Electrode containing artificial solid electrolyte interface layer, preparation method of electrode and application of electrode in alkali metal-mediated ammonia synthesis

Abstract

The invention provides an electrode containing an artificial solid electrolyte interface layer, a preparation method of the electrode and application of the electrode in alkali metal-mediated ammonia synthesis, and belongs to the technical field of electrochemical ammonia synthesis. The invention provides an electrode containing an artificial solid electrolyte interface layer. The artificial solid electrolyte interface layer comprises a solid electrolyte and a binder. The artificial solid electrolyte interface layer is arranged on the electrode in advance and can slow down the formation of an in-situ SEI layer, so that the structure defect is slowed down, and the stability of alkali metal mediated synthesis ammonia is further improved; meanwhile, a binder is added into the artificial solid electrolyte interface layer, so that the bonding strength with an electrode can be improved, falling is avoided, and the stability of alkali metal mediated synthesis ammonia is further improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of electrochemical ammonia synthesis, and particularly relates to an electrode containing an artificial solid electrolyte interface layer, a preparation method thereof, and application in alkali metal-mediated electrochemical ammonia synthesis. Background Art

[0002] Ammonia (NH3) is a key raw material for synthetic fertilizers and chemicals and a potential carbon-free energy source. Within the strategic context of reducing energy consumption and carbon emissions, alkali metal-mediated electrochemical nitrogen reduction of ammonia has attracted significant attention. By injecting renewable electricity, a slow nitrogen reduction reaction can be achieved at room temperature. However, the formation of an unstable solid electrolyte interface (SEI) still poses a challenge to the practical application of alkali metal-mediated ammonia synthesis. Currently, the SEI is formed in situ on the electrode using alkali metal salts in organic solvents. During long-term device cycling, the repeated deposition and consumption of alkali metals leads to significant volume changes that further detach the fragile native SEI. This vicious cycle of formation, shedding, and regeneration of the native SEI leads to structural defects that ultimately destabilize alkali metal-mediated ammonia synthesis. Summary of the Invention

[0003] The present invention aims to provide an electrode containing an artificial solid electrolyte interface layer, a preparation method thereof, and its application in alkali metal-mediated ammonia synthesis. The electrode containing an artificial solid electrolyte interface layer provided by the present invention can improve the stability of alkali metal-mediated ammonia synthesis.

[0004] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0005] The present invention provides an electrode containing an artificial solid electrolyte interface layer. The artificial solid electrolyte interface layer comprises a solid electrolyte and a binder.

[0006] Preferably, the artificial solid electrolyte interface layer covers the electrode.

[0007] Preferably, the thickness of the artificial solid electrolyte interface layer is 1 to 100 μm.

[0008] Preferably, the solid electrolyte includes at least one of oxides, sulfides, hydrides, nitrides, carbides, halides, COF-based materials, MOF-based materials, graphene-based materials and polymers.

[0009] The present invention also provides a method for preparing an electrode containing an artificial solid electrolyte interface layer as described in the above technical solution, comprising the following steps:

[0010] (1) mixing a solid electrolyte, an organic solvent, and a binder to obtain a slurry;

[0011] (2) coating the slurry obtained in step (1) on an electrode to obtain an electrode containing an artificial solid electrolyte interface layer.

[0012] Preferably, based on the mass of the slurry being 100%, the mass of the solid electrolyte in step (1) is 60-95%, the mass of the organic solvent is 3-20%, and the mass of the binder is 2-20%.

[0013] The present invention also provides the use of the electrode containing the artificial solid electrolyte interface layer described in the above technical solution or the electrode containing the artificial solid electrolyte interface layer prepared by the preparation method described in the above technical solution in alkali metal-mediated electrosynthesis of ammonia.

[0014] Preferably, the alkali metal-mediated method for synthesizing ammonia comprises:

[0015] An electrode containing an artificial solid electrolyte interface layer is used as the cathode, an alkali metal salt solution is used as the electrolyte, nitrogen is introduced into the electrolytic cell, and an electrochemical reaction is carried out to produce ammonia.

[0016] Preferably, the flow rate of the nitrogen gas is 5 to 25 sccm.

[0017] Preferably, the current density of the electrochemical reaction is 0.01 to 1 mA cm -2 .

[0018] The present invention provides an electrode containing an artificial solid electrolyte interface layer, wherein the composition of the artificial solid electrolyte interface layer includes a solid electrolyte and a binder. The present invention pre-arranges an artificial solid electrolyte interface layer on the electrode, which can slow down the formation of an in-situ SEI layer, thereby slowing down structural defects, and further improving the stability of alkali metal-mediated ammonia synthesis; at the same time, a binder is added to the artificial solid electrolyte interface layer, which can increase the bonding strength with the electrode and avoid falling off, thereby further improving the stability of alkali metal-mediated ammonia synthesis. Experimental results show that when the electrode containing the artificial solid electrolyte interface layer provided by the present invention is used as a cathode and is used in alkali metal-mediated ammonia synthesis, the ammonia generation rate is 9.8 to 13.1 nmol s -1 cm -2 The Faradaic efficiency of ammonia is 73-97%. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 The mechanism of the electrochemical reaction of the present invention;

[0020] Figure 2 1 is the XRD pattern of the electrodes of Example 1 and Comparative Example 1;

[0021] Figure 3N2-TPD diagram of the cathode before nitrogen reduction reaction in Application Example 1 and Comparative Application Example 1;

[0022] Figure 4 UV-vis graphs of ammonia production in Application Example 1 and Comparative Application Example 1;

[0023] Figure 5 1H NMR diagram of ammonia produced in Application Examples 2 to 10. DETAILED DESCRIPTION

[0024] The present invention provides an electrode containing an artificial solid electrolyte interface layer, comprising a solid electrolyte and a binder. The present invention pre-installs the artificial solid electrolyte interface layer on the electrode, which can slow the formation of an in-situ SEI layer, thereby reducing structural defects and improving the stability of alkali metal-mediated ammonia synthesis. Simultaneously, the addition of a binder to the artificial solid electrolyte interface layer strengthens the bond with the electrode, preventing it from falling off, further improving the stability of alkali metal-mediated ammonia synthesis.

[0025] In the present invention, the artificial solid electrolyte interface layer preferably covers the electrode. The present invention uses the artificial solid electrolyte interface layer to completely cover the electrode, which can further improve the stability of alkali metal-mediated ammonia synthesis.

[0026] The present invention has no particular limitation on the sources of the raw materials, and commercially available products known to those skilled in the art may be used.

[0027] In the present invention, the electrode is preferably a cathode loaded with copper foam; the cathode is preferably a current collector, stainless steel mesh, or a carbon material. The present invention does not specifically limit the shape and size of the cathode and can be adjusted according to actual needs. The copper foam provided on the cathode in the present invention has excellent conductivity and a porous structure, which can enhance electron transfer efficiency and catalytic activity in electrochemical reactions.

[0028] In the present invention, the thickness of the artificial solid electrolyte interface layer is preferably 1 to 100 μm. As an embodiment, the thickness of the artificial solid electrolyte interface layer can be 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, or 90 μm. Limiting the thickness of the artificial solid electrolyte interface layer to the above range can further improve the stability of alkali metal-mediated ammonia synthesis.

[0029] In the present invention, the solid electrolyte preferably includes at least one of an oxide, a sulfide, a hydride, a nitride, a carbide, a halide, a COF-based material, a MOF-based material, a graphene-based material, and a polymer; the oxide preferably includes at least one of lithium oxide and calcium oxide; the sulfide preferably includes at least one of lithium sulfide and calcium sulfide; the hydride preferably includes at least one of lithium hydride and calcium hydride; the nitride preferably includes at least one of lithium nitride and calcium nitride; the carbide preferably includes at least one of lithium carbide and calcium carbide; the halide preferably includes at least one of lithium fluoride and calcium fluoride; the COF-based material preferably includes at least one of COF-1 and COF-5; the MOF-based material preferably includes ZIF-8; the graphene-based material preferably includes at least one of Fe / rGO and Fe-NC; and the polymer preferably includes at least one of PEO and PMMA. Limiting the type of solid electrolyte to the above range can further improve the stability of alkali metal-mediated ammonia synthesis.

[0030] In the present invention, the binder preferably includes at least one of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyacrylic acid (PAA), polyvinyl alcohol (PVA), styrene-butadiene rubber (SBR), carboxymethyl cellulose (CMC), polyamide (PA), fluoride binder (PFA) and polyimide (PI).

[0031] The present invention pre-constructs an artificial solid electrolyte interface layer that stabilizes alkali metal ion channels, solving the problem of decreased ammonia synthesis performance caused by side reactions and structural defects during in-situ SEI formation. The artificial solid electrolyte interface layer provided by the present invention can adsorb nitrogen. Compared with the in-situ generated SEI, its structure is controllable, and its nitrogen adsorption capacity can be enhanced by increasing active sites.

[0032] The present invention also provides a method for preparing an electrode containing an artificial solid electrolyte interface layer as described in the above technical solution, comprising the following steps:

[0033] (1) mixing a solid electrolyte, an organic solvent, and a binder to obtain a slurry;

[0034] (2) coating the slurry obtained in step (1) on an electrode to obtain an electrode containing an artificial solid electrolyte interface layer.

[0035] The present invention mixes a solid electrolyte, an organic solvent and a binder to obtain slurry.

[0036] In the present invention, the organic solvent preferably includes at least one of N-methylpyrrolidone, N,N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, acetone, chloroform, dichloromethane, acetonitrile, toluene, cyclohexanone, ethyl acetate, isopropyl alcohol, ethanol, methanol, butanone, cyclohexane, and ethylene glycol dimethyl ether. The present invention uses an organic solvent to dissolve other raw materials to prepare a slurry.

[0037] In the present invention, based on the mass of the slurry being 100%, the mass of the solid electrolyte is preferably 60-95%; the mass of the organic solvent is preferably 3-20%; and the mass of the binder is preferably 2-20%. In one embodiment, the mass of the solid electrolyte can be 65%, 70%, 75%, 80%, 85%, or 90%; the mass of the organic solvent can be 5%, 10%, or 15%; and the mass of the binder can be 5%, 10%, or 15%. Limiting the contents of the solid electrolyte, organic solvent, and binder within the aforementioned ranges can further improve the stability of the alkali metal-mediated ammonia synthesis.

[0038] The present invention has no special limitation on the mixing of the solid electrolyte, organic solvent and binder, and the technical scheme for preparing the mixed material well known to those skilled in the art can be adopted.

[0039] After obtaining the slurry, the present invention coats the slurry on an electrode to obtain an electrode containing an artificial solid electrolyte interface layer.

[0040] The present invention has no particular limitation on the coating operation, and any operation well known to those skilled in the art may be used.

[0041] After coating is completed, the present invention preferably dries the coated product to obtain an electrode containing an artificial solid electrolyte interface layer.

[0042] The present invention has no particular limitation on the drying operation, and the product may be dried to a constant weight.

[0043] The preparation method provided by the invention has simple process.

[0044] The present invention also provides the use of the electrode containing the artificial solid electrolyte interface layer described in the above technical solution or the electrode containing the artificial solid electrolyte interface layer prepared by the preparation method described in the above technical solution in alkali metal-mediated electrosynthesis of ammonia.

[0045] In the present invention, the alkali metal-mediated method for synthesizing ammonia preferably comprises:

[0046] An electrode containing an artificial solid electrolyte interface layer is used as the cathode, an alkali metal salt solution is used as the electrolyte, nitrogen is introduced into the electrolytic cell, and an electrochemical reaction is carried out to produce ammonia.

[0047] In the present invention, the electrolyte preferably comprises an alkali metal salt, an organic solvent and a proton donor.

[0048] In the present invention, the alkali metal salt is preferably lithium tetrafluoroborate; the organic solvent is preferably diethylene glycol dimethyl ether; the proton donor preferably includes acids or alcohols; the acid preferably includes inorganic acids and organic acids; the inorganic acid preferably includes hydrochloric acid, sulfuric acid, nitric acid, hydrobromic acid, hydroiodic acid, perchloric acid, phosphoric acid, hydrofluoric acid, sulfurous acid, hypochlorous acid, chloric acid, bromic acid, silicic acid, nitrous acid or boric acid; the organic acid preferably includes formic acid, acetic acid, citric acid, malic acid, tartaric acid, oxalic acid, pyruvic acid, lactic acid, benzoic acid, salicylic acid, caffeic acid, Ascorbic acid, cinnamic acid, glutamic acid, aspartic acid, stearic acid, oleic acid, linoleic acid, phenylacetic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acid, acetylsalicylic acid, fumaric acid or sorbic acid; the alcohol preferably includes ethanol, methanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, tert-butanol, ethylene glycol, glycerol, benzyl alcohol, cinnamyl alcohol, stearyl alcohol, palmitol, lauryl alcohol, oleyl alcohol, dodecanol, tetradecanol, hexadecanol, octadecyl alcohol, cyclohexanol, furfuryl alcohol, mannitol, sorbitol, xylitol, maltitol, lactitol or inositol. In the present invention, the alkali metal salt is used to provide alkali metal ions; the proton donor is used to provide hydrogen ions.

[0049] In the present invention, the concentration of the alkali metal salt in the electrolyte is preferably 0.01 to 80 M; the concentration of the proton donor in the electrolyte is preferably 0.001 to 5 M. As an embodiment, the concentration of the alkali metal salt in the electrolyte may be 0.05 M, 0.1 M, 1 M, 2 M, 5 M, 10 M, 20 M, 30 M, 40 M, 50 M, 60 M, or 70 M; the concentration of the proton donor in the electrolyte may be 0.01 M, 0.1 M, 0.2 M, 0.5 M, 1 M, 2 M, 3 M, or 4 M.

[0050] In the present invention, the flow rate of the nitrogen gas is preferably 5 to 25 sccm. As an embodiment, the flow rate of the nitrogen gas can be 10 sccm, 15 sccm or 20 sccm.

[0051] In the present invention, the anode used in the electrochemical reaction is preferably a catalyst-loaded anode; the catalyst is preferably a platinum catalyst. The present invention has no particular restrictions on the material, shape, and size of the anode, which can be adjusted according to actual needs.

[0052] As an embodiment, the anode may be a stainless steel mesh loaded with a platinum catalyst.

[0053] In the present invention, the electrochemical reaction is preferably carried out under anaerobic conditions; the oxygen content of the anaerobic conditions is preferably ≤0.1 ppm. The present invention has no particular limitation on the control of the anaerobic conditions; nitrogen can be introduced to remove oxygen before the electrochemical reaction.

[0054] In the present invention, the current density of the electrochemical reaction is preferably 0.01 to 1 mA cm -2 As an embodiment, the current density of the electrochemical reaction can be 0.02Acm -2 、0.05Acm -2 、0.1Acm -2 or 0.5Acm -2 .

[0055] In the present invention, the mechanism of the electrochemical reaction is as follows, where M is an alkali metal element:

[0056] The nitrogen reduction electrode reaction formula is: N2+6M + +6e - →2M3N;

[0057] The reaction formula for the electrochemical nitrogen reduction product to react with hydrogen ions to generate ammonia is: M3N+3H + →NH3+3M + .

[0058] The mechanism of the electrochemical reaction of the present invention is as follows Figure 1 As shown in the figure, M is an alkali metal element, HA is an acid, H is a proton, and A is a proton acceptor.

[0059] according to Figure 1 It can be seen that the electrochemical reaction includes two steps, the first step is nitrogen reduction reaction, and the second step is hydrogenation to synthesize ammonia.

[0060] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions of the present invention. Obviously, the embodiments described are only some of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0061] The experimental equipment used in the examples and comparative examples are: electrochemical workstation CHI 660E (Shanghai Chenhua), X-ray diffractometer (MiniFlex II), chemical adsorption instrument (AutoChem II 2950HP), ultraviolet-visible spectrometer (UV-vis 2600), and NMR spectrometer (Adance III Bruker).

[0062] Example 1

[0063] An electrode comprising an artificial solid electrolyte interface layer, wherein the artificial solid electrolyte interface layer is composed of a solid electrolyte and a binder;

[0064] The artificial solid electrolyte interface layer covers the electrode;

[0065] The solid electrolyte is COF-5;

[0066] The binder is PVDF;

[0067] The thickness of the artificial solid electrolyte interface layer is 50 μm;

[0068] The electrode is a stainless steel mesh loaded with copper foam; the copper foam is deposited on the stainless steel mesh by electroplating, and the electroplating method is: applying -1Acm -2 The current density was set to 1 min to obtain a stainless steel mesh loaded with foam copper; the size of the stainless steel mesh was 25 cm 2 ; The electrolyte was prepared by dissolving CuSO4 (Merck, 98%) in 1.5 M H2SO4 (SigmaAldrich, 99.999%), and the CuSO4 concentration in the electrolyte was 0.4 M;

[0069] The preparation method of the electrode containing the artificial solid electrolyte interface layer is:

[0070] (1) mixing a solid electrolyte, an organic solvent, and a binder to obtain a slurry; the organic solvent is ethanol; based on the mass of the slurry being 100%, the mass of the solid electrolyte is 85%, the mass of the organic solvent is 10%, and the mass of the binder is 5%;

[0071] (2) coating the slurry obtained in step (1) on an electrode to obtain an electrode containing an artificial solid electrolyte interface layer;

[0072] The preparation method of COF-5 is as follows: 1,4-phenylenediboronic acid (BDBA) (25 mg, 0.15 mmol, Aldrich) and 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) (16 mg, 0.05 mmol, Aldrich) are added to 1 mL of a mixed solution of 1,3,5-trimethylbenzene and dioxane (volume ratio of 1:1), rapidly frozen under 77K liquid nitrogen, evacuated to 150 mTorr and sealed, then heated at 100°C for 72 hours, then filtered, washed with 30 mL of tetrahydrofuran, and dried to obtain COF-5.

[0073] Comparative Example 1

[0074] On the basis of Example 1, COF-5 was omitted and other conditions remained unchanged, that is, the stainless steel mesh was loaded with foam copper.

[0075] The X-ray diffractometer was used to test Example 1 and Comparative Example 1. Figure 2 As shown, Figure 2 2 are XRD patterns of the electrodes of Example 1 and Comparative Example 1.

[0076] from Figure 2 It can be seen that COF-5 was successfully synthesized in Example 1.

[0077] Application Example 1

[0078] The electrode of Example 1 was used as the cathode, the stainless steel mesh loaded with platinum catalyst was used as the anode, and the alkali metal salt solution was used as the electrolyte. Under anaerobic conditions, nitrogen gas with a flow rate of 5 sccm was introduced to the cathode side. The mixture was allowed to stand for 30 minutes, and then the mixture was heated at 0.01 mA cm -2 An electrochemical reaction is performed to obtain ammonia; the electrolyte comprises an alkali metal salt, an organic solvent, and a proton donor, wherein the alkali metal salt is lithium tetrafluoroborate; the organic solvent is diethylene glycol dimethyl ether, and the proton donor is ethanol; the concentration of the alkali metal salt in the electrolyte is 2M; the concentration of the proton donor in the electrolyte is 0.2M; the flow rate of nitrogen during the electrochemical reaction is 5 seem; and the oxygen content of the anaerobic state is ≤0.1ppm;

[0079] The platinum catalyst was deposited on the stainless steel mesh by electrodeposition. The electrodeposition method was as follows: two Pt meshes were connected and used as counter electrodes. The stainless steel mesh was placed between the two counter electrodes and a -0.2A cm -2 The current density is 2min, and the size of the stainless steel mesh is 25cm 2 The electrolyte used for electrodeposition was prepared by dissolving H2PtCl6·6H2O (SigmaAldrich, 99.999%) and HAuCl4·3H2O (SigmaAldrich, 99%) in 3M H2SO4 (SigmaAldrich, 99.999%), with the concentrations of H2PtCl6·6H2O and HAuCl4·3H2O in the electrolyte being 10 mM.

[0080] Comparative Application Example 1

[0081] Based on Application Example 1, the cathode was modified to Comparative Example 1, and other conditions remained unchanged.

[0082] Under anhydrous and oxygen-free conditions (oxygen content ≤ 0.1 ppm, water content ≤ 0.1 ppm), the nitrogen adsorption capacity of the cathode before the nitrogen reduction reaction in Example 1 and Comparative Application Example 1 was tested using a chemical adsorption instrument. The results are as follows: Figure 3 As shown, Figure 3 2-TPD diagram of the cathode before the nitrogen reduction reaction in Application Example 1 and Comparative Application Example 1.

[0083] from Figure 3 It can be seen that physical adsorption occurs at 173°C and chemical adsorption occurs at 358°C, indicating that COF-5 in the electrode of Example 1 has a better adsorption capacity for nitrogen.

[0084] Under anhydrous and oxygen-free conditions (oxygen content ≤ 0.1 ppm, water content ≤ 0.1 ppm), the ammonia production performance of Example 1 and Comparative Example 1 was tested using a UV-visible spectrometer. The results are as follows: Figure 4 As shown, Figure 4 UV-vis graphs of ammonia production in Application Example 1 and Comparative Application Example 1.

[0085] from Figure 4 It can be seen that the nitrogen reduction product reacts with the proton donor to generate ammonia.

[0086] Example 2

[0087] An electrode comprising an artificial solid electrolyte interface layer, wherein the artificial solid electrolyte interface layer is composed of a solid electrolyte and a binder;

[0088] The artificial solid electrolyte interface layer covers the electrode;

[0089] The solid electrolyte is ZIF-8;

[0090] The binder is PVDF;

[0091] The thickness of the artificial solid electrolyte interface layer is 50 μm;

[0092] The electrode is a stainless steel mesh loaded with copper foam; the copper foam is deposited on the stainless steel mesh by electroplating, and the electroplating method is: applying -1Acm -2 The current density was set to 1 min to obtain a stainless steel mesh loaded with foam copper; the size of the stainless steel mesh was 25 cm 2 ; The electrolyte was prepared by dissolving CuSO4 (Merck, 98%) in 1.5 M H2SO4 (SigmaAldrich, 99.999%), and the CuSO4 concentration in the electrolyte was 0.4 M;

[0093] The preparation method of the electrode containing the artificial solid electrolyte interface layer is:

[0094] (1) mixing a solid electrolyte, an organic solvent, and a binder to obtain a slurry; the organic solvent is ethanol; based on the mass of the slurry being 100%, the mass of the solid electrolyte is 80%, the mass of the organic solvent is 15%, and the mass of the binder is 5%;

[0095] (2) coating the slurry obtained in step (1) on an electrode to obtain an electrode containing an artificial solid electrolyte interface layer;

[0096] The preparation method of ZIF-8 is as follows: zinc nitrate (0.297 g, 1 mmol) is dissolved in 20 mL of methanol and stirred until completely dissolved to obtain solution A; 2-methylimidazole (0.328 g, 4 mmol) is dissolved in 20 mL of methanol to obtain solution B; solution B is quickly poured into solution A, mixed, and then transferred to a polytetrafluoroethylene-lined high-pressure reactor, reacted at 100° C. for 24 hours, naturally cooled, and then centrifuged, washed with methanol three times, and vacuum dried at 60° C. to obtain ZIF-8.

[0097] Example 3

[0098] An electrode comprising an artificial solid electrolyte interface layer, wherein the artificial solid electrolyte interface layer is composed of a solid electrolyte and a binder;

[0099] The artificial solid electrolyte interface layer covers the electrode;

[0100] The solid electrolyte is Fe / rGO;

[0101] The binder is PVDF;

[0102] The thickness of the artificial solid electrolyte interface layer is 50 μm;

[0103] The electrode is a stainless steel mesh loaded with copper foam; the copper foam is deposited on the stainless steel mesh by electroplating, and the electroplating method is: applying -1Acm -2 The current density was set to 1 min to obtain a stainless steel mesh loaded with foam copper; the size of the stainless steel mesh was 25 cm 2 ; The electrolyte was prepared by dissolving CuSO4 (Merck, 98%) in 1.5 M H2SO4 (SigmaAldrich, 99.999%), and the CuSO4 concentration in the electrolyte was 0.4 M;

[0104] The preparation method of the electrode containing the artificial solid electrolyte interface layer is:

[0105] (1) mixing a solid electrolyte, an organic solvent, and a binder to obtain a slurry; the organic solvent is ethanol; based on the mass of the slurry being 100%, the mass of the solid electrolyte is 80%, the mass of the organic solvent is 15%, and the mass of the binder is 5%;

[0106] (2) coating the slurry obtained in step (1) on an electrode to obtain an electrode containing an artificial solid electrolyte interface layer;

[0107] The Fe / rGO preparation method comprises: ultrasonically dispersing 50 mg of graphene oxide in 50 mL of deionized water for 1 hour to obtain a dispersion; then dissolving 0.5 g of FeCl3·6H2O in the dispersion and stirring for 30 minutes; adding 0.2 g of ascorbic acid as a reducing agent and stirring for 10 minutes; then transferring the dispersion to an autoclave and hydrothermally reacting it at 180°C for 12 hours; then cooling and centrifuging the mixture; washing it with ethanol and water three times; and then vacuum drying it at 60°C for 12 hours to obtain Fe / rGO.

[0108] Example 4

[0109] An electrode comprising an artificial solid electrolyte interface layer, wherein the artificial solid electrolyte interface layer is composed of a solid electrolyte and a binder;

[0110] The artificial solid electrolyte interface layer covers the electrode;

[0111] The solid electrolyte is PEO with a molecular weight of 1 million;

[0112] The binder is PVDF;

[0113] The thickness of the artificial solid electrolyte interface layer is 50 μm;

[0114] The electrode is a stainless steel mesh loaded with copper foam; the copper foam is deposited on the stainless steel mesh by electroplating, and the electroplating method is: applying -1Acm -2 The current density was set to 1 min to obtain a stainless steel mesh loaded with foam copper; the size of the stainless steel mesh was 25 cm 2 ; The electrolyte was prepared by dissolving CuSO4 (Merck, 98%) in 1.5 M H2SO4 (SigmaAldrich, 99.999%), and the CuSO4 concentration in the electrolyte was 0.4 M;

[0115] The preparation method of the electrode containing the artificial solid electrolyte interface layer is:

[0116] (1) mixing a solid electrolyte, an organic solvent, and a binder to obtain a slurry; the organic solvent is ethanol; based on the mass of the slurry being 100%, the mass of the solid electrolyte is 80%, the mass of the organic solvent is 15%, and the mass of the binder is 5%;

[0117] (2) coating the slurry obtained in step (1) on an electrode to obtain an electrode containing an artificial solid electrolyte interface layer.

[0118] Example 5

[0119] An electrode comprising an artificial solid electrolyte interface layer, wherein the artificial solid electrolyte interface layer is composed of a solid electrolyte and a binder;

[0120] The artificial solid electrolyte interface layer covers the electrode;

[0121] The solid electrolyte is lithium oxide, purchased from Adamas, with a purity of 99.9%;

[0122] The binder is PVDF;

[0123] The thickness of the artificial solid electrolyte interface layer is 50 μm;

[0124] The electrode is a stainless steel mesh loaded with copper foam; the copper foam is deposited on the stainless steel mesh by electroplating, and the electroplating method is: applying -1Acm -2 The current density was set to 1 min to obtain a stainless steel mesh loaded with foam copper; the size of the stainless steel mesh was 25 cm 2 ; The electrolyte was prepared by dissolving CuSO4 (Merck, 98%) in 1.5 M H2SO4 (SigmaAldrich, 99.999%), and the CuSO4 concentration in the electrolyte was 0.4 M;

[0125] The preparation method of the electrode containing the artificial solid electrolyte interface layer is:

[0126] (1) mixing a solid electrolyte, an organic solvent, and a binder to obtain a slurry; the organic solvent is ethanol; based on the mass of the slurry being 100%, the mass of the solid electrolyte is 80%, the mass of the organic solvent is 15%, and the mass of the binder is 5%;

[0127] (2) coating the slurry obtained in step (1) on an electrode to obtain an electrode containing an artificial solid electrolyte interface layer.

[0128] Example 6

[0129] An electrode comprising an artificial solid electrolyte interface layer, wherein the artificial solid electrolyte interface layer is composed of a solid electrolyte and a binder;

[0130] The artificial solid electrolyte interface layer covers the electrode;

[0131] The solid electrolyte is lithium sulfide, purchased from Adamas, with a purity of 99.9%;

[0132] The binder is PVDF;

[0133] The thickness of the artificial solid electrolyte interface layer is 50 μm;

[0134] The electrode is a stainless steel mesh loaded with copper foam; the copper foam is deposited on the stainless steel mesh by electroplating, and the electroplating method is: applying -1Acm-2 The current density was set to 1 min to obtain a stainless steel mesh loaded with foam copper; the size of the stainless steel mesh was 25 cm 2 ; The electrolyte was prepared by dissolving CuSO4 (Merck, 98%) in 1.5 M H2SO4 (SigmaAldrich, 99.999%), and the CuSO4 concentration in the electrolyte was 0.4 M;

[0135] The preparation method of the electrode containing the artificial solid electrolyte interface layer is:

[0136] (1) mixing a solid electrolyte, an organic solvent, and a binder to obtain a slurry; the organic solvent is ethanol; based on the mass of the slurry being 100%, the mass of the solid electrolyte is 80%, the mass of the organic solvent is 15%, and the mass of the binder is 5%;

[0137] (2) coating the slurry obtained in step (1) on an electrode to obtain an electrode containing an artificial solid electrolyte interface layer.

[0138] Example 7

[0139] An electrode comprising an artificial solid electrolyte interface layer, wherein the artificial solid electrolyte interface layer is composed of a solid electrolyte and a binder;

[0140] The artificial solid electrolyte interface layer covers the electrode;

[0141] The solid electrolyte is lithium hydride, purchased from Adamas, with a purity of 99.9%;

[0142] The binder is PVDF;

[0143] The thickness of the artificial solid electrolyte interface layer is 50 μm;

[0144] The electrode is a stainless steel mesh loaded with copper foam; the copper foam is deposited on the stainless steel mesh by electroplating, and the electroplating method is: applying -1Acm -2 The current density was set to 1 min to obtain a stainless steel mesh loaded with foam copper; the size of the stainless steel mesh was 25 cm 2 ; The electrolyte was prepared by dissolving CuSO4 (Merck, 98%) in 1.5M H2SO4 (SigmaAldrich, 99.999%), and the CuSO4 concentration in the electrolyte was 0.4M; the preparation method of the electrode containing the artificial solid electrolyte interface layer was as follows:

[0145] (1) mixing a solid electrolyte, an organic solvent, and a binder to obtain a slurry; the organic solvent is ethanol; based on the mass of the slurry being 100%, the mass of the solid electrolyte is 80%, the mass of the organic solvent is 15%, and the mass of the binder is 5%;

[0146] (2) coating the slurry obtained in step (1) on an electrode to obtain an electrode containing an artificial solid electrolyte interface layer.

[0147] Example 8

[0148] An electrode comprising an artificial solid electrolyte interface layer, wherein the artificial solid electrolyte interface layer is composed of a solid electrolyte and a binder;

[0149] The artificial solid electrolyte interface layer covers the electrode;

[0150] The solid electrolyte is lithium nitride Li3N, purchased from adamas, with a purity of 99.9%;

[0151] The binder is PVDF;

[0152] The thickness of the artificial solid electrolyte interface layer is 50 μm;

[0153] The electrode is a stainless steel mesh loaded with copper foam; the copper foam is deposited on the stainless steel mesh by electroplating, and the electroplating method is: applying -1Acm -2 The current density was set to 1 min to obtain a stainless steel mesh loaded with foam copper; the size of the stainless steel mesh was 25 cm 2 ; The electrolyte was prepared by dissolving CuSO4 (Merck, 98%) in 1.5 M H2SO4 (SigmaAldrich, 99.999%), and the CuSO4 concentration in the electrolyte was 0.4 M;

[0154] The preparation method of the electrode containing the artificial solid electrolyte interface layer is:

[0155] (1) mixing a solid electrolyte, an organic solvent, and a binder to obtain a slurry; the organic solvent is ethanol; based on the mass of the slurry being 100%, the mass of the solid electrolyte is 80%, the mass of the organic solvent is 15%, and the mass of the binder is 5%;

[0156] (2) coating the slurry obtained in step (1) on an electrode to obtain an electrode containing an artificial solid electrolyte interface layer.

[0157] Example 9

[0158] An electrode comprising an artificial solid electrolyte interface layer, wherein the artificial solid electrolyte interface layer is composed of a solid electrolyte and a binder;

[0159] The artificial solid electrolyte interface layer covers the electrode;

[0160] The solid electrolyte is lithium carbide Li2C2, purchased from adamas, with a purity of 99.9%;

[0161] The binder is PVDF;

[0162] The thickness of the artificial solid electrolyte interface layer is 50 μm;

[0163] The electrode is a stainless steel mesh loaded with copper foam; the copper foam is deposited on the stainless steel mesh by electroplating, and the electroplating method is: applying -1Acm -2 The current density was set to 1 min to obtain a stainless steel mesh loaded with foam copper; the size of the stainless steel mesh was 25 cm 2 ; The electrolyte was prepared by dissolving CuSO4 (Merck, 98%) in 1.5M H2SO4 (SigmaAldrich, 99.999%), and the CuSO4 concentration in the electrolyte was 0.4M; the preparation method of the electrode containing the artificial solid electrolyte interface layer was as follows:

[0164] (1) mixing a solid electrolyte, an organic solvent, and a binder to obtain a slurry; the organic solvent is ethanol; based on the mass of the slurry being 100%, the mass of the solid electrolyte is 80%, the mass of the organic solvent is 15%, and the mass of the binder is 5%;

[0165] (2) coating the slurry obtained in step (1) on an electrode to obtain an electrode containing an artificial solid electrolyte interface layer.

[0166] Example 10

[0167] An electrode comprising an artificial solid electrolyte interface layer, wherein the artificial solid electrolyte interface layer is composed of a solid electrolyte and a binder;

[0168] The artificial solid electrolyte interface layer covers the electrode;

[0169] The solid electrolyte is lithium fluoride LiF, purchased from Adamas, with a purity of 99.9%;

[0170] The binder is PVDF;

[0171] The thickness of the artificial solid electrolyte interface layer is 50 μm;

[0172] The electrode is a stainless steel mesh loaded with copper foam; the copper foam is deposited on the stainless steel mesh by electroplating, and the electroplating method is: applying -1Acm -2The current density was set to 1 min to obtain a stainless steel mesh loaded with foam copper; the size of the stainless steel mesh was 25 cm 2 ; The electrolyte was prepared by dissolving CuSO4 (Merck, 98%) in 1.5 M H2SO4 (SigmaAldrich, 99.999%), and the CuSO4 concentration in the electrolyte was 0.4 M;

[0173] The preparation method of the electrode containing the artificial solid electrolyte interface layer is:

[0174] (1) mixing a solid electrolyte, an organic solvent, and a binder to obtain a slurry; the organic solvent is ethanol; based on the mass of the slurry being 100%, the mass of the solid electrolyte is 80%, the mass of the organic solvent is 15%, and the mass of the binder is 5%;

[0175] (2) coating the slurry obtained in step (1) on an electrode to obtain an electrode containing an artificial solid electrolyte interface layer.

[0176] Application Examples 2-10

[0177] Based on Application Example 1, the cathode was modified to Examples 2 to 10 in sequence, with other conditions remaining unchanged.

[0178] Under anhydrous and oxygen-free conditions (oxygen content ≤ 0.1 ppm, water content ≤ 0.1 ppm), the ammonia production in Examples 2 to 10 was tested using an NMR spectrometer. The results are as follows: Figure 5 As shown, Figure 5 1H NMR diagram of ammonia produced in Application Examples 2 to 10.

[0179] from Figure 5 It can be seen that the proton signal of ammonia in the product is strong and clear, and the product contains ammonia.

[0180] The ammonia generation rate and Faradaic efficiency of Examples 1 to 10 were tested, and the results are shown in Table 1.

[0181] Table 1 Ammonia generation rate and Faraday efficiency of application examples 1 to 10

[0182] Application Examples Faradaic efficiency of ammonia (%) <![CDATA[Rate of ammonia production (nmols -1 cm -2 )]]> 1 95 12.8 2 97 13.1 3 84 11.3 4 86 11.6 5 73 9.8 6 75 10.1 7 84 11.3 8 92 12.4 9 94 12.7 10 83 11.2

[0183] As can be seen from Table 1, the ammonia generation rate of the present invention is 9.8-13.1 nmol s -1 cm -2 The Faradaic efficiency of ammonia is 73-97%, indicating that the present invention can improve the stability of alkali metal-mediated ammonia synthesis.

[0184] It can be seen from the above embodiments and comparative examples that the electrode containing the artificial solid electrolyte interface layer provided by the present invention can improve the stability of alkali metal-mediated ammonia synthesis.

[0185] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. An electrode comprising an artificial solid electrolyte interface layer, wherein the artificial solid electrolyte interface layer comprises a solid electrolyte and a binder.

2. The electrode according to claim 1, characterized in that The artificial solid electrolyte interface layer covers the electrode.

3. The electrode according to claim 1, characterized in that The thickness of the artificial solid electrolyte interface layer is 1 to 100 μm.

4. The electrode according to claim 1, characterized in that The solid electrolyte includes at least one of oxides, sulfides, hydrides, nitrides, carbides, halides, COF-based materials, MOF-based materials, graphene-based materials, and polymers.

5. The method for preparing an electrode containing an artificial solid electrolyte interface layer according to any one of claims 1 to 4, comprising the following steps: (1) mixing a solid electrolyte, an organic solvent, and a binder to obtain a slurry; (2) coating the slurry obtained in step (1) on an electrode to obtain an electrode containing an artificial solid electrolyte interface layer.

6. The preparation method according to claim 5, characterized in that Based on the mass of the slurry being 100%, the mass of the solid electrolyte in step (1) is 60-95%, the mass of the organic solvent is 3-20%, and the mass of the binder is 2-20%.

7. Use of the electrode containing an artificial solid electrolyte interface layer according to any one of claims 1 to 4 or the electrode containing an artificial solid electrolyte interface layer prepared by the preparation method according to claim 5 or 6 in alkali metal-mediated electrosynthesis of ammonia.

8. The use according to claim 7, characterized in that The method for synthesizing ammonia through alkali metal mediation comprises: An electrode containing an artificial solid electrolyte interface layer is used as the cathode, an alkali metal salt solution is used as the electrolyte, nitrogen is introduced into the electrolytic cell, and an electrochemical reaction is carried out to produce ammonia.

9. The use according to claim 8, characterized in that The flow rate of the nitrogen gas is 5-25 sccm.

10. The use according to claim 8, characterized in that The current density of the electrochemical reaction is 0.01-1 mA cm -2 .

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