A solid oxide electrolysis cell for high temperature electrolysis of carbon dioxide and a method of manufacture

Abstract

A solid oxide electrolysis cell for high temperature electrolysis of carbon dioxide and a method of making. The cell comprises a solid electrolyte substrate, a separator layer on one side of the solid electrolyte substrate, a cathode on the separator layer, and an anode on the other side of the solid electrolyte substrate. The solid electrolyte substrate material is La 0.9 Sr 0.1 Ga 0.8 Mg 0.2 O3(LSGM). The separator layer material is Ce 0.8 Sm 0.2 O 1.9 (SDC). The cathode material is a composite of Sr2Fe 1.5 Mo 0.5 O6(SFM) and Ce 0.8 Sm 0.2 O 1.9 (SDC) with La 0.8 Sr 0.2 Cr 0.5 Mn 0.5 O3(LSCM) or CuO nanoparticles attached to the cathode material. The anode material is a composite of La 0.7 Sr 0.3 Co 0.2 Fe 0.8 O3(LSCF) and Ce 0.8 Sm 0.2 O 1.9 (SDC). The nanoparticles provide additional active sites and sufficient reaction interfaces and gas diffusion channels to effectively promote the reduction of CO2 and help reduce the local carbon concentration and the incidence of carbon deposition.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of solid oxide electrolysis cells, in particular to a solid oxide electrolysis cell for high-temperature electrolysis of carbon dioxide and a preparation method thereof. BACKGROUND

[0002] Due to the large use of fossil fuels such as oil and natural gas, the emission of CO2 has increased sharply. The emission of greenhouse gases (mainly CO2) has been considered as the main factor leading to global warming. Therefore, while developing clean and renewable energy, carbon dioxide emission reduction or conversion technology should be explored. Solid oxide electrolysis cell (SOEC) is one of the most promising technologies for high-temperature electrolysis of CO2, and has great commercial prospects. SOEC contains electrolyte, anode and cathode. Under the driving of external voltage, CO2 is electrochemically dissociated on the cathode side to form CO and O 2- . The generated CO can be used as a valuable fuel or industrial raw material. O 2- is transferred to the anode side through the electrolyte and eventually loses electrons to generate oxygen. In SOEC, the CO2 reduction reaction occurring at the cathode has a greater polarization loss than the oxygen evolution reaction at the anode, so the development and research of electrolysis cell materials mainly focus on the optimization design of cathode structure and material.

[0003] Nickel yttrium stabilized zirconia (Ni-YSZ) is widely used as a cathode material in solid oxide electrolysis cells (SOEC) due to its excellent electrocatalytic performance and low cost. However, carbon deposition easily occurs on Ni-YSZ, and Ni is easily oxidized during the redox process, resulting in poor electrolysis performance. SUMMARY

[0004] The purpose of the present application is to provide a solid oxide electrolysis cell for high-temperature electrolysis of carbon dioxide to solve the technical problem of poor catalytic performance of the cathode material in the prior art. Meanwhile, the purpose of the present application is also to provide a preparation method of the above-mentioned solid oxide electrolysis cell.

[0005] To achieve the above-mentioned purpose, a solid oxide electrolysis cell for high-temperature electrolysis of carbon dioxide adopts the following technical scheme: a solid oxide electrolysis cell for high-temperature electrolysis of carbon dioxide, comprising a solid electrolyte substrate, a separation layer located on one side of the solid electrolyte substrate, a cathode located on the separation layer, and an anode located on the other side of the solid electrolyte substrate.

[0006] The material of the solid electrolyte substrate is La 0.9 Sr 0.1 Ga 0.8 Mg 0.2 O3(LSGM), and the material of the separation layer is Ce 0.8 Sm 0.2 O 1.9(SDC) and the cathode material is Sr2Fe 1.5 Mo 0.5 O6(SFM) and Ce 0.8 Sm 0.2 O 1.9 (SDC) and the cathode material is attached with La 0.8 Sr 0.2 Cr 0.5 Mn 0.5 O3(LSCM) or CuO nanoparticles; the anode material is La 0.7 Sr 0.3 Co 0.2 Fe 0.8 O3(LSCF) and Ce 0.8 Sm 0.2 O 1.9 (SDC).

[0007] The attached amount of the CuO nanoparticles or La 0.8 Sr 0.2 Cr 0.5 Mn 0.5 O3(LSCM) nanoparticles is 2wt%-8wt% of the mass ratio of the nanoparticles to the cathode material.

[0008] A preparation method of a solid oxide electrolysis cell for high-temperature electrolysis of carbon dioxide, comprising the following steps,

[0009] I. preparing Sr2Fe 1.5 Mo 0.5 O6(SFM) powder, La 0.7 Sr 0.3 Co 0.2 Fe 0.8 O3(LSCF) powder and Ce 0.8 Sm 0.2 O 1.9 (SDC) powder;

[0010] II. preparing the powders in step I into cathode slurry, anode slurry and separator layer slurry;

[0011] III. using the method of screen printing to brush the separator layer slurry in step II on one side of the solid electrolyte substrate, drying and calcining to obtain the separator layer; then using the method of screen printing to brush the cathode slurry on the separator layer and drying to form the cathode; then using the method of screen printing to brush the anode slurry on the other side of the solid electrolyte substrate and drying to form the anode; finally calcining to obtain the complete solid oxide electrolysis cell;

[0012] IV. The cathode of the solid oxide electrolysis cell in step III is subjected to an impregnation modification treatment to make La adhere to the cathode material 0.8 Sr 0.2 Cr 0.5 Mn 0.5 O3(LSCM) nanoparticles or CuO nanoparticles.

[0013] In step I, Sr2Fe 1.5 Mo 0.5 O6(SFM) powder is prepared by the following method,

[0014] 1) Sr(NO3)2, Fe(NO3)3·9H2O and (NH4)6Mo7O 24 ·4H2O are dissolved in deionized water as raw materials to form a nitrate solution;

[0015] 2) Citric acid and ethylenediaminetetraacetic acid are added to the above solution, and the molar ratio of the total amount of metal ions to ethylenediaminetetraacetic acid and citric acid is 1:1:1.5;

[0016] 3) Ammonia solution is added to the solution in step 2) to adjust the pH to 6-8;

[0017] 4) The solution in step 3) is stirred in a water bath to obtain a wet gel;

[0018] 5) The wet gel is dried to obtain a dry gel;

[0019] 6) The dry gel is calcined to obtain Sr2Fe 1.5 Mo 0.5 O6(SFM) powder.

[0020] In step I, La 0.7 Sr 0.3 Co 0.2 Fe 0.8 O3(LSCF) powder is prepared by the following method,

[0021] 1) La(NO3)3·6H2O, Sr(NO3)2, Fe(NO3)3·9H2O and Co(NO3)2·6H2O are dissolved in deionized water as raw materials to form a nitrate solution;

[0022] 2) Citric acid and ethylenediaminetetraacetic acid are added to the above solution, and the molar ratio of the total amount of metal ions to ethylenediaminetetraacetic acid and citric acid is 1:1:1.5;

[0023] 3) Ammonia solution is added to the solution in step 2) to adjust the pH to 6-8;

[0024] 4) The solution in step 3) is stirred in a water bath to obtain a wet gel;

[0025] 5) drying the wet gel to obtain a dry gel;

[0026] 6) calcining the dry gel to obtain La 0.7 Sr 0.3 Co 0.2 Fe 0.8 O3(LSCF) powder.

[0027] In Step I, Ce 0.8 Sm 0.2 O 1.9 (SDC) powder is prepared by the following method,

[0028] 1) dissolving Ce(NO3)3·6H2O and Sm(NO3)3·6H2O as raw materials in deionized water to form a nitrate solution;

[0029] 2) adding citric acid and ethylenediaminetetraacetic acid to the above solution, and the molar ratio of the total amount of metal ions to ethylenediaminetetraacetic acid and citric acid is 1:1:1.5;

[0030] 3) adding an ammonia solution to the solution in step 2) to adjust the pH to 6-8;

[0031] 4) stirring the solution in step 3) in a water bath to obtain a wet gel;

[0032] 5) drying the wet gel to obtain a dry gel;

[0033] 6) calcining the dry gel to obtain Ce 0.8 Sm 0.2 O 1.9 (SDC) powder.

[0034] The SFM powder, the SDC powder and the terpineol are placed in a cup-shaped container in a mass ratio of 65:35:150, ground until uniformly mixed to form a cathode slurry with viscosity; the LSCF powder, the SDC powder and the terpineol are placed in a cup-shaped container in a mass ratio of 65:35:150, ground until uniformly mixed to form an anode slurry with viscosity; the SDC powder and the terpineol are placed in a cup-shaped container in a mass ratio of 1:1.5, ground until uniformly mixed to form a separator layer slurry with viscosity.

[0035] In Step IV, the preparation of the impregnation solution is as follows,

[0036] Cu(NO3)2·3H2O is dissolved in anhydrous ethanol to prepare a first type of nitrate solution with a Cu(NO3)2·3H2O concentration of 0.1 moL·L -1 .

[0037] In step IV, the preparation of the impregnation solution is as follows,

[0038] 1) La(NO3)3·6H2O, Sr(NO3)2, Cr(NO3)3·9H2O, Mn(NO3)2 are dissolved in anhydrous ethanol to form a nitrate solution,

[0039] 2) Citrate and ethylenediaminetetraacetic acid are added to the above solution, and the molar ratio of the total amount of metal ions: ethylenediaminetetraacetic acid: citric acid is 1:1:1.5;

[0040] 3) The prepared solution is heated in a water bath and stirred, and ammonia water is added to control the pH value of the solution to 6-8, to prepare a La 0.8 Sr 0.2 Cr 0.5 Mn 0.5 O3(LSCM) concentration of 0.1 moL·L -1 second type of nitrate solution.

[0041] In step IV, the first type of nitrate solution or the second type of nitrate solution is dropped on the cathode material, dried, and then calcined, so that CuO nanoparticles or La 0.8 Sr 0.2 Cr 0.5 Mn 0.5 O3(LSCM) nanoparticles are attached to the cathode.

[0042] The beneficial effects of the present application: the La 0.8 Sr 0.2 Cr 0.5 Mn 0.5 O3(LSCM) nanoparticles or CuO nanoparticles attached to the cathode material have strong oxygen storage capacity (LSCM nanoparticles) and carbon deposition resistance and enhanced CO2 reduction capacity (CuO nanoparticles), which can effectively improve the current density of electrochemical reduction of CO2 and reduce the polarization resistance. At the same time, these nanoparticles also effectively increase the specific surface area of the electrode and produce additional active sites, providing sufficient reaction interface and gas diffusion channels, which can effectively promote the reduction of CO2 and help to reduce the local carbon concentration and reduce the incidence of carbon deposition. Moreover, the production cost is low, and the operation is simple and convenient. BRIEF DESCRIPTION OF DRAWINGS

[0043] Figure 1 is a structural schematic diagram of a high-temperature carbon dioxide electrolysis solid oxide electrolysis cell of the present application;

[0044] Figure 2 is the XRD pattern of the electrode of the SFM obtained by the comparative example and the Cu-SFM and LSCM-SFM obtained by the experimental example one;

[0045] Figure 3 These are surface scanning electron microscope (SEM) images of the electrodes of the SFM obtained in the comparative example and the Cu-SFM and LSCM-SFM obtained in Experimental Example 1.

[0046] Figure 4 The impedance spectrum curve of a symmetrical cell at 800℃ in a CO2 atmosphere is shown.

[0047] Figure 5 The impedance spectrum curves of the SFM obtained in the comparative example and the Cu-SFM and LSCM-SFM obtained in Experimental Example 1 during the electrolysis of CO2 at 800℃ and open circuit voltage (OCV) are shown.

[0048] Figure 6 The current density of the SFM obtained in the comparative example and the Cu-SFM and LSCM-SFM obtained in Experimental Example 1 during the electrolysis of CO2 at 800℃ is shown. Detailed Implementation

[0049] The present invention provides a solid oxide electrolytic cell for high-temperature electrolysis of carbon dioxide, such as... Figure 1 As shown, it includes a solid electrolyte substrate, an isolation layer located on one side of the solid electrolyte substrate, a cathode located on the isolation layer, and an anode located on the other side of the solid electrolyte substrate. The solid electrolyte substrate material is La. 0.9 Sr 0.1 Ga 0.8 Mg 0.2 O3 (LSGM). The insulating layer material is Ce. 0.8 Sm 0.2 O 1.9 (SDC). The cathode material is Sr2Fe. 1.5 Mo 0.5 O6 (SFM) and Ce 0.8 Sm 0.2 O 1.9 A composite material consisting of (SDC) and La attached to the cathode material. 0.8 Sr 0.2 Cr 0.5 Mn 0.5 O3 (LSCM) nanoparticles or CuO nanoparticles. The anode material is La. 0.7 Sr 0.3 Co 0.2 Fe 0.8 O3 (LSCF) and Ce 0.8 Sm 0.2 O 1.9 A complex composed of (SDC).

[0050] Among them, the above-mentioned La 0.8 Sr 0.2 Cr 0.5 Mn 0.5The attachment amount of O3(LSCM) nanoparticles or CuO nanoparticles is 2wt%-8wt% of the mass ratio of the nanoparticles to the cathode material.

[0051] The preparation method of the solid electrolyte reactor is described in detail below by way of examples:

[0052] Example 1

[0053] I. Preparation of Sr2FeMoO6(SFM) powder 1.5 Mo 0.5 O6(SFM) powder, La 0.7 Sr 0.3 Co 0.2 Fe 0.8 O3(LSCF) powder and Ce 0.8 Sm 0.2 O 1.9 (SDC) powder.

[0054] Sr2Fe 1.5 Mo 0.5 O6(SFM) powder:

[0055] 1) Sr(NO3)2, Fe(NO3)3·9H2O and (NH4)6Mo7O 24 ·4H2O in a certain stoichiometric ratio (molar ratio of 2:1.5:0.5) were dissolved in deionized water.

[0056] 2) Citric acid and ethylenediaminetetraacetic acid were added to the uniformly dissolved solution, and the molar ratio of the total amount of metal ions to ethylenediaminetetraacetic acid and citric acid was 1:1:1.5.

[0057] 3) After the solution was uniformly mixed, ammonia water was slowly added to adjust the pH to 7, and stirring was continuously performed.

[0058] 4) Then, a stirring rod was added to continue stirring in warm water at 80°C until a yellow-brown transparent wet gel with viscosity was formed.

[0059] 5) The prepared wet gel was quickly transferred to a cup-shaped vessel, dried in an oven at 160°C for 7h to obtain a porous dry gel.

[0060] 6) Then, the dry gel was transferred to a muffle furnace and calcined at 1050°C for 5h to obtain SFM powder.

[0061] La 0.7 Sr 0.3 Co 0.2 Fe 0.8 O3(LSCF) powder:

[0062] 1) Weigh a certain stoichiometric ratio (molar ratio of 7:3:8:2) of La(NO3)3.6H2O, Sr(NO3)2, Fe(NO3)3.9H2O and Co(NO3)2.6H2O and dissolve them in deionized water.

[0063] 2) Add citric acid and ethylenediaminetetraacetic acid to the uniformly dissolved solution, and the molar ratio of the total amount of metal ions to ethylenediaminetetraacetic acid and citric acid is 1:1:1.5.

[0064] 3) After the solution is uniformly mixed, slowly add ammonia water to adjust the pH to 7, and continuously stir.

[0065] 4) Then add a stirring rod to the warm water at 80°C and continue stirring until a yellowish-brown, transparent, and sticky wet gel is formed.

[0066] 5) Quickly transfer the prepared wet gel to a cup-shaped vessel and dry it in an oven at 160°C for 7h to obtain a porous dry gel.

[0067] 6) Then transfer the dry gel to a muffle furnace and calcine it at 1050°C for 3h to obtain LSCF powder.

[0068] Ce 0.8 Sm 0.2 O 1.9 Preparation of SDC powder:

[0069] 1) Weigh a certain stoichiometric ratio (molar ratio of 4:1) of Ce(NO3)3.6H2O and Sm(NO3)3.6H2O and dissolve them in deionized water.

[0070] 2) Add citric acid and ethylenediaminetetraacetic acid to the uniformly dissolved solution, and the molar ratio of the total amount of metal ions to ethylenediaminetetraacetic acid and citric acid is 1:1:1.5.

[0071] 3) After the solution is uniformly mixed, slowly add ammonia water to adjust the pH to 7, and continuously stir.

[0072] 4) Then add a stirring rod to the warm water at 80°C and continue stirring until a yellowish-brown, transparent, and sticky wet gel is formed.

[0073] 5) Quickly transfer the prepared wet gel to a cup-shaped vessel and dry it in an oven at 160°C for 7h to obtain a porous dry gel.

[0074] 6) Then transfer the dry gel to a muffle furnace and calcine it at 1050°C for 3h to obtain LSCF powder.

[0075] Ⅱ, prepare the powder in step I into cathode slurry, anode slurry and separator slurry.

[0076] Preparation of cathode slurry: SFM powder, SDC powder and terpineol were put in a small cup-shaped vessel in a mass ratio of 65:35:150, and grinded for 1 h until mixed uniformly to form an electrode slurry with viscosity.

[0077] Preparation of anode slurry: LSCF powder, SDC powder and terpineol were put in a small cup-shaped vessel in a mass ratio of 65:35:150, and grinded for 1 h until mixed uniformly to form an electrode slurry with viscosity.

[0078] Preparation of isolation layer slurry: SDC powder and terpineol were put in a small cup-shaped vessel in a mass ratio of 1:1.5, and grinded for 1 h until mixed uniformly to form an electrode slurry with viscosity.

[0079] III, the isolation layer slurry in step 2) was brushed on one side of the solid electrolyte substrate by the method of screen printing, and was dried and calcined to obtain the isolation layer; then the cathode slurry was brushed on the isolation layer by the method of screen printing, and was dried to obtain the cathode; then the anode slurry was brushed on the other side of the solid electrolyte substrate by the method of screen printing, and was dried to form the anode; finally, calcination was performed to obtain the complete solid oxide electrolysis cell.

[0080] Preparation of solid electrolyte substrate: LSGM powder (obtained by direct purchase) was dry-pressed into an electrolyte green body under a pressure of 200 MPa, and then was calcined at 1400°C for 4 h to obtain the solid electrolyte substrate.

[0081] Specifically, the isolation layer slurry was uniformly brushed on one side of the electrolyte substrate by the method of screen printing, and was dried in an oven at 100°C and then was transferred to a muffle furnace for calcination at 1200°C for 5 h. Then the prepared cathode slurry was uniformly brushed on the same side of the electrolyte substrate by the method of screen printing, and was dried in an oven at 100°C. After taking out, the prepared anode slurry was uniformly brushed on the other side of the electrolyte substrate by the method of screen printing, and was dried in an oven at 100°C. After taking out, the sample was transferred to a muffle furnace for calcination at 1100°C for 2 h to obtain the complete solid oxide electrolysis cell.

[0082] IV, the cathode of the solid oxide electrolysis cell in step III was subjected to impregnation modification treatment, so that La 0.8 Sr 0.2 Cr 0.5 Mn 0.5 O3(LSCM) nanoparticles or CuO nanoparticles were attached to the base layer of the cathode.

[0083] Preparation of impregnation solution:

[0084] First type of nitrate solution:

[0085] Cu(NO3)2·3H2O was dissolved in anhydrous ethanol to prepare a 0.1 moL·L -1 nitrate solution.

[0086] Second type of nitrate solution:

[0087] 1) La(NO3)3·6H2O, Sr(NO3)2, Cr(NO3)3·9H2O, Mn(NO3)2 were mixed in a certain stoichiometric ratio (molar ratio of 8:2:5:5) to prepare a nitrate solution;

[0088] 2) Citrate and ethylenediaminetetraacetic acid were added to the above solution, and the molar ratio of total metal ions: ethylenediaminetetraacetic acid: citric acid was 1:1:1.5.

[0089] 3) The prepared solution was stirred in a water bath at 80℃, and a certain amount of ammonia water was slowly added while the pH was controlled at 7, to prepare a 0.1 moL·L -1 nitrate solution.

[0090] Electrode modification: pipette the first type of nitrate solution or the second type of nitrate solution on the cathode side of the solid oxide electrolysis cell, dry in an oven at 80℃, and then calcine the cell in a muffle furnace at 600℃ for 2h to obtain the modified electrode with CuO nanoparticles or LSCM nanoparticles attached to the cathode. The content of attached CuO nanoparticles or LSCM nanoparticles accounts for 5wt% of the mass ratio of the cathode material. The CuO and LSCM impregnated electrodes are named Cu-SFM and LSCM-SFM respectively.

[0091] Example Two

[0092] I. Preparation of Sr2Fe 1.5 Mo 0.5 O6(SFM) powder, La 0.7 Sr 0.3 Co 0.2 Fe 0.8 O3(LSCF) powder and Ce 0.8 Sm 0.2 O 1.9 (SDC) powder.

[0093] Preparation of Sr2Fe 1.5 Mo 0.5 O6(SFM) powder:

[0094] 1) Sr(NO3)2, Fe(NO3)3·9H2O and (NH4)6Mo7O 24 ·4H2O were dissolved in deionized water in a certain stoichiometric ratio (molar ratio of 2:1.5:0.5).

[0095] 2) To the uniformly dissolved solution, add citric acid and ethylenediaminetetraacetic acid, the molar ratio of total metal ions to ethylenediaminetetraacetic acid and citric acid is 1:1:1.5.

[0096] 3) After the solution is uniformly mixed, slowly add ammonia water to adjust the pH to 6, and continuously stir.

[0097] 4) Then add a stirring rod to the warm water at 80°C and continue stirring until a yellow-brown sticky transparent wet gel is formed.

[0098] 5) Quickly transfer the prepared wet gel to a cup-shaped vessel, dry it in an oven at 160°C for 7h to obtain a porous dry gel.

[0099] 6) Then transfer the dry gel to a muffle furnace and calcine it at 1050°C for 5h to obtain SFM powder.

[0100] La 0.7 Sr 0.3 Co 0.2 Fe 0.8 O3(LSCF) powder preparation:

[0101] 1) Weigh a certain stoichiometric ratio (molar ratio of 7:3:8:2) of La(NO3)3·6H2O, Sr(NO3)2, Fe(NO3)3·9H2O and Co(NO3)2·6H2O and dissolve them in deionized water.

[0102] 2) To the uniformly dissolved solution, add citric acid and ethylenediaminetetraacetic acid, the molar ratio of total metal ions to ethylenediaminetetraacetic acid and citric acid is 1:1:1.5.

[0103] 3) After the solution is uniformly mixed, slowly add ammonia water to adjust the pH to 6, and continuously stir.

[0104] 4) Then add a stirring rod to the warm water at 80°C and continue stirring until a yellow-brown sticky transparent wet gel is formed.

[0105] 5) Quickly transfer the prepared wet gel to a cup-shaped vessel, dry it in an oven at 160°C for 7h to obtain a porous dry gel.

[0106] 6) Then transfer the dry gel to a muffle furnace and calcine it at 1050°C for 3h to obtain LSCF powder.

[0107] Ce 0.8 Sm 0.2 O 1.9 (SDC) powder preparation:

[0108] 1) Take a certain stoichiometric ratio (molar ratio of 4:1) of Ce(NO3)3.6H2O and Sm(NO3)3.6H2O, and dissolve them in deionized water.

[0109] 2) Add citric acid and ethylenediaminetetraacetic acid to the uniformly dissolved solution, and the molar ratio of the total amount of metal ions to ethylenediaminetetraacetic acid and citric acid is 1:1:1.5.

[0110] 3) After the solution is uniformly mixed, slowly add ammonia water to adjust the pH to 6, and continuously stir.

[0111] 4) Then add a stirring rod to continue stirring in warm water at 80°C until a light yellow, transparent, and viscous wet gel is formed.

[0112] 5) Quickly transfer the prepared wet gel to a cup-shaped vessel, and dry it in an oven at 180°C for 12h to obtain a porous dry gel.

[0113] 6) Then transfer the dry gel to a muffle furnace and calcine it at 900°C for 3h to obtain SDC powder.

[0114] II. Prepare the powder in step I into cathode slurry, anode slurry, and separator layer slurry.

[0115] Preparation of cathode slurry: Put SFM powder, SDC powder, and terpineol in a small cup-shaped vessel at a mass ratio of 65:35:150, and grind for 1h until uniformly mixed to form an electrode slurry with viscosity.

[0116] Preparation of anode slurry: Put LSCF powder, SDC powder, and terpineol in a small cup-shaped vessel at a mass ratio of 65:35:150, and grind for 1h until uniformly mixed to form an electrode slurry with viscosity.

[0117] Preparation of separator layer slurry: Put SDC powder and terpineol in a small cup-shaped vessel at a mass ratio of 1:1.5, and grind for 1h until uniformly mixed to form a separator layer slurry with viscosity.

[0118] III. Use the screen printing method to apply the separator layer slurry in step 2) to one side of the solid electrolyte substrate, and dry and calcine it to obtain a separator layer; then use the screen printing method to apply the cathode slurry to the separator layer, and dry it to obtain a cathode; then use the screen printing method to apply the anode slurry to the other side of the solid electrolyte substrate, and dry it to form an anode; finally, calcine it to obtain a complete solid oxide electrolyte.

[0119] The preparation of the solid electrolyte substrate involves: dry pressing LSGM powder (obtained directly from the market) into an electrolyte green blank under a pressure of 200 MPa, followed by calcination at 1400℃ for 4 hours to obtain the solid electrolyte substrate.

[0120] Specifically, the separator paste is uniformly coated onto one side of the electrolyte substrate using screen printing, dried in an oven at 100°C, and then calcined in a muffle furnace at 1200°C for 5 hours. Subsequently, the prepared cathode paste is uniformly coated onto the same side of the electrolyte substrate using screen printing and dried in an oven at 100°C. The prepared anode paste is then uniformly coated onto the other side of the electrolyte substrate using screen printing and dried in an oven at 100°C. Finally, the anode paste is calcined in a muffle furnace at 1100°C for 2 hours to obtain a complete solid oxide electrolytic cell.

[0121] IV. The cathode of the solid oxide electrolyte in step III is subjected to impregnation modification treatment to attach La to the substrate layer of the cathode. 0.8 Sr 0.2 Cr 0.5 Mn 0.5 O3 (LSCM) nanoparticles or CuO nanoparticles.

[0122] Preparation of impregnation solution:

[0123] Type I nitrate solutions:

[0124] Cu(NO3)2·3H2O was dissolved in anhydrous ethanol to prepare a 0.1 mol·L⁻¹ solution. -1 nitrate solution.

[0125] Type II nitrate solutions:

[0126] 1) Mix La(NO3)3·6H2O, Sr(NO3)2, Cr(NO3)3·9H2O and Mn(NO3)2 in a certain stoichiometric ratio (molar ratio of 8:2:5:5) to form a nitrate solution;

[0127] 2) Add citrate and ethylenediaminetetraacetic acid to the above solution. The molar ratio of total metal ions to ethylenediaminetetraacetic acid to citrate is 1:1:1.5.

[0128] 3) Stir the prepared solution in an 80℃ water bath, and slowly add a certain amount of ammonia water while maintaining the pH at 6, to prepare a 0.1 mol·L⁻¹ solution. -1 nitrate solution.

[0129] Electrode modification: pipette the first type of nitrate solution or the second type of nitrate solution on the cathode side of the solid oxide electrolysis cell, dry in the oven at 80°C, and then calcine the cell in a muffle furnace at 600°C for 2h to obtain the modified electrode with CuO nanoparticles or LSCM nanoparticles attached on the cathode. The content of the attached CuO nanoparticles or LSCM nanoparticles is 2wt% of the mass ratio of the cathode material.

[0130] Example Three

[0131] I. Preparation of Sr2FeMoO6(SFM) powder, LaSrCoFeO3(LSCF) powder and CeSmO2(SDC) powder. 1.5 Mo 0.5 O6(SFM) powder, La 0.7 Sr 0.3 Co 0.2 Fe 0.8 O3(LSCF) powder and Ce 0.8 Sm 0.2 O 1.9 (SDC) powder.

[0132] Sr2Fe 1.5 Mo 0.5 O6(SFM) powder:

[0133] 1) Weigh a certain stoichiometric ratio (molar ratio of 2:1.5:0.5) of Sr(NO3)2, Fe(NO3)3·9H2O and (NH4)6Mo7O 24 ·4H2O and dissolve them in deionized water.

[0134] 2) Add citric acid and ethylenediaminetetraacetic acid to the uniformly dissolved solution, and the molar ratio of the total amount of metal ions to ethylenediaminetetraacetic acid and citric acid is 1:1:1.5.

[0135] 3) After the solution is uniformly mixed, slowly add ammonia water to adjust the pH to 8, and continuously stir.

[0136] 4) Then add a stirrer to continue stirring in warm water at 80°C until a yellow-brown transparent wet gel with viscosity is formed.

[0137] 5) Quickly transfer the prepared wet gel to a cup-shaped container and dry it in an oven at 160°C for 7h to obtain a porous dry gel.

[0138] 6) Then transfer the dry gel to a muffle furnace and calcine it at 1050°C for 5h to obtain SFM powder.

[0139] La 0.7 Sr 0.3 Co 0.2 Fe 0.8 O3(LSCF) powder:

[0140] 1) Weigh a certain stoichiometric ratio (molar ratio of 7:3:8:2) of La(N03)3-6H20, Sr(N03)2, Fe(N03)3-9H20 and Co(N03)2-6H20 and dissolve them in deionized water.

[0141] 2) Add citric acid and ethylenediaminetetraacetic acid to the uniformly dissolved solution, and the molar ratio of the total amount of metal ions to ethylenediaminetetraacetic acid and citric acid is 1:1:1.5.

[0142] 3) After the solution is uniformly mixed, slowly add ammonia water to adjust the pH to 8, and continuously stir.

[0143] 4) Then add a stirring rod to the warm water at 80°C and continue stirring until a yellow-brown transparent wet gel with viscosity is formed.

[0144] 5) Quickly transfer the prepared wet gel to a cup-shaped vessel, dry it in an oven at 160°C for 7h, and obtain a porous dry gel.

[0145] 6) Then transfer the dry gel to a muffle furnace and calcine it at 1050°C for 3h to obtain LSCF powder.

[0146] Ce 0.8 Sm 0.2 O 1.9 Preparation of SDC powder:

[0147] 1) Weigh a certain stoichiometric ratio (molar ratio of 4:1) of Ce(N03)3-6H20 and Sm(N03)3-6H20 and dissolve them in deionized water.

[0148] 2) Add citric acid and ethylenediaminetetraacetic acid to the uniformly dissolved solution, and the molar ratio of the total amount of metal ions to ethylenediaminetetraacetic acid and citric acid is 1:1:1.5.

[0149] 3) After the solution is uniformly mixed, slowly add ammonia water to adjust the pH to 8, and continuously stir.

[0150] 4) Then add a stirring rod to the warm water at 80°C and continue stirring until a yellow-brown transparent wet gel with viscosity is formed.

[0151] 5) Quickly transfer the prepared wet gel to a cup-shaped vessel, dry it in an oven at 160°C for 7h, and obtain a porous dry gel.

[0152] 6) Then transfer the dry gel to a muffle furnace and calcine it at 1050°C for 3h to obtain LSCF powder.

[0153] Ⅱ, prepare the powder in step I into cathode slurry, anode slurry and separator slurry.

[0154] Preparation of cathode slurry: SFM powder, SDC powder and terpineol were put in a small cup-shaped vessel in a mass ratio of 65:35:150, and grinded for 1 h until mixed uniformly to form an electrode slurry with viscosity.

[0155] Preparation of anode slurry: LSCF powder, SDC powder and terpineol were put in a small cup-shaped vessel in a mass ratio of 65:35:150, and grinded for 1 h until mixed uniformly to form an electrode slurry with viscosity.

[0156] Preparation of interlayer slurry: SDC powder and terpineol were put in a small cup-shaped vessel in a mass ratio of 1:1.5, and grinded for 1 h until mixed uniformly to form an interlayer slurry with viscosity.

[0157] Ⅲ, the interlayer slurry in step 2) is coated on one side of the solid electrolyte substrate by screen printing, dried and calcined to obtain an interlayer; then the cathode slurry is coated on the interlayer by screen printing and dried to obtain a cathode; then the anode slurry is coated on the other side of the solid electrolyte substrate by screen printing and dried to form an anode; finally, calcination is performed to obtain a complete solid oxide electrolysis cell.

[0158] Preparation of solid electrolyte substrate: LSGM powder (obtained by direct purchase) is dry-pressed into an electrolyte green body under a pressure of 200 MPa, and then calcined at 1400°C for 4 h to obtain a solid electrolyte substrate.

[0159] Specifically, the interlayer slurry is uniformly coated on one side of the electrolyte substrate by screen printing, dried in an oven at 100°C, and transferred to a muffle furnace for calcination at 1200°C for 5 h. Then the prepared cathode slurry is uniformly coated on the same side of the electrolyte substrate by screen printing, dried in an oven at 100°C. Take out, and uniformly coat the prepared anode slurry on the other side of the electrolyte substrate by screen printing, and dry in an oven at 100°C. Take out, transfer to a muffle furnace, and calcine at 1100°C for 2 h to obtain a complete solid oxide electrolysis cell.

[0160] Ⅳ, the cathode of the solid oxide electrolysis cell in step III is subjected to immersion modification treatment, so that La 0.8 Sr 0.2 Cr 0.5 Mn 0.5 O3(LSCM) nanoparticles or CuO nanoparticles are attached to the base layer of the cathode.

[0161] Preparation of immersion solution:

[0162] First type of nitrate solution:

[0163] Cu(NO3)2*3H2O was dissolved in anhydrous ethanol to prepare a 0.1 moL*L -1 nitrate solution.

[0164] The second type of nitrate solution:

[0165] 1) La(NO3)3*6H2O, Sr(NO3)2, Cr(NO3)3*9H2O, and Mn(NO3)2 were mixed in a stoichiometric ratio (molar ratio of 8:2:5:5) to prepare a nitrate solution;

[0166] 2) Citrate and ethylenediaminetetraacetic acid were added to the above solution, and the molar ratio of total metal ions: ethylenediaminetetraacetic acid: citric acid was 1:1:1.5.

[0167] 3) The prepared solution was stirred in a water bath at 80°C, and a certain amount of ammonia was slowly added while controlling the pH at 8 to prepare a 0.1 moL*L -1 nitrate solution.

[0168] Electrode modification: The first type of nitrate solution or the second type of nitrate solution was dropped on the cathode side of the solid oxide electrolysis cell using a pipette, dried in an oven at 80°C, and then the cell was calcined in a muffle furnace at 600°C for 2h to obtain the modified electrode with CuO nanoparticles or LSCM nanoparticles attached to the cathode. The content of the attached CuO nanoparticles or LSCM nanoparticles accounted for 8wt% of the mass ratio of the cathode material.

[0169] Comparative example: The difference from Example 1 is only that the cathode is not modified by immersion solution. It is named SFM.

[0170] In order to verify the performance of the solid oxide electrolysis cell obtained by the present application, the solid oxide electrolysis cell obtained in Experimental Example 1 was tested as follows.

[0171] (1) The chemical stability of the SFM electrode of the comparative example, and the Cu-SFM and LSCM-SFM electrode materials obtained in Experimental Example 1 were studied by X-ray diffraction method, as shown in Figure 2 , the diffraction peaks of the modified electrode materials are consistent with those of the original SFM, and the SFM, SDC, and LSGM have good chemical compatibility.

[0172] (2) The microstructure of the surface of the original SFM electrode, Cu-SFM, and LSCM-SFM electrode materials was characterized by scanning electron microscopy (SEM), as shown in Figure 3As shown, (a) is a scanning electron microscope picture of the original SFM (comparative example) electrode material surface, (b) is a scanning electron microscope picture of the Cu-SFM electrode material surface, and (c) is a scanning electron microscope picture of the LSCM-SFM electrode material surface. A large number of nanoparticles are observed to be deposited on the SFM surface. The number of nanoparticles on the LSCM infiltrated electrode is less than that of the CuO infiltrated electrode. These nanoparticles cover the surface of the SFM, effectively increasing the specific surface area of the electrode and generating additional active sites.

[0173] Preparation of symmetric cells: In order to test the impedance change of the electrode material in a CO2 atmosphere, symmetric cells were prepared and tested. The specific preparation method is as follows: the prepared SDC separator layer slurry was symmetrically brushed on both sides of the electrolyte substrate using a screen printing method, dried in an oven at 100°C, and transferred to a muffle furnace at 1200°C for calcination for 5h. Subsequently, the prepared SFM cathode slurry was uniformly brushed on both sides of the electrolyte substrate using a screen printing method, dried in an oven at 100°C. After taking out, it was transferred to a muffle furnace at 1100°C for calcination for 2h to obtain a complete symmetric cell. A dropper was used to drop the impregnation solution on both sides of the symmetric cell, dried in an oven at 80°C, and then the cell was calcined in a muffle furnace at 600°C for 2h to obtain a modified symmetric cell. The symmetric cell modified by the first type of nitrate solution is named Cu-SFM, and the symmetric cell modified by the second type of nitrate solution is named LSCM-SFM. Similarly, the SFM electrode without modification on both sides of the symmetric cell is used as a comparative example. The above three symmetric cells were tested, and the EIS curves in a pure CO2 atmosphere are as shown in Figure 4 As shown, the results show that the ohmic resistance and polarization resistance of the Cu-SFM and LSCM-SFM electrodes are reduced, and the polarization resistance values are 14.1 and 16.8Ωcm 2 , respectively, which are about 36.2% and 24.0% lower than that of the SFM (22.1Ωcm 2 ).

[0174] The two solid oxide electrolysis cells obtained in Experimental Example One and the solid oxide electrolysis cell obtained in the comparative example were tested using an electrochemical workstation (CHI-660E), and the test results are as shown in Figure 5 and Figure 6 .

[0175] The EIS curves under open circuit voltage Figure 5 show that the ohmic resistance and polarization resistance of the electrode infiltrated with nanoparticles are reduced. Compared with the SFM (2.60Ωcm 2 ), the CuO modified cell has the smallest polarization resistance (1.61Ωcm 2 ), and the performance improvement is more significant than that of the LSCM (2.25Ωcm 2 ).

[0176] I-V curves Figure 6 ) show that the current density of the electrodes impregnated with nanoparticles is increased. The current density of the solid oxide electrolysis cells based on Cu-SFM and LSCM-SFM cathodes at 1.8 V is 510 and 405 mA cm -2 , respectively, higher than that of the solid oxide electrolysis cell based on SFM cathode (383 mA cm -2 ).

Claims

1. A solid oxide electrolytic cell for high-temperature electrolysis of carbon dioxide, characterized in that: It includes a solid electrolyte substrate, an isolation layer located on one side of the solid electrolyte substrate, a cathode located on the isolation layer, and an anode located on the other side of the solid electrolyte substrate; The solid electrolyte substrate material is La 0.9 Sr 0.1 Ga 0.8 Mg 0.2 O3(LSGM), the insulating layer material is Ce 0.8 Sm 0.2 O 1.9 (SDC), the cathode material is Sr2Fe 1.5 Mo 0.5 O6 (SFM) and Ce 0.8 Sm 0.2 O 1.9 A composite material consisting of (SDC) and La attached to the cathode material. 0.8 Sr 0.2 Cr 0.5 Mn 0.5 O3 (LSCM) nanoparticles or CuO nanoparticles; the anode material is La. 0.7 Sr 0.3 Co 0.2 Fe 0.8 O3 (LSCF) and Ce 0.8 Sm 0.2 O 1.9 A complex composed of (SDC).

2. The solid oxide electrolytic cell for high-temperature electrolysis of carbon dioxide according to claim 1, characterized in that: The CuO nanoparticles or La 0.8 Sr 0.2 Cr 0.5 Mn 0.5 The amount of O3 (LSCM) nanoparticles attached is 2wt%-8wt% of the mass of the nanoparticles in the cathode material.

3. A method for preparing a solid oxide electrolytic cell for high-temperature electrolysis of carbon dioxide as described in claim 1, characterized in that: Includes the following steps, I. Preparation of Sr2Fe 1.5 Mo 0.5 O6(SFM) powder, La 0.7 Sr 0.3 Co 0.2 Fe 0.8 O3 (LSCF) powder and Ce 0.8 Sm 0.2 O 1.9 (SDC) powder; II. Prepare the powder from step I into cathode slurry, anode slurry, and isolation layer slurry; Ⅲ. The isolation layer paste from step Ⅱ is applied to one side of the solid electrolyte substrate using screen printing. After drying and calcination, the isolation layer is obtained. Then, the cathode paste is applied to the isolation layer using screen printing and dried to form the cathode. Then, the anode paste is applied to the other side of the solid electrolyte substrate using screen printing and dried to form the anode. Finally, calcination is performed to obtain a complete solid oxide electrolytic cell. IV. The cathode of the solid oxide electrolytic cell in step III is subjected to impregnation modification treatment to allow La to adhere to the cathode material. 0.8 Sr 0.2 Cr 0.5 Mn 0.5 O3 (LSCM) nanoparticles or CuO nanoparticles.

4. The method for preparing a solid oxide electrolytic cell for high-temperature carbon dioxide electrolysis according to claim 3. Its features are: In step I, Sr2Fe 1.5 Mo 0.5 O6(SFM) powder is prepared by the following method. 1) Combine Sr(NO3)2, Fe(NO3)3·9H2O and (NH4)6Mo7O 24 • 4H2O is dissolved in deionized water as a raw material to form a nitrate solution; 2) Add citric acid and ethylenediaminetetraacetic acid to the above solution, with the total amount of metal ions in a molar ratio of ethylenediaminetetraacetic acid to citric acid being 1:1:1.5; 3) Add ammonia solution to the solution in step 2) to adjust the pH to 6-8; 4) The solution in step 3) is stirred while being heated in a water bath to obtain a wet gel; 5) Dry the wet gel to obtain a dry gel; 6) Calcination of the dried gel yields Sr2Fe 1.5 Mo 0.5 O6(SFM) powder.

5. The method for preparing a solid oxide electrolytic cell for high-temperature electrolysis of carbon dioxide according to claim 3, characterized in that: In step I, La 0.7 Sr 0.3 Co 0.2 Fe 0.8 O3(LSCF) powder is prepared by the following method. 1) Dissolve La(NO3)3·6H2O, Sr(NO3)2, Fe(NO3)3·9H2O and Co(NO3)2·6H2O as raw materials in deionized water to form a nitrate solution; 2) Add citric acid and ethylenediaminetetraacetic acid to the above solution, with the total amount of metal ions in a molar ratio of ethylenediaminetetraacetic acid to citric acid being 1:1:1.5; 3) Add ammonia solution to the solution in step 2) to adjust the pH to 6-8; 4) The solution in step 3) is stirred while being heated in a water bath to obtain a wet gel; 5) Dry the wet gel to obtain a dry gel; 6) Calcine the dried gel to obtain La 0.7 Sr 0.3 Co 0.2 Fe 0.8 O3(LSCF) powder.

6. The method for preparing a solid oxide electrolytic cell for high-temperature electrolysis of carbon dioxide according to claim 3, Its features are: In step I, Ce 0.8 Sm 0.2 O 1.9 (SDC) powder is prepared by the following method. 1) Dissolve Ce(NO3)3·6H2O and Sm(NO3)3·6H2O as raw materials in deionized water to form a nitrate solution; 2) Add citric acid and ethylenediaminetetraacetic acid to the above solution, with the total amount of metal ions in a molar ratio of ethylenediaminetetraacetic acid to citric acid being 1:1:1.5; 3) Add ammonia solution to the solution in step 2) to adjust the pH to 6-8; 4) The solution in step 3) is stirred while being heated in a water bath to obtain a wet gel; 5) Dry the wet gel to obtain a dry gel; 6) Calcining the dried gel yields Ce. 0.8 Sm 0.2 O 1.9 (SDC) powder.

7. The method for preparing a solid oxide electrolytic cell for high-temperature electrolysis of carbon dioxide according to claim 3, characterized in that: SFM powder, SDC powder and terpineol were placed in a cup-shaped container at a mass ratio of 65:35:150 and ground until they were evenly mixed to form a viscous cathode slurry. LSCF powder, SDC powder and terpineol were placed in a cup-shaped vessel at a mass ratio of 65:35:150 and ground until uniformly mixed to form a viscous anode slurry; SDC powder and terpineol were placed in a cup-shaped vessel at a mass ratio of 1:1.5 and ground until uniformly mixed to form a viscous isolation layer slurry.

8. The method for preparing a solid oxide electrolytic cell for high-temperature electrolysis of carbon dioxide according to claim 3, characterized in that: In step IV, the impregnation solution is prepared as follows: Cu(NO3)2·3H2O was prepared by dissolving Cu(NO3)2·3H2O in anhydrous ethanol to obtain Cu(NO3)2·3H2O with a concentration of 0.1 mol·L⁻¹. -1 The first type of nitrate solution.

9. The method for preparing a solid oxide electrolytic cell for high-temperature electrolysis of carbon dioxide according to claim 3, characterized in that: In step IV, the impregnation solution is prepared as follows: 1) Dissolve La(NO3)3·6H2O, Sr(NO3)2, Cr(NO3)3·9H2O, and Mn(NO3)2 in anhydrous ethanol to prepare a nitrate solution. 2) Add citrate and ethylenediaminetetraacetic acid to the above solution. The molar ratio of total metal ions to ethylenediaminetetraacetic acid to citrate is 1:1:1.

5. 3) Heat the prepared solution in a water bath while stirring, add ammonia to control the pH of the solution to 6-8, and prepare La. 0.8 Sr 0.2 Cr 0.5 Mn 0.5 The concentration of O3 (LSCM) was 0.1 mol·L⁻¹. -1 The second type of nitrate solution.

10. The method for preparing a solid oxide electrolytic cell for high-temperature electrolysis of carbon dioxide according to claim 8 or 9, characterized in that: In step IV, a type I nitrate solution or a type II nitrate solution is dropped onto the cathode material, dried, and then calcined to deposit CuO nanoparticles or La onto the cathode material. 0.8 Sr 0.2 Cr 0.5 Mn 0.5 O3(LSCM) nanoparticles.

Images