KR20240072592A - Electrochemical ammonia synthesis module and electrochemical ammonia synthesis method using the same - Google Patents

Abstract

The present invention relates to an electrochemical ammonia synthesis module and an electrochemical ammonia synthesis method using the same. More specifically, the electrochemical ammonia synthesis module according to the present invention is an ion separation membrane using a conductive ceramic composite electrolyte containing an oxygen ion conductor and a proton conductor. By applying it, it has excellent selective ion permeability to oxygen ions and hydrogen ions, lowering the operating temperature and promoting N ₂ activation, thereby increasing the rate of ammonia synthesis. In addition, the separation process can be relatively simplified due to the gaseous product, and there is an advantage in that ammonia can be produced using only water and nitrogen. This can be applied to various processes and designs, including the actual industrial production process of energy ceramic materials, parts, stacks, and systems.

Description

Electrochemical ammonia synthesis module and electrochemical ammonia synthesis method using the same {Electrochemical ammonia synthesis module and electrochemical ammonia synthesis method using the same}

The present invention relates to an electrochemical ammonia synthesis module and an electrochemical ammonia synthesis method using the same.

Due to the demand for green ammonia and the importance of carbon neutrality, electrochemical green ammonia production technology based on renewable energy is very important in terms of industrial applicability. Electrochemical ammonia synthesis can be largely performed under low-temperature and commercial conditions and under high-temperature synthesis conditions. First, electrochemical ammonia synthesis under low temperature and normal pressure conditions is difficult to commercialize due to problems with low N ₂ activation, ammonia production, and Faradaic efficiency.

On the other hand, ammonia synthesis at high temperature can use an electrolyte with conductivity for oxygen ions to synthesize green ammonia using nitrogen and water as reactants. However, solid electrolytes that are permeable to oxygen ions must be operated at high temperatures, so they have the disadvantage of being expensive to manufacture and having to consider stability due to high temperatures.

Therefore, these existing methods still have limitations in increasing the synthesis speed of ammonia while lowering the operating temperature, so new research and development is needed to improve this.

Korean Patent No. 10-1392828

In order to solve the above problems, the purpose of the present invention is to provide an electrochemical ammonia synthesis module with low operating temperature and high ammonia synthesis rate.

Another object of the present invention is to provide a method for electrochemical ammonia synthesis.

The present invention relates to an ion separation membrane comprising a conductive ceramic composite electrolyte containing an oxygen ion conductor and a proton conductor; An anode formed on one side of the ion separation membrane; and a reduction electrode formed on the other side of the ion separation membrane. It provides an electrochemical ammonia synthesis module including a.

In addition, the present invention is an electrochemical ammonia synthesis method using an ammonia synthesis module including an oxidation electrode, an ion separation membrane, and a reduction electrode. Electrons (e ^- ), hydrogen ions (H ⁺ ), and oxygen gas are generated from the anode part including the oxidation electrode. generating (O ₂ ); passing the hydrogen ions through an ion separation membrane disposed between the oxidation electrode and the reduction electrode; And a step of producing ammonia gas (NH ₃ gas) or ammonium ion (NH ₄ ⁺ ) by allowing the hydrogen ions that have passed through the ion separation membrane to reach the cathode portion including the cathode, wherein the ion separation membrane produces oxygen ions. An electrochemical ammonia synthesis method comprising a conductor and a proton conductor is provided.

The electrochemical ammonia synthesis module according to the present invention has excellent selective ion permeability to oxygen ions and hydrogen ions by applying a conductive ceramic composite electrolyte containing an oxygen ion conductor and a proton conductor as an ion separation membrane, thereby lowering the operating temperature and promoting N ₂ activation. It can accelerate the rate of ammonia synthesis. In addition, the separation process can be relatively simplified due to the gaseous product, and there is an advantage in that ammonia can be produced using only water and nitrogen. This can be applied to various processes and designs, including the actual industrial production process of energy ceramic materials, parts, stacks, and systems.

The effects of the present invention are not limited to the effects mentioned above. The effects of the present invention should be understood to include all effects that can be inferred from the following description.

Figure 1 schematically shows the ammonia synthesis process of the electrochemical ammonia synthesis module according to the present invention.

Hereinafter, the present invention will be described in more detail by way of example.

The present invention relates to an electrochemical ammonia synthesis module and an electrochemical ammonia synthesis method using the same.

As previously explained, the existing electrochemical ammonia synthesis is difficult to commercialize due to low N ₂ activation, ammonia production, and Faraday efficiency problems under low temperature and normal pressure conditions, and high manufacturing costs and stability problems due to high temperature under high temperature conditions. There were limitations that had to be taken into consideration.

Accordingly, in the present invention, by applying a conductive ceramic composite electrolyte containing an oxygen ion conductor and a proton conductor as an ion separation membrane, ammonia is removed at a low operating temperature due to selective ion permeability to not only oxygen ions (O ^2- ) but also hydrogen ions (H ⁺ ). There is an advantage in improving synthesis yield. In addition, by using only water and nitrogen as reactants, equipment equipment and process are simple, and process stability is excellent. This can be applied to various processes and designs, including the actual industrial production process of energy ceramic materials, parts, stacks, and systems.

Specifically, the present invention relates to an ion separation membrane comprising a conductive ceramic composite electrolyte containing an oxygen ion conductor and a proton conductor; An anode formed on one side of the ion separation membrane; and a reduction electrode formed on the other side of the ion separation membrane. It provides an electrochemical ammonia synthesis module including a.

The oxygen ion conductor is an electrolyte having oxygen ion conductivity, and specific examples include YSZ (Y ₂ O ₃ stabilized-Zr0 _2, yttria-stabilized zirconia), SSZ (Sc ₂ O ₃ stabilized-Zr0 ₂ , scandia-stabilized zirconia), It may be at least one selected from the group consisting of SDC (Sm ₂ O ₃ doped-Ce0 ₂ , Sm-doped ceria), GDC (Gd ₂ O ₃ doped-Ce0 ₂ , Gd-doped ceria), and LaGaO ₃ , preferably It may be one or more selected from the group consisting of YSZ(Y ₂ O ₃ stabilized-Zr0 ₂ ), SSZ(Sc ₂ O ₃ stabilized-Zr0 ₂ ) and LaCaO ₃ , and most preferably YSZ(Y ₂ O ₃ stabilized-Zr0 ₂ ), LaCaO ₃ or a mixture thereof.

The oxygen ion conductor requires a high operating temperature of 700°C or higher to ensure oxygen ion conductivity when used alone as an ion separation membrane. In this case, the synthesized ammonia may be decomposed, so the operating temperature must be lowered. In the present invention, the operating temperature can be significantly lowered by simultaneously using the oxygen ion conductor as a proton conductor, which is advantageous for ammonia synthesis as it can secure high ionic conductivity below 600°C.

The proton conductor has high ionic conductivity even at lower temperatures than the oxygen ion conductor, and can significantly improve ammonia synthesis yield at low operating temperatures. The proton conductor is a ceramic compound, and specific examples include the proton conductor being one selected from the group consisting of BaCeO ₃ , BaZrO ₃ , Ba(ZrY)O ₃ , Ba(ZrCeY)O ₃ , SrCeO ₃ , CaZrO ₃ and SrZrO ₃ It may be any of the above perovskite structural compounds, preferably at least one selected from the group consisting of Ba(ZrCeY)O ₃ , BaZrO ₃ , BaCeO ₃ , SrCeO ₃ and CaZrO ₃ , and most preferably Ba(ZrCeY )O ₃ may be.

The conductive ceramic composite electrolyte may be a mixture of an oxygen ion conductor and a proton conductor in a weight ratio of 30:70 to 70:30, preferably 40:60 to 60:40, and most preferably 50:50. In particular, if the content of the oxygen ion conductor exceeds 70 weight ratio, the operating temperature during ammonia synthesis is high and the synthesized ammonia may be decomposed. Conversely, if the content of the oxygen ion conductor is less than 30 weight ratio, the content of the oxygen ion conductor is small, so the synthesis yield of ammonia is not at the expected level. You may not be able to reach it.

The ion separation membrane has excellent selective ion permeability by being conductive to oxygen ions and hydrogen ions, thereby improving the synthesis yield of ammonia. In addition, the ion separation membrane is a mixture of the oxygen ion conductor and the proton conductor in an appropriate amount, so that the operating temperature can be lowered and the synthesis rate of ammonia can be rapidly increased.

The ion separation membrane may have a thickness of 1 to 500 ㎛, preferably 5 to 300 ㎛, more preferably 8 to 200 ㎛, and most preferably 10 to 100 ㎛. At this time, if the thickness of the ion separator is less than 1 ㎛, durability and cell manufacturing may be difficult. Conversely, if it is more than 500 ㎛, the ion conduction path becomes too long, so ammonia synthesis takes a long time, and ion transfer is not effective, so ammonia The synthesis yield may decrease.

The anode may include one or more metals selected from the group consisting of Ir, Pt, Ti, and Ni, and a first catalyst, and preferably may include Pt, Ti, or a mixture thereof, and a first catalyst, Most preferably, it may include a Pt/Ti mixture and a first catalyst.

The first catalyst of the oxidation electrode is [(La _1-x Sr _x )CoO _3-δ ](LSC), [(La _1-x Sr _x )FeO _3-δ ] (LSF), [(La _1-x Sr _x )(Co _1-y Fe _y )O _3-δ ](LSCF), [(La _x Sr _1-x )TiO _3-δ ](LST), [(Ba _x Sr _1-x )(Co _y Fe _1-y )O ₃ ](BSCF), LaCoO ₃ , LaNiO ₃ , (La _x Sr _1-x )VO ₃ , Ca(V _x Mo _1-x )O ₃ , [Ba(Zr _x Ce _y Y _{1 -(x+y)} )O ₃ ](BZCY) and [Pr(Ba _1-x Sr _x )(Fe _2-y Ge _y )O ₆ ](PBSFG) where 0<x<1, 0<y <1, 0<δ<3, preferably 0<x<0.7, 0<y<0.7, 0<δ<3).

The cathode may be a conductive catalyst, a second catalyst, or a mixture thereof, and preferably may be a mixture of a conductive catalyst and a second catalyst.

The conductive catalyst is the same as the first catalyst, specifically [(La _1-x Sr _x )CoO _3-δ ] (LSC), [(La _1-x Sr _x )FeO _3-δ ] (LSF), [(La _1-x Sr _x )(Co _1-y Fe _y )O _3-δ ](LSCF), [(La _x Sr _1-x )TiO _3-δ ](LST), [(Ba _x Sr _{1 -x} )(Co _y Fe _1-y )O ₃ ](BSCF), LaCoO ₃ , LaNiO ₃ , (La _x Sr _1-x )VO ₃ , Ca(V _x Mo _1-x )O ₃ , [Ba( Zr _x Ce _y Y _{1-(x+y) ) O 3} ](BZCY) and [Pr(Ba _{1 -x Sr} <1, 0<y<1, 0<δ<3, preferably 0<x<0.7, 0<y<0.7, 0<δ<3).

The second catalyst of the reduction electrode may be one or more selected from the group consisting of V, Cr, Mn, Fe, Co, Ni, Cu, Nb, Mo, Ru, Rh, Pd, Ag, Au, and Bi.

Preferably, although not explicitly described in the following examples or comparative examples, in the electrochemical ammonia synthesis method according to the present invention, ammonia is synthesized under each of the following six conditions, and then the ammonia production rate and ion The ionic conductivity and durability of the separator can be measured.

As a result, unlike other conditions and other numerical ranges, when all of the following conditions were satisfied, the ammonia production rate was significantly improved compared to the separation membrane using either the oxygen ion conductor or the proton conductor, and the ion conductivity and It was confirmed that durability was excellent and that long-term stability was improved as a result.

① The oxygen ion conductor is YSZ (Y ₂ O ₃ stabilized-Zr0 ₂ ), LaCaO ₃ or a mixture thereof, ② The proton conductor is at least one selected from the group consisting of BaCeO ₃ , SrCeO ₃ and CaZrO ₃ , ③ The conductive ceramic composite electrolyte is a mixture of an oxygen ion conductor and a proton conductor in a weight ratio of 40:60 to 60:40, ④ the ion separator has a thickness of 8 to 200 ㎛, ⑤ the oxidizing electrode is Pt, Ti or their It includes a mixture and a first catalyst, and ⑥ the cathode may include a catalyst composed of a mixture of a conductive catalyst and a second catalyst.

However, if any of the six conditions above are not met, the ammonia production rate may be low, the ion conductivity and durability of the ion separator will also be drastically reduced, and long-term stability will be poor.

As such, the electrochemical ammonia synthesis module of the present invention has excellent selective ion permeability to oxygen ions and hydrogen ions by applying a conductive ceramic composite electrolyte containing an oxygen ion conductor and a proton conductor as an ion separation membrane, thereby lowering the operating temperature and N ₂ By promoting activation, the rate of ammonia synthesis can be increased. In addition, the separation process can be relatively simplified due to the gaseous product, and there is an advantage in that ammonia can be produced using only water and nitrogen. This can be applied to various processes and designs, including the actual industrial production process of energy ceramic materials, parts, stacks, and systems.

In addition, the present invention is an electrochemical ammonia synthesis method using an ammonia synthesis module including ^{an oxidation} electrode, an ion separation membrane, and a reduction electrode. Generating gas (O ₂ ); passing the hydrogen ions through an ion separation membrane disposed between the oxidation electrode unit and the reduction electrode unit; And a step of producing ammonia gas (NH ₃ gas) or ammonium ion (NH ₄ ⁺ ) by allowing the hydrogen ions that have passed through the ion separation membrane to reach the cathode portion including the cathode, wherein the ion separation membrane produces oxygen ions. An electrochemical ammonia synthesis method comprising a conductor and a proton conductor is provided.

Figure 1 schematically shows the ammonia synthesis process of the electrochemical ammonia synthesis module according to the present invention. Referring to FIG. 1, it is shown that water is decomposed on the anode surface of the anode part to generate electrons and hydrogen ions, and oxygen gas is generated. In addition, on the cathode surface of the cathode part, ammonia is synthesized as nitrogen gas and water are decomposed, and in the ion separation membrane located in the middle, hydrogen ions move from the anode electrode to the cathode electrode, and oxygen ions move from the anode electrode to the cathode electrode. shows that

The oxygen ion conductor is YSZ (Y ₂ O ₃ stabilized-Zr0 _2, yttria-stabilized zirconia), SSZ (Sc ₂ O ₃ stabilized-Zr0 ₂ , scandia-stabilized zirconia), SDC (Sm ₂ O ₃ doped-Ce0 ₂ , It may be one or more selected from the group consisting of Sm-doped ceria), GDC (Gd ₂ O ₃ doped-Ce0 ₂ , Gd-doped ceria), and LaGaO ₃ , and preferably YSZ (Y ₂ O ₃ stabilized-Zr0 ₂ ) , SSZ (Sc ₂ O ₃ stabilized-Zr0 ₂ ) and LaCaO ₃ , and most preferably YSZ (Y ₂ O ₃ stabilized-Zr0 ₂ ), LaCaO ₃ or a mixture thereof. there is.

The proton conductor may be one or more perovskite structural compounds selected from the group consisting of BaCeO ₃ , BaZrO ₃ , Ba(ZrY)O ₃ , Ba(ZrCeY)O ₃ , SrCeO ₃ , CaZrO ₃ and SrZrO ₃ , Preferably, it may be one or more selected from the group consisting of Ba(ZrCeY)O ₃ , BaZrO ₃ , BaCeO ₃ , SrCeO ₃ and CaZrO ₃ , and most preferably Ba(ZrCeY)O ₃ .

The conductive ceramic composite electrolyte may be a mixture of an oxygen ion conductor and a proton conductor in a weight ratio of 30:70 to 70:30, preferably 40:60 to 60:40, and most preferably 50:50.

In the step of producing ammonia gas (NH ₃ gas) or ammonium ions (NH ₄ ⁺ ), the concentration of ammonia may vary depending on operating conditions such as the size of the electrode and the number of electrodes used.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to the following examples.

Example 1: Preparation of electrochemical ammonia module

YSZ (Y ₂ O ₃ stabilized-Zr0 ₂ ) as an oxygen ion conductor and BaCeO ₃ as a proton conductor were added to 100 parts by weight of a slurry containing a mixture of polyvinyl butyral, an organic binder, and ethanol and propyl acetate, as solvents. A conductive ceramic composite electrolyte solution was prepared by mixing at a weight ratio of 50:50 and adding a total of 100 parts by weight. Next, the conductive ceramic electrolyte slurry was coated on the release surface using a tape casting method, and then a green sheet was manufactured, laminated, and sintered to prepare an ion separation membrane with a thickness of 10 to 100 ㎛.

Next, an electrochemical ammonia synthesis module was manufactured by placing the ion separator between the anode and the cathode electrode and brush painting it using a conventional method. At this time, a Pt/Ti mixture in which Pt was electrochemically deposited was used as an oxidizing electrode in the reactor, and LaCoO ₃ was used as a reducing electrode. Additionally, 0.1 M Na ₂ SO ₄ was used as the oxidizing electrode solution, and 0.05 M LiClO ₄ was used as the reducing electrode solution.

Comparative Example 1: Electrochemical ammonia module production using oxygen ion conductor

A conductive ceramic electrolyte solution was prepared by mixing 100 parts by weight of LaGaO _3, an oxygen ion conductor, with 100 parts by weight of the slurry containing the organic binder and solvent of Example 1. Next, the conductive ceramic electrolyte slurry was coated on the release surface using a tape casting method, and then a green sheet was manufactured, laminated, and sintered to prepare an ion separation membrane with a thickness of 10 to 100 ㎛.

Next, an electrochemical ammonia synthesis module was manufactured by brush painting the anode and cathode electrodes on the ion separation membrane by a conventional method.

Comparative Example 2: Preparation of electrochemical ammonia module using proton ion conductor

A conductive ceramic electrolyte solution was prepared by mixing 100 parts by weight of Ba(ZrCeY)O ₃ , a proton ion conductor, with 100 parts by weight of the slurry containing the organic binder and solvent of Example 1.

Next, the conductive ceramic electrolyte slurry was coated on the release surface using a tape casting method, and then a green sheet was manufactured, laminated, and sintered to prepare an ion separation membrane with a thickness of 10 to 100 ㎛.

Next, an electrochemical ammonia synthesis module was manufactured by brush painting the anode and cathode electrodes on the ion separation membrane using a conventional method.

Experimental Example 1: Electrochemical ammonia synthesis

Ammonia synthesis was performed according to a conventional ammonia synthesis method using the electrochemical ammonia synthesis module prepared in Example 1 and Comparative Examples 1 and 2. Ammonia synthesis was performed by applying an electrochemical reduction voltage in an atmosphere where nitrogen gas was sufficiently injected at room temperature and pressure for more than 30 minutes, and the resulting ammonia concentration was measured.

The obtained synthetic concentration of ammonia was measured using the indophenol blue method using an indophenol indicator and a UV-vis optical meter. For accurate measurement, cation chromatography (IC) and ¹ H using ¹⁵ N ₂ isotope nitrogen gas were used. The synthesized concentration of ammonia was verified by measuring ¹⁵ NH ₄ ⁺ ions using NMR (nuclear magnetic resonance spectrometry).

As a result ^, when the oxygen ion conductor of Comparative Example 1 was used ^, it was 6.0 x 10 ^-11 mol/cm ² ·sec ¹ , and when the proton conductor of Comparative Example 2 was used ^, the Ammonia production rates are shown, respectively.

On the other hand, when both the oxygen ion conductor and the proton conductor of Example 1 were included, an ammonia production rate of 2.0 x 10 ^-10 mol/cm ² ·sec ¹ was shown, which was further improved compared to Comparative Examples 1 and 2. Through this, it was found that using an ion separation membrane containing both the oxygen ion conductor and the proton conductor had a lower operating temperature and excellent ammonia production rate compared to the existing ammonia synthesis process.

Claims (14)

An ion separation membrane containing a conductive ceramic composite electrolyte containing an oxygen ion conductor and a proton conductor;
An anode formed on one side of the ion separation membrane; and
a reduction electrode formed on the other side of the ion separation membrane;
Electrochemical ammonia synthesis module comprising:
According to paragraph 1,
The oxygen ion conductor is YSZ (Y ₂ O ₃ stabilized-Zr0 _2, yttria-stabilized zirconia), SSZ (Sc ₂ O ₃ stabilized-Zr0 ₂ , scandia-stabilized zirconia), SDC (Sm ₂ O ₃ doped-Ce0 ₂ , An electrochemical ammonia synthesis module that is at least one selected from the group consisting of Sm-doped ceria), GDC (Gd ₂ O ₃ doped-Ce0 ₂ , Gd-doped ceria), and LaGaO ₃ .
According to paragraph 1,
The proton conductor is one or more perovskite structural compounds selected from the group consisting of BaCeO ₃ , BaZrO ₃ , Ba(ZrY)O ₃ , Ba(ZrCeY)O ₃ , SrCeO ₃ , CaZrO ₃ and SrZrO ₃ Chemical ammonia synthesis module.
According to paragraph 1,
The electrochemical ammonia synthesis module wherein the conductive ceramic composite electrolyte is a mixture of an oxygen ion conductor and a proton conductor in a weight ratio of 30:70 to 70:30.
According to paragraph 1,
The electrochemical ammonia synthesis module wherein the ion separation membrane has a thickness of 1 to 500 ㎛.
According to paragraph 1,
The electrochemical ammonia synthesis module wherein the oxidizing electrode includes at least one metal selected from the group consisting of Ir, Pt, Ti, and Ni and a first catalyst.
According to clause 6,
The first catalyst is [(La _1-x Sr _x )CoO _3-δ ](LSC), [(La _1-x Sr _x )FeO _3-δ ] (LSF), [(La _1-x Sr _x ) (Co _1-y Fe _y )O _3-δ ] (LSCF), [(La _x Sr _1-x )TiO _3-δ ] (LST), [(Ba _x Sr _1-x )(Co _y Fe _{1- y} )O ₃ ](BSCF), LaCoO ₃ , LaNiO ₃ , (La _x Sr _1-x )VO ₃ , Ca(V _x Mo _1-x )O ₃ , [Ba(Zr _x Ce _y Y _{1-(x) +y)} )O ₃ ] (BZCY), and [Pr(Ba _1-x Sr _x )(Fe _2-y Ge _y )O ₆ ] (PBSFG), where 0<x<1, 0<y<1 , 0<δ<3.) An electrochemical ammonia synthesis module that is one or more types selected from the group consisting of.
According to paragraph 1,
The electrochemical ammonia synthesis module wherein the cathode includes a conductive catalyst and a second catalyst.
According to clause 8,
The conductive catalyst is the same as the first catalyst,
The electrochemical ammonia synthesis module wherein the second catalyst is one or more selected from the group consisting of V, Cr, Mn, Fe, Co, Ni, Cu, Nb, Mo, Ru, Rh, Pd, Ag, Au and Bi.
According to paragraph 1,
The oxygen ion conductor is YSZ (Y ₂ O ₃ stabilized-Zr0 ₂ ), LaCaO ₃ or a mixture thereof,
The proton conductor is at least one selected from the group consisting of BaCeO ₃ , SrCeO ₃ and CaZrO ₃ ,
The conductive ceramic composite electrolyte is a mixture of oxygen ion conductor and proton conductor in a weight ratio of 40:60 to 60:40,
The ion separation membrane has a thickness of 8 to 200 ㎛,
The oxidizing electrode includes Pt, Ti, or a mixture thereof, and a first catalyst,
The electrochemical ammonia synthesis module wherein the cathode is a mixture of a conductive catalyst and a second catalyst.
An electrochemical ammonia synthesis method using an ammonia synthesis module including an anode, an ion separation membrane, and a reduction electrode,
Generating electrons (e ^- ), hydrogen ions (H ⁺ ), and oxygen gas (O ₂ ) in the oxidation electrode unit including the oxidation electrode;
passing the hydrogen ions through an ion separation membrane disposed between the oxidation electrode and the reduction electrode; and
A step of producing ammonia gas (NH ₃ gas) or ammonium ion (NH ₄ ⁺ ) by allowing hydrogen ions passing through the ion separation membrane to reach the cathode portion including the cathode,
An electrochemical ammonia synthesis method wherein the ion separation membrane includes an oxygen ion conductor and a proton conductor.
According to clause 11,
The oxygen ion conductor is YSZ (Y ₂ O ₃ stabilized-Zr0 _2, yttria-stabilized zirconia), SSZ (Sc ₂ O ₃ stabilized-Zr0 ₂ , scandia-stabilized zirconia), SDC (Sm ₂ O ₃ doped-Ce0 ₂ , An electrochemical ammonia synthesis method comprising at least one selected from the group consisting of Sm-doped ceria), GDC (Gd ₂ O ₃ doped-Ce0 ₂ , Gd-doped ceria), and LaGaO ₃ .
According to clause 11,
The proton conductor is one or more perovskite structural compounds selected from the group consisting of BaCeO ₃ , BaZrO ₃ , Ba(ZrY)O ₃ , Ba(ZrCeY)O ₃ , SrCeO ₃ , CaZrO ₃ and SrZrO ₃ Chemical ammonia synthesis method.
According to clause 11,
The conductive ceramic composite electrolyte is an electrochemical ammonia synthesis method in which an oxygen ion conductor and a proton conductor are mixed in a weight ratio of 30:70 to 70:30.