CN114214643A - Lithium ion cycle method electrochemical ammonia synthesis process and application - Google Patents
Lithium ion cycle method electrochemical ammonia synthesis process and application Download PDFInfo
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- CN114214643A CN114214643A CN202111300867.5A CN202111300867A CN114214643A CN 114214643 A CN114214643 A CN 114214643A CN 202111300867 A CN202111300867 A CN 202111300867A CN 114214643 A CN114214643 A CN 114214643A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/27—Ammonia
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B11/00—Oxides or oxyacids of halogens; Salts thereof
- C01B11/16—Perchloric acid
- C01B11/18—Perchlorates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/005—Lithium hexafluorophosphate
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/50—Processes
Abstract
The invention relates to a lithium ion cycle method electrochemical ammonia synthesis process and application: the synthesis of ammonia from nitrogen and water is realized under normal pressure by adopting an electrochemical lithium ion circulation strategy. The reaction process comprises nitridation of Li, and Li3N hydrolysis and Li salt preparation can be carried out circularly, the new process successfully avoids the competition of hydrogen evolution reaction in the direct electrochemical ammonia synthesis process, and the Faraday efficiency is as high as more than 85.0 percent. The lithium ion cycle method electrochemical ammonia synthesis process provided by the invention can be realized at normal temperature and normal pressure, hydrogen is not used as a proton source, fossil energy can be avoided, and greenhouse gas CO is reduced2Solves the problems of fossil energy consumption and carbon emission which troubles the H-B processAnd (5) problems are solved.
Description
Technical Field
The invention belongs to the field of electrochemical nitrogen fixation ammonia synthesis, and particularly relates to a lithium ion cycle method electrochemical ammonia synthesis process and application.
Background
In the electrochemical synthesis of ammonia in aqueous solution, the faradaic efficiency is low due to competition of hydrogen evolution reaction, and although some great developments have been made in recent years, the faradaic efficiency of most of the electrocatalytic synthesis of ammonia is still low (ii) ((<15%). The lithium ion cycle method electrochemical ammonia synthesis process developed by the invention avoids the use of fossil energy, does not use hydrogen as a proton source, and reduces CO2And (5) discharging. The new process for synthesizing ammonia includes the nitridation of Li and the reaction of Li3Three step-by-step circulating steps of N hydrolysis and Li salt preparation avoid the competition of hydrogen evolution reaction in the direct electrochemical ammonia synthesis process, and the Faraday efficiency of the ammonia production process can reach more than 85.0 percent.
Disclosure of Invention
Aiming at the problems in the current ammonia synthesis industry and the research of electrochemical ammonia synthesis, the invention provides a lithium ion cycle method electrochemical ammonia synthesis process and application. Using rich Li+Reduction of organic electrolyte at cathode to produce Li3N, realization of Li under ambient conditions3And (3) electrochemically synthesizing ammonia by using an N-dominated lithium ion cycle method. The invention avoids the competition of hydrogen evolution reaction in the direct electrochemical ammonia synthesis process, and the Faraday efficiency is as high as more than 85.0 percent.
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:
the invention provides a high-efficiency electrochemical ammonia synthesis process by a lithium ion circulation method, which comprises three step-by-step circulation procedures, wherein the step-by-step circulation procedure is specifically a first procedure: nitriding of Li; a second step: li3N hydrolysis; a third step: and (3) preparing a Li salt.
The three step-by-step circulating processes are sequentially circulated, and the first process is started after the third process is finished, so that the lithium ion circulation is realized.
Further, the first step employs a lithium-rich organic electrolyte system.
Further, the organic electrolyte system comprises a lithium salt, and the lithium salt can be an organic lithium salt and can also be an inorganic lithium salt; furthermore, the material can be one or a combination of more of lithium perchlorate, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium trifluoromethanesulfonate and the like.
Further, the organic electrolyte system comprises a solvent, wherein the solvent can be carbonic ester, carboxylic ester or ether; furthermore, the compound can be one or a combination of several of ethylene carbonate, propylene carbonate, diethyl carbonate, ethyl methyl carbonate and the like.
Further, in the organic electrolyte system, the organic electrolyte is a mixed solution (LiPF) of ethylene carbonate and diethyl carbonate in which lithium hexafluorophosphate is dissolved6/EC+DEC)。
Further, the concentration of lithium salt in the organic electrolyte is 0.1-2 mol/L.
Further, the first process includes: the prepared electrolyte and the electrode assembly are arranged in an electrolytic cell; a three-electrode system is adopted, wherein a Pt sheet electrode is adopted as an anode, a porous electrode material is adopted as a cathode, and an Ag/Ag + electrode is adopted as a reference electrode; continuous introduction of N around the cathode2And the gas flow and the electrochemical workstation provide power to carry out the nitridation reaction of the Li. Preferably, the capacity of the electrolytic cell is 50 mL.
Further, the cathode material may be nickel, iron, copper, titanium, stainless steel, graphite, nickel-iron alloy, and the like.
Preferably, the cathode material is a porous material.
Further, in the second step, a proton source and Li3N is hydrolyzed and reacts quickly at normal temperature and pressure to generate dissolved ammonia or ammonium salt.
Further, the proton source is water or an acid solution or the like.
Further, in the third step, LiOH generated in the second step is reacted to generate a lithium salt corresponding to the first step, thereby realizing circulation of lithium ions.
Furthermore, the lithium ion cycle method electrochemical synthesis ammonia reaction is carried out at normal temperature and normal pressure.
The invention provides an application of a lithium ion cycle method electrochemical ammonia synthesis process in ammonia synthesis.
In the invention, the high-efficiency electrochemical ammonia synthesis process by the lithium ion circulation method comprises the steps of nitriding of Li and Li3N hydrolysis and Li salt preparation. And the three step-by-step circulating processes are sequentially circulated, and the first process is started after the third process is finished, so that the lithium ion circulation is realized. Based on the circulation of lithium ions in the reaction, the electrification and the proton addition in the process of electrochemically synthesizing ammonia are carried out step by step, the hydrogen evolution reaction is avoided, and the Li under normal temperature and normal pressure is realized+→Li3N→NH3High-efficiency ammonia synthesis in linkage circulation.
The invention can be used in the process of electrochemically synthesizing ammonia at normal temperature and normal pressure, the faradaic efficiency can reach more than 85 percent based on the lithium ion cycle method electrochemical ammonia synthesis process, and the yield of the product ammonia can reach 89 mu g h-1cm-2The above.
The invention has the beneficial effects that:
(1) the lithium ion cycle method electrochemical ammonia synthesis process provided by the invention can be realized at normal temperature and normal pressure, hydrogen is not used as a proton source, fossil energy can be avoided, and greenhouse gas CO is reduced2Solves the problems of fossil energy consumption and carbon emission which troubles the H-B process.
(2) Compared with the conventional aqueous electrolyte electrochemical ammonia synthesis system, the lithium ion cycle method electrochemical ammonia synthesis process provided by the invention has the advantages that the power-up and mass addition sub-steps are separately carried out, the competition of hydrogen evolution reaction in the ammonia production process is directly avoided, and the electric efficiency of the ammonia synthesis reaction is greatly improved. Experiments show that the Faraday efficiency of the ammonia synthesis process by adopting the process can reach 85.0 percent.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the application and, together with the description, serve to explain the application and are not intended to limit the application.
FIG. 1 is a schematic diagram of electrochemical synthesis of ammonia by a lithium ion cycle method;
FIG. 2 is a schematic diagram of an electrolytic cell for electrochemical synthesis of ammonia by lithium ion cycle method, wherein WE is a working electrode, CE is a counter electrode, and RE is a reference electrode;
FIG. 3 is a standard curve of the Nassler reagent for ammonia content determination.
Detailed Description
In order to make the technical solutions of the present disclosure more clearly understood by those skilled in the art, the technical solutions of the present disclosure will be described in detail below with reference to specific embodiments. It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available by commercial purchase.
Example 1
In the high-efficiency electrochemical ammonia synthesis process by lithium ion cycling method of this embodiment, the electrolyte used in the nitridation step is a mixed solution (LiClO) of ethylene carbonate and diethyl carbonate (volume ratio 1: 1) in which 0.5M lithium perchlorate is dissolved4(0.5M)/(EC + DEC) (1:1v/v, 50mL)), tested with a carbon cloth electrode.
The treatment method of the carbon cloth electrode specifically comprises the following steps: cutting a piece of carbon cloth with the side length of 1x1.5 cm, respectively carrying out ultrasonic treatment on the carbon cloth in acetone, absolute ethyl alcohol and deionized water for 20 minutes, then carrying out ultrasonic treatment in dilute hydrochloric acid for 20 minutes, and finally carrying out ultrasonic treatment in deionized water for 10 minutes.
50mL of electrolyte and carbon cloth are assembled into an electrolytic cell, a three-electrode system is adopted, a Pt sheet electrode is used as an anode, a carbon cloth electrode is used as a cathode, and an Ag/Ag + electrode is adopted as a reference electrode. High-purity nitrogen is introduced near the cathode, and the flow rate is 5mL min-1. The nitridation experiment of lithium was carried out at a constant potential of-6V (vs. Ag/Ag +) by means of an electrochemical workstation, the reaction time being 0.5 h.
After the nitridation step of lithium is completed, the Li formed at the cathode is removed3N is collected and sent to the second process, Li3And (N) hydrolyzing. Using deionized water and Li3The N reacts to generate ammonia and LiOH, the content of the ammonia is detected by using a nano reagent method, the ammonia yield is calculated to be 89.97 mu g h-1cm-2, and the Faraday efficiency is 86.7%.
LiOH generated in the hydrolysis procedure reacts with perchloric acid to finally generate lithium perchlorate, so that the circulation of lithium ions is realized.
Example 2
In the high-efficiency electrochemical ammonia synthesis process by the lithium ion cycle method of this embodiment, the electrolyte used in the nitridation step is a mixed solution (LiPF) of ethylene carbonate and diethyl carbonate (volume ratio of 1: 1) dissolved with 1.0M lithium hexafluorophosphate6(1.0M)/(EC + DEC) (1:1v/v, 50mL)), was tested with a foam iron electrode.
The method for processing the foamed iron electrode specifically comprises the following steps: cutting a piece of foam iron with the side length of 1x1.5 cm, and respectively carrying out ultrasonic treatment on the foam iron in acetone, absolute ethyl alcohol and deionized water for 20 minutes.
50mL of electrolyte and an electrode are assembled into an electrolytic cell, a three-electrode system is adopted, a Pt sheet electrode is used as an anode, foam iron is used as a cathode, and an Ag/Ag + electrode is adopted as a reference electrode. High-purity nitrogen is introduced near the cathode at the flow rate of 5mLmin-1. The nitridation experiment of lithium was carried out at a constant potential of-6V (vs. Ag/Ag +) by means of an electrochemical workstation, the reaction time being 0.5 h.
After the nitridation step of lithium is completed, the Li formed at the cathode is removed3N is collected and sent to the second process, Li3And (N) hydrolyzing. Using deionized water and Li3N reaction to generate ammonia and LiOH, detecting the content of ammonia by using a nano reagent method, and calculating the ammonia yield to be 96.17 mu g h-1cm-2Faraday efficiency was 87.5%.
LiOH generated in the hydrolysis step and ammonium hexafluorophosphate undergo an ion exchange reaction in a mixed solvent of ethylene carbonate and diethyl carbonate (volume ratio of 1: 1), and lithium hexafluorophosphate is finally generated, so that the circulation of lithium ions is realized.
Example 3
In the high-efficiency electrochemical ammonia synthesis process by the lithium ion cycle method of this embodiment, the electrolyte used in the nitridation step is a mixed solution (LiPF) of ethylene carbonate and diethyl carbonate (volume ratio of 1: 1) dissolved with 1.0M lithium hexafluorophosphate6(1.0M)/(EC + DEC) (1:1v/v, 50mL)), was tested with a nickel foam electrode.
The treatment method of the foamed nickel electrode specifically comprises the following steps: a piece of foam nickel with the side length of 1x1.5 cm is cut out and is respectively treated by ultrasonic treatment in acetone, absolute ethyl alcohol and deionized water for 20 minutes.
50mL of electrolyte and an electrode are assembled into an electrolytic cell, a three-electrode system is adopted, a Pt sheet electrode is taken as an anode, a foam nickel electrode is taken as a cathode, and a reference electrode is Ag/Ag+And an electrode. Introducing high-purity nitrogen near the cathode at the flow rate of 10mL min-1. at-5V (vs. Ag/Ag) by electrochemical workstation+) The reaction time was 0.5 h.
After the nitridation step of lithium is completed, the Li formed at the cathode is removed3N is collected and sent to the second process, Li3And (N) hydrolyzing. Using deionized water and Li3N reaction to generate ammonia and LiOH, detecting the content of ammonia by using a nano reagent method, and calculating the ammonia yield to be 102.43 mu g h-1cm-2Faraday efficiency 89.3%.
LiOH generated in the hydrolysis step and ammonium hexafluorophosphate undergo an ion exchange reaction in a mixed solvent of ethylene carbonate and diethyl carbonate (volume ratio of 1: 1), and lithium hexafluorophosphate is finally generated, so that the circulation of lithium ions is realized.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited thereto, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications and equivalents can be made in the technical solutions described in the foregoing embodiments, or equivalents thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention. Although the embodiments of the present invention have been described with reference to the accompanying drawings, it is not intended to limit the scope of the present invention, and it should be understood by those skilled in the art that various modifications and variations can be made without inventive efforts by those skilled in the art based on the technical solution of the present invention.
Claims (10)
1. The high-efficiency electrochemical ammonia synthesis process by the lithium ion circulation method is characterized by comprising three step-by-step circulation procedures, wherein the step-by-step circulation procedure is specifically a first procedure: nitriding of Li; a second step: li3N hydrolysis; a third step: and (3) preparing a Li salt.
2. The process for electrochemically synthesizing ammonia according to claim 1, wherein the first step employs a lithium-rich organic electrolyte solution in which the concentration of lithium salt is 0.1-2 mol/L.
3. The lithium ion cycling electrochemical ammonia synthesis process of claim 2, wherein the lithium salt is an organic lithium salt and/or an inorganic lithium salt; further, the material can be one or a combination of more of lithium perchlorate, lithium hexafluorophosphate, lithium tetrafluoroborate and lithium trifluoromethanesulfonate.
4. The lithium ion cycle electrochemical ammonia synthesis process according to claim 2, wherein the organic electrolyte comprises a solvent, and the solvent is one or more of carbonates, carboxylates and ethers; furthermore, the solvent is one or a combination of ethylene carbonate, propylene carbonate, diethyl carbonate and ethyl methyl carbonate.
5. The lithium ion cycle electrochemical ammonia synthesis process of claim 1, wherein the first process comprises the following steps: the prepared organic electrolyte and the electrode are assembled into an electrolytic cell; adopts a three-electrode system, wherein a Pt sheet electrode is adopted as an anode, a porous electrode material is adopted as a cathode, and Ag/A is adoptedg+The electrode is used as a reference electrode; continuous introduction of N around the cathode2The gas flow and the electrochemical workstation provide power to carry out the nitridation reaction of the Li; preferably, the capacity of the electrolytic cell is 50 mL.
6. The lithium ion cycle electrochemical ammonia synthesis process of claim 5, wherein the porous electrode material is one or more of nickel, iron, copper, titanium, stainless steel, graphite, and nickel-iron alloy.
7. The lithium-ion cycling electrochemical ammonia synthesis process of claim 1, wherein in the second step, the proton source and Li are used3N is hydrolyzed and reacts quickly at normal temperature and normal pressure to generate dissolved ammonia or ammonium salt; preferably, the proton source is water or an acid solution.
8. The process for electrochemically synthesizing ammonia according to claim 1, wherein in the third step, LiOH generated in the second step is reacted to generate a lithium salt corresponding to the first step, thereby realizing lithium ion circulation.
9. The process for electrochemically synthesizing ammonia by lithium ion cycling according to claim 1, wherein the reaction for electrochemically synthesizing ammonia by lithium ion cycling is carried out at normal temperature and pressure.
10. Use of the lithium ion cycle electrochemical ammonia synthesis process of any one of claims 1 to 9 for ammonia synthesis.
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| CN117157252A (en) * | 2023-06-30 | 2023-12-01 | 广东邦普循环科技有限公司 | Method for producing ammonia by extracting lithium from salt lake in combined manner through full chain integration |
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| CN117157252A (en) * | 2023-06-30 | 2023-12-01 | 广东邦普循环科技有限公司 | Method for producing ammonia by extracting lithium from salt lake in combined manner through full chain integration |
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