present invention for achieving the above technical problem is a catalyst body included in the electrode for oxygen generation reaction of the solid oxide water electrolysis cell, and the catalyst body is a compound represented by the following Formula 1 Includes.

<Formula 1>

PrBa _{0 . 5} Sr _{0 . 5} Co _{2 - x} Fe _x O _{5 +δ}

In Formula 1, x is a number in the range of more than 0 to 1.0 or less, and δ is a positive number of 1 or less, which is a value that makes the compound of Formula 1 electrically neutral.

In one embodiment of the present invention, in the catalyst body, x may be a number in the range of 0.25 or more to 1 or less.

In one embodiment of the present invention, in the catalyst body, x may be a number in the range of more than 0.4 to less than 0.8.

The solid oxide electrolytic cell according to the technical idea of the present invention is PrBa _{0 . 5} Sr _{0 .} As cobalt was replaced with iron in ₅ Co ₂ O _{5 +d} , the oxygen generation activity increased. In particular, PrBa ₀ containing 25% iron _{. 5} Sr _{0 . 5} Co _{1 . 5} Fe _{0 . In} the case of ₅ O _{5 + d} , the oxygen generating activity was the highest. Accordingly, it is possible to provide a solid oxide electrolytic cell having excellent oxygen generation reaction.

The above-described effects of the present invention have been exemplified, and the scope of the present invention is not limited by these effects.

1 is a diagram schematically showing a solid oxide hydrolysis cell including a catalyst body according to an embodiment of the present invention.
FIG. 2 is a schematic diagram showing a double-layer perovskite crystal structure constituting the catalyst body applied to the anode of FIG. 1 according to an embodiment of the present invention.
FIG. 3 is a schematic diagram illustrating a case in which some atoms are substituted in a double-layer perovskite crystal structure constituting the catalyst body applied to the anode of FIG. 1 according to an embodiment of the present invention.
4 is a flow chart illustrating a method of manufacturing a solid oxide electrolytic cell according to an embodiment of the present invention.
5 is a graph measuring the oxygen generation activity of the catalyst body applied to the solid oxide water electrolysis cell according to an embodiment of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. The embodiments of the present invention are provided to more completely explain the technical idea of the present invention to those of ordinary skill in the art, and the following examples may be modified in various other forms, and The scope of the technical idea is not limited to the following examples. Rather, these embodiments are provided to make the present disclosure more faithful and complete, and to completely convey the technical idea of the present invention to those skilled in the art. In this specification, the same reference numerals mean the same elements. Furthermore, various elements and areas in the drawings are schematically drawn. Therefore, the technical idea of the present invention is not limited by the relative size or spacing drawn in the accompanying drawings.

As alkaline water electrolysis technology for hydrogen production is attracting attention, efficient electrode catalysts are also being widely studied. In order to replace the expensive platinum-based catalyst used as an electrode catalyst for hydrogen evolution, catalysts based on precious metals such as ruthenium (Ru) or iridium (Ir) have been researched and developed. However, since the bottleneck in the water electrolysis system depends on the slow rate of oxygen evolution, it is necessary to develop a catalyst for efficient oxygen evolution. As a catalyst for the oxygen evolution reaction, a catalyst based on perovskite oxide is being studied.

1 is a view schematically showing a solid oxide hydrolysis cell 300 including a catalyst body according to an embodiment of the present invention.

Referring to FIG. 1, a solid oxide electrolytic cell 300 includes an anode 310, a cathode 320 disposed facing the anode 310, and oxygen ions disposed between the anode 310 and the cathode 320. It includes an electrolyte 330 which is a conductive solid oxide. The cathode 320 may be referred to as a hydrogen electrode because it contacts hydrogen gas, and the anode 310 may be referred to as an oxygen electrode because it contacts oxygen gas.

The electrochemical reaction of the solid oxide aqueous electrolysis cell 300 is a cathodic reaction in which water (H ₂ O) of the cathode 320 is changed into hydrogen gas (H ₂ ) and oxygen ions (O ^2- ), as shown in the following reaction equation. The oxygen ions moved through the electrolyte 330 are converted into oxygen gas (O ₂ ). This reaction is contrary to the reaction principle of conventional fuel cells.

<Reaction Scheme>

Cathode ^{_{reaction: H 2 O + 2e - -}} > O 2- + H 2

Anode _{^{reaction: O 2- -> 1/2 O 2}} + 2e -

When power is applied to the solid oxide electrolytic cell 300 from the external power source 340, electrons are provided to the solid oxide electrolytic cell 300 from the external power source 340. The electrons react with water provided to the cathode 320 to generate hydrogen gas and oxygen ions. The hydrogen gas is discharged to the outside, and the oxygen ions pass through the electrolyte 330 and move to the anode 310. The oxygen ions moved to the anode 310 lose electrons and are converted into oxygen gas and discharged to the outside. The electrons flow to the external power source 340. Through this electron transfer, the solid oxide electrolysis cell 300 may electrolyze water to form hydrogen gas at the cathode 320 and oxygen gas at the anode 310.

The anode 310 may be configured to include a catalyst body made of a double-layer perovskite material according to the technical idea of the present invention.

The cathode 320 is not particularly limited, and a known cathode may be used. The cathode 320 may include the same material as or have the same structure as the anode 210 of the solid oxide fuel cell 200 described above. In addition, a case in which the cathode 320 is configured to include a catalyst body according to the technical idea of the present invention is also included in the technical idea of the present invention.

The electrolyte 330 is not particularly limited as long as it can be generally used in the art. The electrolyte 330 may include the same material or have the same structure as the electrolyte 230 of the solid oxide fuel cell 200 described above.

Since the solid oxide electrolytic cell 300 can be manufactured using a conventional method known in various documents in the relevant technical field, a detailed description thereof will be omitted here. In addition, the solid oxide electrolytic cell 300 may be applied to various structures such as a tubular stack, a flat tubular stack, and a planar type stack. The solid oxide electrolytic cell 300 may be in the form of a stack of unit cells. For example, unit cells composed of an anode 310, a cathode 320, and an electrolyte 330 are stacked in series, and a separator electrically connecting them is interposed between the unit cells, A stack can be obtained.

Hereinafter, a catalyst body, which is a constituent element constituting the anode 310 of the solid oxide water electrolysis cell 300, will be described in detail. The catalyst body according to the technical idea of the present invention may have a perovskite structure.

FIG. 2 is a schematic diagram showing a double-layer perovskite crystal structure constituting the catalyst body applied to the anode of FIG. 1 according to an embodiment of the present invention.

Referring to FIG. 2, the catalyst body may be composed of a perovskite crystal structure material, for example, a single perovskite crystal structure material or a double layer perovskite crystal structure material.

Hereinafter, the perovskite crystal structure material will be described.

A simple perovskite crystal structure represented by ABO ₃ is an element with a large ionic radius such as rare earth elements, alkaline rare earth, and alkaline in the A-site, which is the corner position of the cubic lattice. Are located and have 12 coordination number (CN) by oxygen ions. Transition metals with a small atomic radius such as Co and Fe are located at the B-site, which is the body center position of the cubic lattice, and forms an octahedron (6 coordination number) by oxygen ions. Finally, oxygen ions are located at the center of each face of the cubic lattice.

Such a simple perovskite crystal structure is generally structurally displaced when another substance is substituted at the A-site, and its maximum is mainly centered on the element located at the B-site. A structural shift occurs in the octahedron of BO ₆ consisting of adjacent oxygen ions (6).

For example, when reduction is performed in a hydrogen atmosphere, a single perovskite structure is changed into a double layer perovskite structure. When this double-packed perovskite structure is formed, movement of oxygen ions can be accelerated and thermal and chemical stability can be improved.

As shown in FIG. 2, the double-layer perovskite crystal structure is a crystal lattice structure in which two or more elements are regularly arranged at the A-site, and may have a formula of AA'B ₂ O _{5 +δ} . . Such a double-layer perovskite crystal structure material has oxygen vacancy clusters to facilitate movement of ions, thereby imparting improved ionic conductivity to the cathode. In the present specification, the ordered double perovskite refers to a crystal lattice structure in which the A-site or B-site ions are substituted with two or more elements in a general unordered simple perovskite in the form of ABO ₃ .

FIG. 3 is a schematic diagram illustrating a case in which some atoms are substituted in a double-layer perovskite crystal structure constituting the catalyst body applied to the anode of FIG. 1 according to an embodiment of the present invention.

As shown in FIG. 3, the double-layer perovskite structure is a crystal lattice structure in which two or more elements are regularly arranged at the A-site, and may have a formula of AA'B ₂ O _{5 +δ} . Specifically, in the lanthanide compound having a double-layer perovskite structure, the stacking permutation of [BO ₂ ]-[AO]-[BO ₂ ]-[A'O] may be repeated along the c-axis. For example, B may be cobalt (Co), A may be a lanthanide including praseodymium (Pr) or the like, and A′ may be barium (Ba). In addition, part of the barium may be substituted with strontium (Sr), and a part of the cobalt may be substituted with iron (Fe). When this substitution occurs, the double-layer perovskite structure is AA'B _{2 -} may have the formula of _{x B 'x O 5 + δ} , for example, PrBa _{0. 5} Sr _{0 . 5} Co _{2 - x} Fe _x O _{5 +δ} may have a formula.

The catalyst body according to the technical idea of the present invention may be used as a catalyst body for a solid oxide water electrolysis cell, and may be a catalyst body included in an electrode for oxygen generation reaction of the solid oxide water electrolysis cell. The catalyst body according to an embodiment of the present invention may include a compound of Formula 1 below.

<Formula 1>

PrBa _{0 . 5} Sr _{0 . 5} Co _{2 - x} Fe _x O _{5 +δ}

In Formula 1, x is a number greater than 0 and less than or equal to 1.0, and δ is a positive number less than or equal to 1, which is a value that makes the compound of Formula 1 electrically neutral. The δ represents interstitial oxygen in the following double-layer perovskite structure, and the value of δ may be determined according to a specific crystal structure.

PrBa ₀ of Formula 1 above _{. 5} Sr _{0 . 5} Co _{2 - x} Fe _x O _{5 + δ} compound is, for example, the above and x may comprise a compound having a range of more to 1.0 or less 0.25, for example, the range of the x is less than 0.4 more than 0.8 Eggplants may contain compounds.

PrBa ₀ of Formula 1 above _{. 5} Sr _{0 . 5} Co _{2 - x} Fe _x O _{5 +δ} compound is, for example, PrBa ₀ of Formula 1 _{. 5} Sr _{0 . 5} Co _{2 - x} Fe _x O _{5 +δ} compound is PrBa _{0 . 5} Sr _{0 . 5} Co _{1 . 75} Fe _{0 . 25} O _{5 +δ} compound, PrBa _0.5 Sr _0.5 Co _1.6 Fe _0.4 O _5+δ compound, PrBa _{0 . 5} Sr _{0 . 5} Co _{1 . 5} Fe _{0 . 5} O _{5 +δ} compound, PrBa _0.5 Sr _0.5 Co _1.25 Fe _0.75 O _5+δ compound, PrBa _{0 . 5} Sr _{0 . 5} Co _{1 . 2} Fe _{0 . 8} O _{5 +δ} compound, or PrBa _0.5 Sr _0.5 Co ₁ Fe ₁ O _{5 +δ} compound may be included.

The catalyst body according to an embodiment of the present invention may include a compound represented by Formula 2 below.

<Formula 2>

LnBa _a Sr _b Co _{2 - x} Fe _x O _{5 +δ}

In Formula 2, Ln is neodymium (Nd), praseodymium (Pr), samarium (Sm), gadolinium (Gd), europium (Eu), terbium (Tb), erbium (Er), or a mixture thereof, and a and b is a number greater than 0 and less than 1, satisfies a+b=1, x is a number greater than 0 and less than 1.0, and δ is a positive number less than or equal to 1, which is a value that makes the compound of Formula 1 electrically neutral.

Hereinafter, a method of manufacturing a catalyst body according to an embodiment of the present invention will be described.

4 is a flow chart illustrating a method of manufacturing a solid oxide electrolytic cell according to an embodiment of the present invention.

The catalyst body applied to the solid oxide water electrolysis cell may be prepared by the following method. As an example of the catalyst body, a method of preparing a catalyst body including the compound of Formula 2, specifically a PrBa _0.5 Sr _0.5 Co _1.5 Fe _0.5 O _5+δ compound will be described. However, the technical idea of the present invention is not limited thereto.

Referring to FIG. 4, in the method of manufacturing the catalyst body (S100), forming a mixture by mixing a plurality of metal precursors (S110), calcining the mixture (S120), reducing the calcined mixture (S130), and annealing the reduced mixture to form a catalyst body having a perovskite crystal structure material (S140).

The step (S110) of forming a mixture by mixing the plurality of metal precursors may be performed as follows.

First, a plurality of metal precursors are mixed to match the composition of the desired perovskite crystal structure material, for example, the PrBa _0.5 Sr _0.5 Co _1.5 Fe _0.5 O _5+δ compound. Such mixing may be performed using a dry method or may be performed using a wet method of mixing metal precursors in a solvent. Examples of the plurality of metal precursors may include nitrides, oxides, halides, etc., respectively, as Pr, Ba, Sr, Co, and Fe, which are metal components constituting the catalyst body, but are not limited thereto.

Water may be used as a solvent in the wet method, but is not limited thereto. Any one capable of dissolving or mixing the metal precursors may be used without limitation. For example, lower alcohols having a total carbon number of 5 or less, such as methanol, ethanol, 1-propanol, 2-propanol, and butanol; Acidic solutions such as nitric acid, hydrochloric acid, sulfuric acid, and citric acid; water; Organic solvents such as toluene, benzene, acetone, diethyl ether, and ethylene glycol; And the like can be used alone or in combination. The mixing process may be performed at a temperature in the range of, for example, about 100°C to about 200°C. The mixing process may be performed for about 1 hour to about 12 hours while stirring so that the metal precursors are sufficiently mixed. After passing through the mixing process, ultra-fine solids can be obtained through the spontaneous combustion process. The mixing process, removal of the solvent, and addition of additives necessary for this are well known, for example, by the glycine-nitrate process or the pechini method, and thus are not detailed here.

The step of calcining the mixture (S120) is in an air atmosphere, for example at a temperature in the range of about 800°C to about 1300°C, for example at a temperature in the range of about 900°C to about 1000°C, for example about 950 It can be carried out for about 1 hour to about 12 hours at a temperature of °C.

The step of reducing the calcined mixture (S130) is in a reducing gas atmosphere, for example, at a temperature in the range of about 700°C to about 900°C, for example, at a temperature of about 800°C, about 1 hour to about 12 hours Can be performed during. The reducing gas may include all kinds of gases that reduce the calcined mixture, and may include, for example, hydrogen gas.

In the step of annealing the reduced mixture to form a catalyst body (S140), in an oxidizing gas atmosphere, for example, in an air atmosphere or an oxygen atmosphere, for example, at a temperature in the range of about 550°C to about 700°C, for example For example, at a temperature in the range of about 600° C. to about 650° C., for example, at a temperature of 650° C., it may be performed for about 1 hour to about 12 hours. The oxidizing gas may include all kinds of gases that oxidize the reduced mixture, and may include, for example, air (a mixture of nitrogen and oxygen) or oxygen gas.

5 is a graph measuring the oxygen generation activity of the catalyst body applied to the solid oxide water electrolysis cell according to an embodiment of the present invention.

In FIG. 5, "PBSC" is a case in which iron is not included, and PrBa _{0 . 5} Sr _{0 . 5} Co ₂ O _{5 +δ} compound, "PBSCF0.25" is PrBa _{0 . 5} Sr _{0 . 5} Co _{1 . 75} Fe _{0 . 25} O _{5 +δ} compound, "PBSCF0.5" is PrBa _0.5 Sr _0.5 Co _1.5 Fe _0.5 O _5+δ compound, "PBSCF0.75" is PrBa _{0 . 5} Sr _{0 . 5} Co _{1 . 25} Fe _{0 . 75} O _{5 +δ} compound, or “PBSCF1” is PrBa _{0 . 5} Sr _{0 . 5} Co ₁ Fe ₁ O _{5 +δ} compound. Oxygen generation activity was measured by the method of measuring a rotating ring disk electrode by loading the catalyst body onto a glossy carbon electrode in 0.1 M KOH electrolyte.

Referring to FIG. 5, when the catalyst body contains iron, the amount of current generated under the same voltage is greatly increased. Specifically, in the case of PBSC containing no iron, the oxygen generating activity was the lowest. In the case of PrBa _0.5 Sr _0.5 Co _1.5 Fe _0.5 O _5+d containing 25% iron, the oxygen generating activity was the highest. PrBa ₀ containing 37.5% iron _{. 5} Sr _{0 . 5} Co _{1 . 25} Fe _{0 . 75} O _{5 +d} also showed similar oxygen generation activity. PrBa ₀ containing 50% iron _{. 5} Sr _{0 . 5} Co _{1 . 0} Fe _{1 . In the case of 0} O _{5 + d} and PrBa ₀ containing 12.5% iron _{. 5} Sr _{0 . 5} Co _{1 . 75} Fe _{0 . In} the case of ₂₅ O _{5 + d,} the oxygen generation activity performance was somewhat lower, but the oxygen generation activity performance was still higher than that of PBSC that does not contain iron. Thus the iron to 20% (that _{is, PrBa 0. 5 Sr 0.} 5 Co 1. 6 Fe 0. 4 O 5 + d) to 40% (that _{is, PrBa 0.5 Sr 0.5 Co 1.2 Fe} 0.8 O 5 + d) ranges It is analyzed that the PBSCF containing shows optimal performance in the oxygen evolution reaction.

Table 1 is a table showing the oxygen generation activity at a current density of 10 mA cm ^-1 of the catalyst body.

PBSC PBSCF0.25 PBSCF0.5 PBSCF0.75 PBSCF1 Voltage at 10 mA cm ^-1 (V) 1.610 1.568 1.529 1.544 1.550

Referring to Table 1, the oxygen generation activity of the catalyst body represents a voltage of 1.52 V to 1.570 V at a current density of 10 mA cm ^-1 . PrBa ₀ with the best oxygen generating activity performance _{. 5} Sr _{0 . 5} Co _{1 . 5} Fe _{0 . 5} O _{5 + d} showed the lowest voltage.

According to the results of Figure 5 and Table 1, according to an embodiment of the present invention, the catalyst body can provide excellent performance for the oxygen generation reaction.

As described above, the present invention has been described with reference to specific contents and some embodiments, but it is to be understood that this is only a description presented as a specific example to help a more general understanding of the present invention. The present invention is not limited only to the above-described embodiments, and those of ordinary skill in the field to which the present invention pertains can make various modifications and variations on these embodiments, and such modifications and variations are also within the technical spirit of the present invention. Is covered in.

Accordingly, not only the above-described embodiments and the claims to be described later, but also all equivalents or equivalent modified embodiments of the claims belong to the scope of the inventive concept.

300: solid oxide electrolytic cell, 310: anode, 320: cathode,
330: electrolyte, 340: external power supply,

Claims (15)

A cathode for discharging hydrogen gas formed by decomposing water;
An anode disposed facing the cathode and discharging oxygen gas formed by decomposing the water; And
As a solid oxide electrolytic cell for generating hydrogen and oxygen, comprising an electrolyte disposed between the anode and the cathode,
At least one of the anode and the cathode comprises a catalyst body,
The catalyst body comprises a compound of the following formula (1), a solid oxide water electrolysis cell.
<Formula 1>
PrBa _{0 . 5} Sr _{0 . 5} Co _{2 - x} Fe _x O _{5 +δ}
In Formula 1, x is a number in the range of more than 0 to 1.0 or less, and δ is a positive number of 1 or less, and is a value that makes the compound of Formula 1 electrically neutral. The method according to claim 1,
In the catalyst body, x is a number in the range of 0.25 or more to 1 or less, a solid oxide aqueous electrolysis cell. The method according to claim 1,
In the catalyst body, the x is a number in the range of more than 0.4 to less than 0.8, a solid oxide electrolysis cell. The method according to claim 1,
The catalyst body is PrBa _{0 . 5} Sr _{0 . 5} Co _{1 . 75} Fe _{0 . 25} O _{5 +δ} compound, PrBa _{0 . 5} Sr _{0 . 5} Co _{1 . 6} Fe _{0 . 4} O _{5 +δ} compound, PrBa _{0 . 5} Sr _{0 . 5} Co _{1 . 5} Fe _{0 . 5} O _{5 +δ} compound, PrBa _{0 . 5} Sr _{0 . 5} Co _{1 . 25} Fe _{0 . 75} O _{5 +δ} compound, PrBa _0.5 Sr _0.5 Co _1.2 Fe _0.8 O _5+δ compound, or PrBa _{0 . 5} Sr _{0 . 5} Co ₁ Fe ₁ O _{5 +δ} compound containing, solid oxide water electrolysis cell. The method according to claim 1,
The oxygen generation activity of the catalyst body represents a voltage of 1.52 V to 1.570 V at a current density of 10 mA cm ^-1 , a solid oxide water electrolysis cell. A cathode for discharging hydrogen gas formed by decomposing water;
An anode disposed facing the cathode and discharging oxygen gas formed by decomposing the water; And
As a solid oxide electrolytic cell for generating hydrogen and oxygen, comprising an electrolyte disposed between the anode and the cathode,
At least one of the anode and the cathode comprises a catalyst body,
The catalyst body comprises a compound of the following formula (2), a solid oxide water electrolysis cell.
<Formula 2>
LnBa _a Sr _b Co _{2 - x} Fe _x O _{5 +δ}
In Formula 2, Ln is neodymium (Nd), praseodymium (Pr), samarium (Sm), gadolinium (Gd), europium (Eu), terbium (Tb), erbium (Er), or a mixture thereof, and a and b is a number greater than 0 and less than 1, satisfies a+b=1, x is a number greater than 0 and less than 1.0, and δ is a positive number less than or equal to 1, which is a value that makes the compound of Formula 1 electrically neutral. The method of claim 6,
In the catalyst body, x is a number in the range of 0.25 or more to 1 or less, a solid oxide aqueous electrolysis cell. The method of claim 7,
In the catalyst body, the x is a number in the range of more than 0.4 to less than 0.8, a solid oxide electrolysis cell. Mixing a plurality of metal precursors to form a mixture;
Calcining the mixture;
Reducing the calcined mixture; And
Annealing the reduced mixture to form a catalyst body including the compound of Formula 1 below.
<Formula 1>
PrBa _{0 . 5} Sr _{0 . 5} Co _{2 - x} Fe _x O _{5 +δ}
In Formula 1, x is a number in the range of more than 0 to 1.0 or less, and δ is a positive number of 1 or less, which is a value that makes the compound of Formula 1 electrically neutral. The method of claim 9,
In the catalyst body, the x is a number in the range of 0.25 or more to 1 or less, the method of producing a solid oxide electrolytic cell. The method of claim 10,
In the catalyst body, the x is a number in the range of more than 0.4 to less than 0.8, the method of producing a solid oxide electrolytic cell. The method of claim 9,
The catalyst body is PrBa _{0 . 5} Sr _{0 . 5} Co _{1 . 75} Fe _{0 . 25} O _{5 +δ} compound, PrBa _{0 . 5} Sr _{0 . 5} Co _{1 . 6} Fe _{0 . 4} O _{5 +δ} compound, PrBa _{0 . 5} Sr _{0 . 5} Co _{1 . 5} Fe _{0 . 5} O _{5 +δ} compound, PrBa _{0 . 5} Sr _{0 . 5} Co _{1 . 25} Fe _{0 . 75} O _{5 +δ} compound, PrBa _0.5 Sr _0.5 Co _1.2 Fe _0.8 O _5+δ compound, or PrBa _{0 . 5} Sr _{0 . 5} Co ₁ Fe ₁ O _{5 + δ A} method for producing a solid oxide electrolytic cell containing a compound. As a catalyst body contained in an electrode for oxygen generation reaction of a solid oxide aqueous electrolysis cell,
The catalyst body is a catalyst body for a solid oxide aqueous electrolytic cell comprising a compound of the following formula (1).
<Formula 1>
PrBa _{0 . 5} Sr _{0 . 5} Co _{2 - x} Fe _x O _{5 +δ}
In Formula 1, x is a number in the range of more than 0 to 1.0 or less, and δ is a positive number of 1 or less, which is a value that makes the compound of Formula 1 electrically neutral. The method of claim 13,
In the catalyst body, the x is a number in the range of 0.25 or more to 1 or less, the catalyst body for a solid oxide aqueous electrolysis cell. The method of claim 14,
In the catalyst body, x is a number in the range of more than 0.4 to less than 0.8, the catalyst body for a solid oxide aqueous electrolysis cell.

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