WO2019182207A1

WO2019182207A1 - Lithium superionic conductor-based ammonia synthesis method

Info

Publication number: WO2019182207A1
Application number: PCT/KR2018/009908
Authority: WO
Inventors: 윤형철; 유충열; 김종남; 김귀용; 한종인
Original assignee: 한국에너지기술연구원
Priority date: 2018-03-23
Filing date: 2018-08-28
Publication date: 2019-09-26
Also published as: KR102128228B1; KR20190111480A

Abstract

The present invention relates to a lithium superionic conductor-based ammonia synthesis method. The synthesis method can synthesize ammonia at a high yield by optimizing synthesis conditions of ammonia required for respective steps.

Description

Lithium Superion Conductor Based Ammonia Synthesis Method

The present invention relates to ammonia synthesis, and to a method for synthesizing ammonia based on lithium superion conductors.

Ammonia is a hydrogen and nitrogen compound with the chemical formula NH ₃ , present in a gaseous state with an irritating odor at room temperature. It contains a small amount in the atmosphere, a small amount in natural water, and may be generated and present in the process of decomposing bacteria nitrogen organic matter in the soil.

Ammonia is used as a raw material for various chemical industries, for the production of ammonia water, and as a solvent for ionic substances. In addition, in order to meet the greenhouse gas reduction target to cope with the depletion of oil resources and to respond to climate change, the use of renewable energy is increasing. Renewable energy has local ubiquitous and intermittent problems, so a means of storage and transportation is essential. Ammonia and hydrogen are attracting attention as energy carriers for solving these problems. Hydrogen has limited storage and transport, but ammonia is easier to store and transport than hydrogen because it is liquid at room temperature of 8.5 atm.

The most common method of producing ammonia is the Haber-Bosch process synthesized from hydrogen and nitrogen. In the presence of an iron or ruthenium catalyst, one nitrogen molecule and three hydrogen molecules combine to form two ammonia molecules as shown in Formula 1 below. It is an exothermic process that generates. However, this is a large industrial process but has a low ammonia yield of 10-20% and requires additional energy and hydrogen.

Formula 1

N ₂ + 3H _2- > 2NH ₃ + 100 kJ

In order to overcome the limitations of the Haber-Bosch process, electrochemical ammonia synthesis using ion-conducting oxide electrolytes has been proposed, and electrochemical ammonia synthesis using electrolytes using water and nitrogen as raw materials has been actively studied (Marnellos et al. ). In the electrochemical ammonia synthesis method, an electrolytic cell based on an aqueous electrolyte undergoes a series of processes as shown in the following formula (2), in which water is decomposed at an anode and divided into hydrogen ions and electrons (2-1) and hydrogen. It includes a reaction (2-2) in which ions and electrons reduce nitrogen molecules to produce ammonia. Since the final product of the ammonia electrochemical synthesis method is only ammonia and oxygen, there is no carbon emission.

Formula 2

Oxide electrode _{^{reaction: 3H 2 O → 6H + +}} 3 / 2O 2 + 6e - (2-1)

Reduction electrode _{^{reaction: N 2 + 6H + + 6e}} - → 2NH 3 (2-2)

The main limiting reaction in the electrochemical ammonia synthesis reaction is a step of reducing nitrogen molecules, which are reactions on the reduction electrode, to ammonia, which is caused by the strong triple bond of the nitrogen molecules. In the case of using an aqueous-based electrolyte, the cathode reaction often generates hydrogen instead of the nitrogen reduction reaction. Indeed, current efficiency is known to be less than 1% when using electrolytic based systems (R. Lan et al.).

US Patent No. 7111442 and European Patent No. 972855 relate to an ammonia synthesis apparatus, and discloses an ammonia synthesis apparatus for synthesizing ammonia by using a proton conductive solid oxide as an electrolyte and applying an external current. However, the above patents require the use of a solid oxide electrolyte, which requires a high operating temperature, which is difficult to obtain a high yield since the temperature at which ammonia can be decomposed into hydrogen and nitrogen gas.

US Patent No. 8916123 discloses ammonia synthesis method using an ammonia synthesis cell partitioned into a cathode and an anode by a lithium ion conductor. However, this has a problem in that the ammonia synthesis yield is low due to side reaction between lithium and a solvent or corrosion of a lithium conductor by lithium.

Therefore, there is a need for an energy-friendly ammonia synthesis apparatus with higher yield and lower manufacturing cost.

The present invention has been made to solve the above-mentioned conventional problems, to provide a lithium superion conductor-based ammonia synthesis method that can obtain a high ammonia synthesis yield.

The present inventors have found that the ammonia synthesis method based on lithium superion conductors can be used to optimize the ammonia synthesis conditions required for each step to synthesize ammonia with a high yield, thus completing the present invention.

The present invention is a lithium superion conductor-based ammonia synthesis method, the method comprising the steps of: preparing a lithium thin metal plate on the cathode using an electrochemical cell in which the anode portion and the cathode portion are partitioned by the lithium superion conductor; Washing the lithium thin film metal plate; A step of manufacturing a lithium nitride thin film metal plate for forming lithium nitride (Li ₃ N) on the lithium thin film by heating the lithium thin film metal plate passed through the washing step in a nitrogen atmosphere reactor; And supporting the lithium nitride thin film metal plate in an acid solution to synthesize ammonia, wherein the anode portion includes an anode and an anode solution, and the cathode portion includes a cathode and a cathode solution. The anolyte is an aqueous solution of Li ₂ SO ₄ , and lithium ions passed by the lithium superion conductor are coated on the cathode, and the reduction electrode solution includes a lithium salt, an organic solvent, and an additive. Provide a synthesis method.

The present invention also provides a method for synthesizing ammonia using a lithium superion conductor-based compartmental ammonia synthesizing apparatus, wherein the method is based on a rotary cathode and has a first compartment, a second compartment, and A cylindrical reaction device divided into a third compartment, comprising: placing an anode and a superion conductor in an electrolyte including an additive in the first compartment so as to face the cathode and electrodepositing a lithium thin film on the cathode; Rotating the portion in which the lithium thin film is formed to supply a nitrogen gas and heating the second compartment to form a lithium nitride thin film; And rotating the portion in which the lithium nitride thin film is formed into a third compartment and contacting with an acid solution to synthesize ammonia, wherein the electrolyte includes Li ₂ SO ₄ and a lithium salt, and synthesizes the ammonia. Li ₂ SO ₄ produced in the step is supplied to the first compartment is reused, the third compartment provides an ammonia synthesis method based on lithium superion conductor, provided with an ammonium selective membrane.

The present invention also provides a method for preparing a lithium thin metal plate on the cathode, wherein the lithium electrode is electrodeposited (electrodeposition) on one surface of the cathode, a lithium superion conductor-based ammonia synthesis method.

In addition, the present invention, the anode is Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, Hf, Ta, At least one alloy selected from the group consisting of W, Re, Os, Ir, Pt, and Au, and the cathode is at least one selected from the group consisting of Ti, Mo, Fe, Co, Ni, Cu, Ag, and Zn A method of synthesizing ammonia based on lithium superion conductors, which is an alloy.

The present invention, the lithium salt is lithium perchlorate, lithium dithionite, lithium sulfate, lithium tetrafluoroborate, lithium hexafluorophosphate, lithium bromide and lithium chloride, lithium bistrifluoromethanesulfonylimide ( LiTFSI), lithium bisfluoromethanesulfonylimide (LiFSI), and lithium bisoxalatoborate (LiBOB) provide at least one lithium superion conductor based ammonia synthesis method.

The present invention also the organic solvent is a group consisting of a solvent containing propylene carbonate, ethylene carbonate, dimethyl carbonate, 1,3-dioxolane (1,3-dioxolane, DOL), dimethoxyethane (DME) Provided is a method of synthesizing ammonia based on lithium superion conductor, which is at least one selected from.

The present invention also provides a lithium superion conductor based, wherein the additive comprises at least one additive selected from the group consisting of sodium, potassium, cesium, rubidium, magnesium, potassium, strontium, fluoroethylene carbonate (FEC) A method for synthesizing ammonia is provided.

The present invention also provides a method for synthesizing ammonia based on lithium superion conductor, wherein the washing is performed using 2-methyl tetrahydrofuran.

The present invention also provides a lithium superion conductor based ammonia synthesis method, wherein the heating is performed at 200 ° C to 230 ° C for 30 minutes to 1 hour.

The present invention also provides a method for synthesizing ammonia based on lithium superion conductor, wherein the acid solution is H ₂ SO ₄ .

The present invention also provides a method for synthesizing ammonia based on lithium superion conductors, wherein the cathode is used to reuse the metal plate that has undergone the step of synthesizing the ammonia.

The present invention also provides a lithium superion conductor-based ammonia synthesis method for reusing the metal plate subjected to the synthesis of the ammonia to the cathode.

The present invention also provides a lithium superion conductor based ammonia synthesis method, wherein the electrodeposition is carried out for 5 to 20 minutes.

The present invention also comprises the step of synthesizing the ammonia to temporarily adjust the pH to 10 or more to convert the ammonium into ammonia gas state, the ammonium selective film is polypropylene (polypropylene, PP), polyvinyl Provided is a lithium superion conductor-based ammonia synthesis method, which is one gas permeable membrane selected from the group consisting of polyvinilidenefluoride (PVDF) and polytetrafluoroethylene (PTFE).

In the lithium superion conductor-based ammonia synthesis method of the present invention, ammonia may be synthesized in high yield as the ammonia synthesis conditions required for each step are optimized.

1 is a schematic diagram illustrating a method for synthesizing ammonia based on a superion conductor according to an embodiment of the present invention.

Figure 2 is a graph showing the synthesis rate of ammonia according to whether the washing and temperature of the lithium thin film metal plate according to an embodiment of the present invention.

Figure 3 is a graph showing the ammonia synthesis yield according to whether the washing and temperature of the lithium thin film metal plate according to an embodiment of the present invention.

Figure 4 is a graph showing the ammonia synthesis yield over time according to an embodiment of the present invention.

5 is a schematic diagram showing a continuous ammonia synthesis reactor according to an embodiment of the present invention.

Figure 6 is a graph comparing the amount of ammonia synthesis with or without an additive in one embodiment of the present invention.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily perform the following. Prior to the description of the invention, the terms or words used in the specification and claims described below should not be construed as limiting in their usual or dictionary meanings. Therefore, the embodiments described in the specification and the drawings shown in the drawings are only one of the most preferred embodiments of the present invention and do not represent all of the technical idea of the present invention, various modifications that can be replaced at the time of the present application It should be understood that there may be equivalents and variations.

In one aspect, the present invention is a lithium superion conductor-based ammonia synthesis method, the method, electrodeposition of lithium on one side of the cathode using an electrochemical cell in which the anode portion and the cathode portion is partitioned by the lithium superion conductor. ) To produce a lithium thin film metal plate; Washing the lithium thin film metal plate; A step of manufacturing a lithium nitride thin film metal plate for forming lithium nitride (Li ₃ N) on the lithium thin film by heating the lithium thin film metal plate passed through the washing step in a nitrogen atmosphere reactor; And synthesizing ammonia by supporting the lithium nitride thin film metal plate in an acid solution.

Lithium super ionic conductor (LISICON) may be represented by the formula Li _{2 + 2x} Zn _1-x GeO ₄ , for example Li _3.5 Zn _0.25 GeO ₄ , a solid material and a lithium ion conductive material. In the present invention, a lithium thin metal plate for ammonia synthesis is manufactured using an electrochemical cell in which an anode portion and a cathode portion are partitioned by a lithium superion conductor. FIG. 1 is a schematic diagram showing a method for synthesizing ammonia of the present invention. FIG. 1 (a) shows an electrochemical cell 1 using a lithium superion conductor 10. An electrochemical cell 1 partitioned by a lithium superion conductor is divided into an anode portion 11 and a cathode portion 12, and the anode portion 11 includes an anode 100 and an anode liquid 110. The cathode part includes a cathode 200 and an anode solution 210. When voltage is applied to the anode 100 and the cathode 200, water is oxidized in the anode 100 to generate electrons as shown in Scheme 1, and the electrons move to the cathode 200 to form a lithium superion conductor ( The lithium ions passed through 10 are reduced on the surface of the cathode 200. Lithium ions are electrodeposited with lithium metal on the surface of the reduction electrode, thereby obtaining a lithium thin film metal plate 201, which is an electrode electrode on which lithium is electrodeposited. The electrodeposition may be performed for 5 to 20 minutes.

Scheme 1

Reduction electrode: 6Li ^{+ +} 6e ^- → 6Li

Anode: 3H ₂ O _{^{→ 3 / 2O 2 + 6H +}} + 6e -

In one embodiment the anode is Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W , Re, Os, Ir, Pt, and Au is at least one alloy selected from the group consisting of, the cathode is preferably a metal material that does not cause side reactions with Li, Ti, Mo, Fe, Co, Ni, Cu, At least one alloy selected from the group consisting of Ag and Zn. Preferably, the anode solution is a Li ₂ SO ₄ aqueous solution, and the cathode solution is a salt capable of transferring lithium ions, such as lithium perchlorate, lithium dithionite, lithium sulfate, lithium tetrafluoroborate, or lithium hexa. Solution comprising fluorophosphate, lithium bromide and lithium chloride, lithium bistrifluoromethanesulfonylimide (LiTFSI), lithium bisfluoromethanesulfonylimide (LiFSI), lithium bisoxalatoborate (LiBOB) Can be used. As the electrolyte solvent, a solvent containing propylene carbonate, ethylene carbonate, dimethyl carbonate, 1,3-dioxolane (DOL), dimethoxyethane (DME) may be used. Preferably, a mixed solution of 1,3-dioxolane and dimethoxyethane containing lithium bisfluoromethanesulfonylimide may be used. In addition, at least one additive selected from the group consisting of sodium, potassium, cesium, rubidium, magnesium, potassium, strontium, and fluoroethylene carbonate (FEC) may be used as the reducing electrode solution. The additive may inhibit side reactions and improve ammonia yield.

FIG. 1 (b) shows washing the lithium thin metal plate 201 manufactured in an electrochemical cell using the lithium superion conductor in the cleaning solution 300. The washing of the lithium thin metal plate 201 may increase the ammonia synthesis yield by washing side reactions generated during the formation of the lithium thin film. In one embodiment the wash is 2-methyl tetrahydrofuran, a simple immersion wash for 30 seconds to 120 seconds, and dried for at least 1 minute in an argon atmosphere. The dried lithium thin metal plate 201 is heated in a reactor in a nitrogen atmosphere as shown in FIG. 1 (c) to form lithium nitride on the surface of the lithium thin film to produce a lithium nitride thin film metal plate 202. In one embodiment the heating is carried out at 200 ℃ to 230 ℃ for 30 minutes to 1 hour. When carried out at 200 ° C. or less, lithium nitride may not be sufficiently produced. In case of 230 ° C. or more, side reactions may occur or uniform lithium nitride may be difficult to form.

Scheme 2

6Li + N ₂ → 2Li ₃ N

The lithium nitride thin film metal plate 202 synthesizes ammonia as shown in FIG. When lithium nitride is in contact with an acid solution, ammonia is synthesized as in Scheme 3.

Scheme 3

2Li ₃ N + 6H ⁺ → 2NH ₃ + 6Li ⁺

The acid solution is HCl, H ₂ SO ₄ , HNO ₃ , H ₃ PO ₄ , H ₂ CO ₃ and the like may be used, but it is preferable to use H ₂ SO ₄ to reuse the used solution as the anolyte 110 in the electrochemical cell 1 of the step of preparing the above-described lithium thin film metal plate. The metal plate that has undergone the ammonia synthesis process can also be reused in the manufacturing process of a lithium nitride thin film metal plate by washing with a reduction electrode or an electrochemical cell. The synthesized ammonia can be collected using any ammonia collection step known to those skilled in the art. In one embodiment of the present invention, ammonia water is obtained by collecting ammonia using water.

In another aspect, the present invention is a method for synthesizing ammonia using the lithium superion conductor-based compartmental ammonia synthesis apparatus shown in FIG. 5. The method may use a cylindrical reaction device having a rotary cathode as a central axis and divided into a first compartment, a second compartment, and a third compartment based on the cathode. In the device, a cathode is rotated so that a reaction occurs in each compartment, and a compartment membrane is a membrane through which a material present in each compartment cannot pass. The method using the compartment-type ammonia synthesizing apparatus comprises the steps of: placing an anode and a superion conductor facing the cathode in the electrolyte containing the additive in the first compartment and electrodepositing a lithium thin film on the cathode; Rotating the portion in which the lithium thin film is formed to supply a nitrogen gas and heating the second compartment to form a lithium nitride thin film; And rotating the portion in which the lithium nitride thin film is formed into a third compartment and contacting with an acid solution to synthesize ammonia. The first compartment may in one embodiment use Li ₂ SO ₄ or LiOH as electrolyte, preferably Li ₂ SO ₄ . A reaction as in Scheme 1 occurs in a section in which a lithium thin film is formed on a surface of the rotary cathode exposed to the first section. In one embodiment the electrolyte comprises one or more additives selected from the group consisting of sodium, potassium, cesium, rubidium, magnesium, potassium, strontium, fluoroethylene carbonate (FEC). The additive may inhibit side reactions and improve ammonia yield.

When the lithium thin film is formed on the cathode in the Li ₂ SO ₄ electrolyte in the first compartment, the cathode is rotated so that the portion where the lithium thin film is formed is directed to the second compartment. In the second compartment, a nitrogen gas is supplied and heat is applied to form a lithium nitride thin film. In one embodiment, the lithium nitride thin film is formed by heating at 200 ° C. to 230 ° C. for 30 minutes to 1 hour. The cathode in which the lithium nitride thin film is formed rotates a portion of the lithium nitride thin film to a third compartment to synthesize ammonia. In the third compartment, the lithium nitride thin film and an acid react, and a reaction similar to that of Scheme 3 occurs to produce ammonia. Li ₂ SO ₄ generated at this time may be supplied to the first zone for reuse, and in one embodiment, the third compartment may temporarily reduce the pH to 9.3, to separate Li ₂ SO ₄ from (NH ₄ ) ₂ SO ₄ . Preferably, the ammonium is converted into an ammonia gas state by adjusting to 10 or more, and then ammonia may be separated using an organic and hydrophobic gas permeable membrane. In one embodiment, the gas permeable membrane may be made of polypropylene (PP), poly It is one selected from the group consisting of vinylidene fluoride (polyvinilidenefluoride, PVDF) and polytetrafluoroethylene (PTFE).

All technical terms used in the present invention, unless defined otherwise, are used in the meaning as commonly understood by those skilled in the art in the related field of the present invention. The contents of all publications described herein by reference are incorporated into the present invention.

Hereinafter, examples are provided to help understand the present invention. However, the following examples are provided only to more easily understand the present invention, and the present invention is not limited to the following examples.

실시예 1. 리튬 초이온 전도체 기반의 암모니아 합성Example 1. Ammonia Synthesis Based on Lithium Superion Conductor

Ammonia was synthesized in the same order as in FIG. 1 for synthesis of ammonia based on lithium superion conductors of the present invention. In the electrochemical cell partitioned by lithium superion conductor, Pt / C was used as an anode and Ni was used as a cathode. 1 ml of Li ₂ SO ₄ was used as the anode and 1 M was LiClO ₄ propylene carbonate as the cathode. 7 ml of solution was used. A lithium thin film metal plate was prepared by electrodepositing lithium on a nickel electrode for 400 to 600 seconds at 6 mA applied current at room temperature. The prepared lithium thin metal plate was washed by immersing in 2-methyltetrahydrofuran (2Me-THF) for 30 seconds and dried in an argon atmosphere for 1 minute. A lithium nitride thin film metal plate was manufactured by heating the washed and dried lithium thin metal plate in a nitrogen atmosphere at a nitrogen flow rate of 1000 sccm. The ammonia synthesis efficiency with temperature and time was performed at various temperature conditions and times, respectively. Ammonia was synthesized by simply immersing the resulting lithium nitride thin film plate in a 50 mM sulfuric acid solution at room temperature to terminate the ammonia synthesis reaction immediately after immersion.

The results regarding the ammonia synthesis efficiency are shown in FIGS. 2 to 4 and 6. A lithium nitride thin film was formed on a lithium thin metal plate for 30 minutes at 20 ° C., 100 ° C., 180 ° C., 200 ° C., 220 ° C. and 240 ° C., respectively, and the ammonia synthesis efficiency was measured according to the lithium nitride formation temperature and the presence or absence of washing. 2 is ammonia production divided by electrode area and reaction time (lithium nitride production time) according to the temperature conditions and the presence or absence of cleaning in the lithium nitride thin film sheet manufacturing step Shows the ammonia synthesis rate, Figure 3 shows the Faraday efficiency. Referring to FIGS. 2 and 3, when ammonia is synthesized by the lithium nitride thin film metal plate subjected to the washing step, it can be seen that high ammonia production and Faraday efficiency are exhibited at most temperature conditions. If it is not subjected to the washing step, it is considered that the residue of propylene carbonate contained in the reducing electrode interferes with the formation of the lithium nitride thin film. Propylene carbonate has low vapor pressure, making it difficult to completely dry and remove, and due to high reactivity with lithium, side reactions occur at a high temperature to form a lithium nitride thin film. However, in the case of washing the lithium thin metal plate with 2Me-THF and forming the lithium nitride thin film, since the reactivity with lithium is very low and the vapor pressure is large, most of the lithium thin film can be removed by simple argon drying alone. Therefore, forming lithium nitride on the lithium thin metal plate subjected to the washing step may exhibit high ammonia efficiency. The ammonia synthesis efficiency according to the lithium nitride thin film formation temperature was the highest efficiency at 220 ℃, side reactions at a higher temperature it is believed that the ammonia synthesis efficiency is lowered.

Figure 4 measures the ammonia synthesis Faraday efficiency according to the lithium nitride thin film formation time. Lithium nitride thin film was formed on the washed lithium thin metal plate for 10 to 120 minutes, and simply immersed in sulfuric acid. As a result, the ammonia produced from the metal plate on which lithium nitride was formed for the first 10 minutes and 20 minutes showed a sharp difference in efficiency, and the metal plate on which lithium nitride was formed over 20 minutes showed a gentle form of ammonia synthesis. Observed. When the metal plate on which lithium nitride was formed in the last 120 minutes was used, the Faraday efficiency was 72%. The lithium superion conductor-based ammonia synthesis method of the present invention can achieve a very high synthesis efficiency of ammonia by forming lithium nitride on the electrochemically produced lithium thin metal plate and simply immersing it.

6 shows ammonia synthesis using cesium additives. In the step of preparing a lithium thin metal plate, the amount of ammonia synthesis was compared using cesium as an additive. The cesium additive was added at 0.03 molarity (0.049 g in the total 7 ml solution), and was carried out in the same manner as described above except adding cesium. As a result, it can be seen that the amount of ammonia synthesis when cesium is included in lithium electrodeposition is improved than that of cesium.

Although the exemplary embodiments of the present application have been described in detail above, the scope of the present application is not limited thereto, and various modifications and improvements of those skilled in the art using the basic concepts of the present invention defined in the following claims are also provided. It belongs to.

[Description of the code]

1. Electrochemical Cell

10. Lithium Superion Conductor

11. The anode

12. Reduction pole

100. Anode

110. Anolyte

200. Reduction electrode

201.Lithium thin film metal plate

202. Lithium nitride thin film metal plate

210. Reduction solution

300. Washing liquid

501. The first compartment

502. Second compartment

503. Third compartment

Claims

Lithium superion conductor based ammonia synthesis method,

The method includes producing a lithium thin metal plate on a cathode using an electrochemical cell in which the anode portion and the cathode portion are partitioned by a lithium superion conductor;

Washing the lithium thin film metal plate;

A step of manufacturing a lithium nitride thin film metal plate for forming lithium nitride (Li 3 N) on the lithium thin film by heating the lithium thin film metal plate passed through the washing step in a nitrogen atmosphere reactor; And

And carrying out the lithium nitride thin film metal plate in an acid solution to synthesize ammonia,

The anode portion includes an anode and an anode solution, the cathode portion includes a cathode and a cathode solution,

The anode solution is Li 2 SO 4 aqueous solution, lithium ions passed by the lithium superion conductor is coated on the cathode,

The reduced electrode solution includes a lithium salt, an organic solvent and an additive,

Ammonia synthesis method based on lithium superion conductor.
Ammonia synthesis method using compartmental ammonia synthesis apparatus based on lithium superion conductor,

The method comprises a cylindrical anode having a rotary cathode as its central axis and divided into a first compartment, a second compartment and a third compartment based on the cathode, in which the anode and the superion are contained in the electrolyte in the first compartment. Positioning the conductor to face the cathode and electrodepositing a lithium thin film on the cathode;

Rotating the portion in which the lithium thin film is formed to supply a nitrogen gas and heating the second compartment to form a lithium nitride thin film; And

Rotating the portion where the lithium nitride thin film is formed into a third compartment and contacting with an acid solution to synthesize ammonia,

The electrolyte comprises Li 2 SO 4 and additives,

Li 2 SO 4 generated in the step of synthesizing the ammonia is supplied to the first compartment and reused,

Wherein said third compartment comprises an ammonium selective membrane;

Ammonia synthesis method based on lithium superion conductor.
The method of claim 1,

The manufacturing of a lithium thin metal plate on the cathode may include electrodepositing lithium on one surface of the cathode,

Ammonia synthesis method based on lithium superion conductor.
The method according to claim 1 or 2,

The anodes are Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Os At least one alloy selected from the group consisting of Ir, Pt, and Au,

The cathode is at least one alloy selected from the group consisting of Ti, Mo, Fe, Co, Ni, Cu, Ag and Zn,

Ammonia synthesis method based on lithium superion conductor.
The method of claim 1,

The lithium salt is lithium perchlorate, lithium dithionite, lithium sulfate, lithium tetrafluoroborate, lithium hexafluorophosphate, lithium bromide and lithium chloride, lithium bistrifluoromethanesulfonylimide (LiTFSI), lithium bis At least one selected from the group consisting of fluoromethanesulfonylimide (LiFSI), lithium bisoxalatoborate (LiBOB),

Ammonia synthesis method based on lithium superion conductor.
The method of claim 1,

The organic solvent is at least one selected from the group consisting of propylene carbonate, ethylene carbonate, dimethyl carbonate, 1,3-dioxolane (DOL), a solvent containing dimethoxyethane (DME). ,

Ammonia synthesis method based on lithium superion conductor.
The method according to claim 1 or 2,

The additive comprises one or more additives selected from the group consisting of sodium, potassium, cesium, rubidium, magnesium, potassium, strontium, fluoroethylene carbonate (FEC),

Ammonia synthesis method based on lithium superion conductor.
The method of claim 1,

The washing step, washing using 2-methyl tetrahydrofuran,

Ammonia synthesis method based on lithium superion conductor.
The method according to claim 1 or 2,

The heating is performed for 30 minutes to 1 hour at 200 ℃ to 230 ℃,

Ammonia synthesis method based on lithium superion conductor.
The method according to claim 1 or 2,

The acid solution is H 2 SO 4 ,

Ammonia synthesis method based on lithium superion conductor.
The method of claim 1,

The cathode, to reuse the metal plate that has been subjected to the step of synthesizing the ammonia,

Ammonia synthesis method based on lithium superion conductor.
The method of claim 2 or 3,

The electrodeposition is carried out for 5 to 20 minutes,

Ammonia synthesis method based on lithium superion conductor.
The method of claim 2,

Synthesizing the ammonia further comprises the step of temporarily adjusting the pH to 10 or more to convert ammonium into ammonia gas state,

The ammonium selective membrane is one gas permeable membrane selected from the group consisting of polypropylene (PP), polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE),

Ammonia synthesis method based on lithium superion conductor.