CN109468661B - Composite oxygen electrode for solid oxide electrolytic cell and preparation method thereof - Google Patents
Composite oxygen electrode for solid oxide electrolytic cell and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a composite oxygen electrode for a solid oxide electrolytic cell and a preparation method thereof, wherein the composite oxygen electrode comprises an electrolyte layer, a substrate layer and an active coating layer; the substrate layer is made of BSCF-SDC composite porous material and covers the electrolyte layer; the active coating layer is coated on the outer surface and the inner surface of the pores of the BSCF-SDC composite porous material. The invention takes BSCF-SDC composite porous material as electrode main material, and forms good conductivity and CO on the surface and in pores of the composite porous material2Ln of tolerance2NiO4The active coating layer obviously improves the electrochemical performance and long-term stability of the composite oxygen electrode material.
Description
Technical Field
The invention belongs to the technical field of solid oxide electrolytic cells, and particularly relates to a composite oxygen electrode for a solid oxide electrolytic cell and a preparation method thereof.
Background
At present, fossil fuels such as coal still account for the main part in the energy structure of China. The long-term use of fossil fuels leads to the rapid increase of the content of pollutants such as carbon dioxide, sulfur dioxide, nitrogen oxides and the like in the atmosphere, causes the frequent occurrence of haze and other extreme weather, and brings great damage to the ecological environment of China.
A Solid Oxide Electrolysis Cell (SOEC) is an electrochemical device that converts electrical energy into chemical energy, and its basic principle is the reverse process of a Solid Oxide Fuel Cell (SOFC). Water can be converted to hydrogen by operation of the SOEC, and carbon dioxide and water can also be co-electrolyzed, with the products being primarily hydrogen and carbon monoxide, i.e., water gas, which can be used as a production fuel. In the co-electrolysis process, carbon dioxide can be recycled, and the emission of carbon dioxide is not increased in the whole energy circulation process, so that the carbon dioxide co-electrolysis can effectively reduce the emission of carbon dioxide compared with the traditional energy production modes such as coal and petroleum. Meanwhile, the SOEC electrolytic process is carried out at high temperature, compared with other low-temperature electrolytic processes, the electrolytic efficiency is higher, and the consumption of electric energy in electrolysis can be reduced by the high temperature. Therefore, the SOEC high-temperature electrolysis has great application prospect in the aspects of energy conservation and emission reduction.
The power generation can be carried out in a large amount in modes of water power, wind power and the like, but the power generation is greatly influenced by weather, seasonality exists, the power consumption of residents is staged, the power consumption demand difference of residents in different time periods is huge, huge impact is caused to the stable load of a power grid, and the utilization of surplus electric energy in the power generation peak and the power consumption peak is of great significance to the full utilization of resources. The use of excess electrical energy for SOEC electrolysis to convert electrical energy into chemical energy for temporary storage, while the utilization of SOFCs to convert chemical energy into electrical energy at peak demand is a beneficial attempt to level off the peak of intermittent power production. By combining SOEC with the surplus electric energy, various chemical raw materials can be produced through different electrolytic processes, the application is wide, and the full utilization of resources can be realized.
Double-doped perovskite material Ba1-xSrxCo0.8Fe0.2O3-δ(BSCF) has mixed ion conductivity and good electrochemical catalytic activity at intermediate temperature, and is expected to become the next generation SOEC oxygen electrode material. However, because of the alkaline earth metal element, BSCF is mixed with CO in the air under the oxygen electrode environment2The reaction activity is high, the performance stability is poor, and the electrode conductivity is low, so that the performance of the BSCF electrode is obviously reduced after the BSCF electrode runs for a long time. It is therefore necessary to improve the long-term stability of BSCF electrodes.
The metal oxide of the tetragonal perovskite intergrowth type structure has a layered perovskite-like structure (typical structure K)2NiF4) Wherein Ln2NiO4(Ln is La, Pr and Nd) has good oxygen surface exchange coefficient at medium temperature, and has higher conductivity and better CO than BSCF2And (4) endurance performance. But Ln has anisotropic ion transport properties due to its layered structure2NiO4When the thickness is large, the electrode activity is low, and the electrode is not suitable as a main body material of an oxygen electrode.
Disclosure of Invention
To is coming toThe invention aims to solve the defects in the prior art and provide a composite oxygen electrode for a solid oxide electrolytic cell, wherein a BSCF-SDC composite porous material is used as an electrode main body material and is then dipped in situ on the surface and pores of the composite porous material to form a composite oxygen electrode with good conductivity and CO2Ln of tolerance2NiO4The active coating layer obviously improves the electrochemical performance and long-term stability of the composite oxygen electrode material.
In the present invention, it is to be noted that: SOEC is a solid oxide electrolytic cell, SOFC is a solid oxide fuel cell, and BSCF is barium-doped strontium cobalt ferrite (Ba)1-xSrxCo0.8Fe0.2O3-δ)，Ln2NiO4Is nickel-based layered material (Ln is La, Pr or Nd), SDC is samarium-doped cerium oxide, PMMA is polymethyl methacrylate, and PVP is polyethylene glycol.
In order to achieve the technical object, the invention provides a composite oxygen electrode for a solid oxide electrolytic cell, which comprises an electrolyte layer, a substrate layer and an active coating layer;
the substrate layer is made of BSCF-SDC composite porous material and covers the electrolyte layer;
the active coating layer is coated on the outer surface and the inner surface of the pores of the BSCF-SDC composite porous material.
Preferably, the electrolyte layer is made of SDC, and the thickness of the electrolyte layer is 500-1000 μm.
Preferably, the molar ratio of the BSCF to the SDC in the BSCF-SDC composite porous material is 1: 4-4: 1, more preferably 3: 2-4: 1, and most preferably 7: 3.
Preferably, the material of the active coating layer is Ln2NiO4The material is characterized in that Ln is La, Pr or Nd, and the coating amount is 2-20 wt% of the composite oxygen electrode.
The invention also provides a preparation method of the composite oxygen electrode for the solid oxide electrolytic cell, which comprises the steps of firstly printing a BSCF-SDC composite porous material substrate layer on an electrolyte layer of an electrolytic cell sheet, and then depositing an active coating layer on the outer surface and the inner surfaces of pores of the BSCF-SDC composite porous material in situ by adopting an immersion method to obtain the composite oxygen electrode.
Preferably, firstly, preparing an electrolyte layer and SDC by adopting a sol-gel method, and preparing BSCF by adopting a glycine-nitrate method; printing the BSCF and SDC mixed slurry on an electrolyte layer of the electrolytic cell sheet by adopting a screen printing method, and calcining to obtain a BSCF-SDC composite porous material substrate layer; and finally, uniformly depositing an active coating layer on the outer surface and the inner surfaces of pores of the BSCF-SDC composite porous material by adopting an immersion method, and then sintering at high temperature to obtain the composite oxygen electrode.
More preferably, the preparation method specifically comprises the following steps:
the method comprises the following steps: the material of the electrolyte layer is SDC and Ce (NO)3)2·6H2O、Sm(NO3)3·6H2Using citric acid monohydrate as a complexing agent and a sintering aid as a raw material, preparing an SDC precursor by a sol-gel method, and finally calcining the SDC precursor for 1-4 hours at the temperature of 600-800 ℃ to prepare SDC powder;
step two: using Ba (NO)3)2、Sr(NO3)2、Co(NO3)2·6H2O、Fe(NO3)3·9H2Taking O as a raw material, adopting glycine as a complexing agent and a sintering aid, preparing a BSCF precursor by a glycine-nitrate method, and calcining the BSCF precursor for 1-4 hours at the temperature of 800-1100 ℃ to prepare BSCF powder;
step three: mixing ethyl cellulose and terpineol to prepare an organic binder; then mixing and grinding the SDC powder, the BSCF powder, the organic binder and the pore-forming agent to obtain mixed slurry, wherein the amount of the pore-forming agent is 2-12 wt% of the total amount of the SDC powder and the BSCF powder; printing the mixed slurry on an electrolyte layer of an electrolytic cell sheet by a screen printing method, and calcining for 1-4 hours at the temperature of 900-1200 ℃ to obtain a BSCF-SDC composite porous material substrate layer;
step four: according to the formula Ln2NiO4Preparing nitrate solution according to the stoichiometric ratio of the elements, adding glycine and PVP, and fully mixing to obtain Ln2NiO4A precursor solution; using a dipping method to dip Ln2NiO4Depositing the precursor solution on the outer surface and the inner surface of the pores of the BSCF-SDC composite porous material; and sintering at 800-1000 ℃ for 1-4 hours to obtain the composite oxygen electrode.
Preferably, the pore-forming agent is at least one of PMMA, starch and activated carbon, and the addition amount of the pore-forming agent is 2-12 wt% of the total amount of the SDC powder and the BSCF powder.
The invention also provides a solid oxide electrolytic cell of the composite oxygen electrode.
The composite oxygen electrode for the solid oxide electrolytic cell is prepared by taking a composite porous material BSCF-SDC as a substrate layer and a nickel-based material Ln2NiO4The surface active layer is a composite oxygen electrode for a solid oxide electrolytic cell with excellent performance.
The invention has the beneficial effects that:
the BSCF material has good bulk phase oxygen anion transfer capability as an electrode main body material, but the surface of the BSCF material can be in contact with CO in the air2Reaction, and the electron conductivity of the material is low; and Ln2NiO4The surface oxygen migration capacity is strong, the electronic conductivity is superior to that of a BSCF material, and the BSCF material has good stability in air, but the BSCF material is not suitable for being used as an electrode main body material with large thickness due to the fact that the ionic conductivity of the BSCF material is anisotropic. By adjusting the electrode structure and taking the latter as a surface active coating layer, the former is taken as a substrate layer to be combined to form the composite cathode, so that the advantages of the two are combined, and the electrochemical performance and the long-term stability of the BSCF oxygen electrode in a solid oxide fuel electrolytic cell are obviously improved.
The invention mainly adjusts the whole structure of the electrode from two aspects, namely, BSCF and Sm are adopted0.2Ce0.8O1.9The (SDC) materials are mixed to form a composite oxygen electrode material, so that an electrode three-phase interface can extend from an electrode and electrolyte interface to an electrode main body, an electrochemical reaction active area is increased, and the electrochemical catalytic activity of the electrode is improved; secondly, the internal surface structure of the electrode is adjusted, the internal surface of the porous oxygen electrode is modified by an in-situ impregnation method, and more uniform load is formed on the surface of the electrode in situThe formed coating layer can combine the advantages of the dipping material and the electrode material, the performance attenuation problem of the BSCF electrode is relieved, meanwhile, the internal surface of the modified electrode has rich microstructures, the internal area of the electrode can be expanded transversely, the internal surface area of the electrode is increased, and the electrocatalytic activity of the electrode is improved.
Drawings
FIG. 1 is a schematic cross-sectional view of a half cell;
FIG. 2 is a partial schematic view of the electrode-electrolyte interface;
wherein 1 is a BSCF-SDC porous oxygen electrode layer, 2 is an SDC electrolyte support layer, 3 is a BSCF material, 4 is an SDC material, and 5 is an LNO active coating layer;
FIG. 3 is a graph of AC impedance comparison of BSCF-SDC composite electrodes at different mole ratios at 700 ℃;
FIG. 4 is a graph of AC impedance at 700 ℃ for a BSCF electrode, a BSCF-SDC (molar ratio of 7:3) electrode, and an LNO/BSCF-SDC (molar ratio of 7:3) electrode prepared by a dipping process and an impregnation process, respectively;
in FIG. 5, a and b are the cross section of the electrode after immersion and the local scanning electron microscope image, respectively.
Detailed Description
To further illustrate the embodiments of the present invention, a novel solid oxide electrolytic cell composite oxygen electrode having a core-shell like structure and a method for preparing the same are illustrated below by way of example.
Example 1
Examples are different molar ratios of Ba0.5Sr0.5Co0.8Fe0.2O3-δ-SDC porous complex phase electrode;
the preparation method comprises the following specific steps of:
the method comprises the following steps: preparation of Sm by sol-gel method0.2Ce0.8O1.9(SDC) electrolyte material powder Sm0.2Ce0.8O1.9Respectively dispose Ce (NO)3)2·6H2O、Sm(NO3)3·6H2O solution, citric acid monohydrate is used as complexing agent and sintering aid, and the addition amount of the citric acid monohydrate is the total metal ion molar quantity1.5 times, heating the mixed solution in water bath at 70 ℃ to be gelatinous, continuously heating the gel in a universal furnace to be combusted to form SDC precursor powder, and finally calcining at 800 ℃ for 2 hours to prepare SDC target powder;
step two: preparation of Ba by glycine-nitrate method (GNP)0.5Sr0.5Co0.8Fe0.2O3-δ(BSCF) material powder
According to Ba0.5Sr0.5Co0.8Fe0.2O3-δConfiguration Ba (NO)3)2、Sr(NO3)2、Co(NO3)2·6H2O、Fe(NO3)3·9H2Adopting glycine as a complexing agent and a sintering aid for the O solution, wherein the total molar ratio of glycine to metal ions is 1.5:1, heating the mixed solution in a universal furnace to burn to prepare BSCF precursor powder, and calcining at 900 ℃ for 2 hours to prepare BSCF target powder;
step three: preparation of electrolyte substrate and printing of BSCF-SDC porous complex phase oxide electrode layer
Preparing an electrolyte substrate sheet with the diameter of about 2cm by adopting the SDC target powder prepared in the step one through a tabletting method, sintering the substrate at 1400 ℃ for 5h for forming, and polishing the surface of the formed SDC substrate for later use;
preparing BSCF electrode slurry by adopting the BSCF powder prepared in the second step:
mixing ethyl cellulose and terpineol, and preparing an organic binder, wherein the ethyl cellulose accounts for 1 wt%, and the terpineol accounts for 99 wt%; mixing and grinding the SDC powder, the BSCF powder and the PMMA for 1 hour, wherein the molar ratio of the SDC to the BSCF powder is 7:3, 5:5 and 3:7, and the mass of the PMMA accounts for 2 percent of the total mass of the powder; finally, adding an organic binder into the mixed powder of the SDC, the BSCF and the PMMA according to the mass ratio of 1:10 (binder: mixed powder), and mixing and grinding for 1 hour to obtain mixed slurry;
printing the mixed slurry on an SDC substrate by a screen printing method, and drying for 30min at 50 ℃; calcining at 1100 deg.C for 3 hr to obtain BSCF-SDC/SDC half cells with molar ratio of 3:7, 5:5 and 7:3, and thickness of electrode layer40 μm, and an area of about 0.25cm2。
Example 2
The example is to use La2NiO4(LNO) as an active material, by a solution in-situ impregnation method, to Ba in a molar ratio of 7:30.5Sr0.5Co0.8Fe0.2O3-δAnd modifying the SDC porous complex phase electrode to finally obtain the LNO/BSCF-SDC novel composite oxygen electrode and the preparation steps thereof.
The preparation method of the novel LNO/BSCF-SDC porous composite oxygen electrode comprises the following specific steps:
the method comprises the following steps: preparation of Sm by sol-gel method0.2Ce0.8O1.9(SDC) electrolyte material powder Sm0.2Ce0.8O1.9Respectively dispose Ce (NO)3)2·6H2O、Sm(NO3)3·6H2Adopting citric acid monohydrate as a complexing agent and a sintering aid, wherein the addition amount of the citric acid monohydrate is 1.5 times of the total metal ion molar weight, heating the mixed solution in a water bath at 70 ℃ to form gel, continuously heating the gel in a universal furnace until the gel is combusted to form SDC precursor powder, and finally calcining at 800 ℃ for 2 hours to obtain SDC target powder;
step two: preparation of Ba by glycine-nitrate method (GNP)0.5Sr0.5Co0.8Fe0.2O3-δ(BSCF) material powder
According to Ba0.5Sr0.5Co0.8Fe0.2O3-δConfiguration Ba (NO)3)2、Sr(NO3)2、Co(NO3)2·6H2O、Fe(NO3)3·9H2Adopting glycine as a complexing agent and a sintering aid for the O solution, wherein the total molar ratio of glycine to metal ions is 1.5:1, heating the mixed solution in a universal furnace to burn to prepare BSCF precursor powder, and calcining at 900 ℃ for 2 hours to prepare BSCF target powder;
step three: preparation of electrolyte substrate and printing of BSCF-SDC porous complex phase oxide electrode layer
Preparing an electrolyte substrate sheet with the diameter of about 2cm by adopting the SDC target powder prepared in the step one through a tabletting method, sintering the substrate at 1400 ℃ for 5h for forming, and polishing the surface of the formed SDC substrate for later use;
preparing BSCF electrode slurry by adopting the BSCF powder prepared in the second step:
mixing ethyl cellulose and terpineol, and preparing an organic binder, wherein the ethyl cellulose accounts for 1 wt%, and the terpineol accounts for 99 wt%; mixing and grinding the SDC powder, the BSCF powder and the PMMA for 1 hour, wherein the molar ratio of the SDC to the BSCF powder is 3:7, and the mass of the PMMA accounts for 2 percent of the total mass of the powder; finally, adding an organic binder into the mixed powder of the SDC, the BSCF and the PMMA according to the mass ratio of 1:10 (binder: mixed powder), and mixing and grinding for 1 hour to obtain mixed slurry;
printing the mixed slurry on an SDC substrate by a screen printing method, and drying for 30min at 50 ℃; calcining at 1100 deg.C for 3 hr to obtain a BSCF-SDC composite porous material substrate layer with thickness of 40 μm and area of 0.25cm2；
Step four: in-situ generation of LNO active coating layer on BSCF-SDC composite porous material substrate layer
Accurately weighing La (NO) according to the molar ratio of 2:13)3·6H2O、Ni(NO3)2·6H2Dissolving O in 2ml of ethanol water solution, wherein the volume ratio of ethanol to water in the ethanol solution is 1: 1; then adding glycine and PVP into the nitrate ethanol water solution, mixing and dissolving, wherein the total mole ratio of glycine to metal ions is 1.5:1, and the mass ratio of PVP to LNO is 5: 100; stirring for 1 hour, transferring to a volumetric flask for constant volume, and preparing LNO metal ion salt solution with the concentration of 0.05, 0.1 and 0.2 mol/L;
determining the volume of the precursor solution soaked each time according to the load capacity of the required active material, uniformly distributing the precursor solution with the required volume on a BSCF-SDC composite porous material substrate layer through a microsyringe, and drying for 30min under negative pressure; and sintering at 850 ℃ for 2 hours to obtain the LNO/BSCF-SDC/SDC half cell, wherein the load capacity of the LNO active material is about 4, 8 and 12wt% and the thickness of the active coating layer is about 300, 500 and 700nm according to different initial concentrations.
Comparative example 1
The present example is Ba0.5Sr0.5Co0.8Fe0.2O3-δA porous electrode;
the method comprises the following specific steps:
the method comprises the following steps: preparation of Sm by sol-gel method0.2Ce0.8O1.9(SDC) electrolyte material powder Sm0.2Ce0.8O1.9Respectively dispose Ce (NO)3)2·6H2O、Sm(NO3)3·6H2Adopting citric acid monohydrate as a complexing agent and a sintering aid, wherein the addition amount of the citric acid monohydrate is 1.5 times of the total metal ion molar weight, heating the mixed solution in a water bath at 70 ℃ to form gel, continuously heating the gel in a universal furnace until the gel is combusted to form SDC precursor powder, and finally calcining at 800 ℃ for 2 hours to obtain SDC target powder;
step two: preparation of Ba by glycine-nitrate method (GNP)0.5Sr0.5Co0.8Fe0.2O3-δ(BSCF) material powder
According to Ba0.5Sr0.5Co0.8Fe0.2O3-δConfiguration Ba (NO)3)2、Sr(NO3)2、Co(NO3)2·6H2O、Fe(NO3)3·9H2Adopting glycine as a complexing agent and a sintering aid for the O solution, wherein the total molar ratio of glycine to metal ions is 1.5:1, heating the mixed solution in a universal furnace to burn to prepare BSCF precursor powder, and calcining at 900 ℃ for 2 hours to prepare BSCF target powder;
step three: preparation of electrolyte substrate and printing of BSCF porous oxygen electrode layer
Preparing an electrolyte substrate sheet with the diameter of about 2cm by adopting the SDC target powder prepared in the step one through a tabletting method, sintering the substrate at 1400 ℃ for 5h for forming, and polishing the surface of the formed SDC substrate for later use;
preparing BSCF electrode slurry by adopting the BSCF powder prepared in the second step:
mixing ethyl cellulose and terpineol, and preparing an organic binder, wherein the ethyl cellulose accounts for 1 wt%, and the terpineol accounts for 99 wt%; then mixing and grinding the BSCF powder and PMMA for 1 hour, wherein the mass of the PMMA accounts for 2 percent of the total mass of the powder; finally, adding an organic binder into the BSCF and PMMA mixed powder according to the mass ratio of 1:10 (binder: mixed powder), and mixing and grinding for 1 hour to obtain mixed slurry;
printing the mixed slurry on an SDC substrate by a screen printing method, and drying for 30min at 50 ℃; calcining at 1100 deg.C for 3 hr to obtain BSCF/SDC half cell with BSCF electrode layer of 40 μm thickness and 0.25cm area2。
Comparative example 2
The example is to use La2NiO4(LNO) powder as an active material, by powder suspension impregnation method to Ba in a molar ratio of 7:30.5Sr0.5Co0.8Fe0.2O3-δAnd modifying the SDC porous complex phase electrode to finally obtain the powder impregnated LNO-BSCF-SDC composite oxygen electrode and the preparation steps thereof.
The method comprises the following specific steps:
the method comprises the following steps: preparation of Sm by sol-gel method0.2Ce0.8O1.9(SDC) electrolyte material powder
According to Sm0.2Ce0.8O1.9Respectively dispose Ce (NO)3)2·6H2O、Sm(NO3)3·6H2Adopting citric acid monohydrate as a complexing agent and a sintering aid, wherein the addition amount of the citric acid monohydrate is 1.5 times of the total metal ion molar weight, heating the mixed solution in a water bath at 70 ℃ to form gel, continuously heating the gel in a universal furnace until the gel is combusted to form SDC precursor powder, and finally calcining at 800 ℃ for 2 hours to obtain SDC target powder;
step two: preparation of Ba by glycine-nitrate method (GNP)0.5Sr0.5Co0.8Fe0.2O3-δ(BSCF) material powder and La2NiO4(LNO) active material powder
According to Ba0.5Sr0.5Co0.8Fe0.2O3-δConfiguration Ba (NO)3)2、Sr(NO3)2、Co(NO3)2·6H2O、Fe(NO3)3·9H2Adopting glycine as a complexing agent and a sintering aid for the O solution, wherein the total molar ratio of glycine to metal ions is 1.5:1, heating the mixed solution in a universal furnace to burn to prepare BSCF precursor powder, and calcining at 900 ℃ for 2 hours to prepare BSCF target powder;
according to La2NiO4Configuration La (NO)3)3·6H2O、Ni(NO3)2·6H2Adopting glycine as a complexing agent and a sintering aid for the O solution, wherein the total molar ratio of glycine to metal ions is 1.1:1, heating the mixed solution in a universal furnace to burn to prepare LNO precursor powder, and calcining at 850 ℃ for 2 hours to prepare LNO active material powder;
step three: preparation of electrolyte substrate and printing of BSCF-SDC porous complex phase oxide electrode layer
Preparing an electrolyte substrate sheet with the diameter of about 2cm by adopting the SDC target powder prepared in the step one through a tabletting method, sintering the substrate at 1400 ℃ for 5h for forming, and polishing the surface of the formed SDC substrate for later use;
preparing BSCF-SDC electrode slurry by adopting the BSCF powder prepared in the second step:
mixing ethyl cellulose and terpineol, and preparing an organic binder, wherein the ethyl cellulose accounts for 1 wt%, and the terpineol accounts for 99 wt%; mixing and grinding the SDC powder, the BSCF powder and the PMMA for 1 hour, wherein the molar ratio of the SDC to the BSCF powder is 3:7, and the mass of the PMMA accounts for 2 percent of the total mass of the powder; finally, adding an organic binder into the mixed powder of the SDC, the BSCF and the PMMA according to the mass ratio of 1:10 (binder: mixed powder), and mixing and grinding for 1 hour to obtain mixed slurry;
printing the mixed slurry on an SDC substrate by a screen printing method, and drying for 30min at 50 ℃; calcining at 1100 deg.C for 3 hr to obtain BSCF-SDC composite porous material with 7:3 molar ratio as substrate layerA thickness of 40 μm and an area of about 0.25cm2；
Step four: generating an LNO active coating layer on a BSCF-SDC composite porous material substrate layer by an infiltration method
Accurately weighing 0.1g of the LNO powder material prepared in the second step, mixing and dissolving in 2mL of ethanol water solution, wherein the volume ratio of ethanol to water in the ethanol water solution is 1:1, ultrasonically stirring for 10 hours, transferring into a volumetric flask, and fixing the volume to obtain 0.1g/mL of LNO powder suspension.
Determining the volume of the powder suspension liquid impregnated each time according to the load capacity of the required active material, uniformly distributing the suspension liquid with the required volume on a BSCF-SDC composite porous material substrate layer through a microsyringe, and drying for 30min under negative pressure; and sintering at 850 ℃ for 2 hours to obtain the LNO/BSCF-SDC/SDC half cell, wherein the load capacity of the LNO active material is about 8 wt%.
The electrode impedance performance of the half-cell was tested using a three-electrode system, i.e., the complex phase porous electrode prepared in each example was used as the working electrode, the Pt-air electrode was used as the reference electrode and the auxiliary electrode, respectively, the platinum wire was used as the electrode lead, the electrochemical workstation was used, 10-2～105And in the Hz frequency range, the alternating current impedance spectrums of different electrodes at 600-800 ℃ are respectively tested with the alternating current amplitude of 10mV under the condition of open circuit voltage.
As shown in fig. 3, which is a comparison graph of alternating current impedance of composite electrodes of BSCF-SDC with different molar ratios at 700 ℃, when the molar ratio of BSCF to SDC is 7:3, the electrode impedance is the smallest, and the electrochemical performance is the best.
As shown in fig. 4, which is a comparison graph of ac impedance at 700 ℃ of the BSCF electrode, the BSCF-SDC (molar ratio 7:3) electrode, and the LNO/BSCF-SDC (molar ratio 7:3) electrode prepared by the dipping method and the impregnation method respectively, it can be seen that the polarization resistance of the BSCF-SDC composite electrode is significantly smaller than that of the BSCF electrode, and the LNO/BSCF-SDC electrode prepared by the solution in-situ dipping method has a smaller polarization resistance than that of the BSCF electrode.
Claims (9)
1. A composite oxygen electrode for a solid oxide electrolytic cell, characterized in that: comprises an electrolyte layer, a substrate layer and an active coating layer;
the substrate layer is made of BSCF-SDC composite porous material and covers the electrolyte layer;
the active coating layer is coated on the outer surface and the inner surface of pores of the BSCF-SDC composite porous material;
the material of the active coating layer is Ln2NiO4The material is characterized in that Ln is La, Pr or Nd, and the coating amount is 2-20 wt% of the composite oxygen electrode.
2. The composite oxygen electrode of claim 1, wherein: the electrolyte layer is made of SDC, and the thickness of the electrolyte layer is 500-1000 mu m.
3. The composite oxygen electrode of claim 1, wherein: the BSCF-SDC composite porous material has the BSCF-SDC molar ratio of 1: 4-4: 1.
4. The composite oxygen electrode of claim 3, wherein: the mole ratio of BSCF to SDC in the BSCF-SDC composite porous material is 7: 3.
5. The method for producing a composite oxygen electrode according to any one of claims 1 to 4, characterized in that: firstly, printing a BSCF-SDC composite porous material substrate layer on an electrolyte layer of an electrolytic cell sheet, and then depositing an active coating layer on the outer surface and the inner surfaces of pores of the BSCF-SDC composite porous material in situ by adopting an immersion method to obtain the composite oxygen electrode.
6. The method of claim 5, wherein: firstly, preparing an electrolyte layer and SDC by adopting a sol-gel method, and preparing BSCF (barium strontium carbonate) by adopting a glycine-nitrate method; printing the BSCF and SDC mixed slurry on an electrolyte layer of the electrolytic cell sheet by adopting a screen printing method, and calcining to obtain a BSCF-SDC composite porous material substrate layer; and finally, uniformly depositing an active coating layer on the outer surface and the inner surfaces of pores of the BSCF-SDC composite porous material by adopting an immersion method, and then sintering at high temperature to obtain the composite oxygen electrode.
7. The method of claim 6, wherein: the preparation method specifically comprises the following steps:
the method comprises the following steps: the material of the electrolyte layer is SDC and Ce (NO)3)2·6H2O、Sm(NO3)3·6H2Using citric acid monohydrate as a complexing agent and a sintering aid as a raw material, preparing an SDC precursor by a sol-gel method, and finally calcining the SDC precursor for 1-4 hours at the temperature of 600-800 ℃ to prepare SDC powder;
step two: using Ba (NO)3)2、Sr(NO3)2、Co(NO3)2·6H2O、Fe (NO3)3·9H2Taking O as a raw material, adopting glycine as a complexing agent and a sintering aid, preparing a BSCF precursor by a glycine-nitrate method, and calcining the BSCF precursor for 1-4 hours at the temperature of 800-1100 ℃ to prepare BSCF powder;
step three: mixing ethyl cellulose and terpineol to prepare an organic binder; then mixing and grinding the SDC powder, the BSCF powder, the organic binder and the pore-forming agent to obtain mixed slurry; printing the mixed slurry on an electrolyte layer of an electrolytic cell sheet by a screen printing method, and calcining for 1-4 hours at the temperature of 900-1200 ℃ to obtain a BSCF-SDC composite porous material substrate layer;
step four: according to the formula Ln2NiO4Preparing nitrate solution according to the stoichiometric ratio of the elements, adding glycine and PVP, and fully mixing to obtain Ln2NiO4A precursor solution; using a dipping method to dip Ln2NiO4Depositing the precursor solution on the outer surface and the inner surface of the pores of the BSCF-SDC composite porous material; and sintering at 800-1000 ℃ for 1-4 hours to obtain the composite oxygen electrode.
8. The method of claim 7, wherein: the pore-forming agent is at least one of PMMA, starch and activated carbon, and the addition amount of the pore-forming agent is 2-12 wt% of the total amount of the SDC powder and the BSCF powder.
9. A solid oxide electrolytic cell comprising the composite oxygen electrode according to any one of claims 1 to 4 or the composite oxygen electrode produced by the production method according to any one of claims 5 to 8.
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