CN111244470B - Nano composite cathode and preparation and application thereof - Google Patents

Nano composite cathode and preparation and application thereof Download PDF

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CN111244470B
CN111244470B CN201811443289.9A CN201811443289A CN111244470B CN 111244470 B CN111244470 B CN 111244470B CN 201811443289 A CN201811443289 A CN 201811443289A CN 111244470 B CN111244470 B CN 111244470B
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程谟杰
黄志东
赵哲
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Dalian Institute of Chemical Physics of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
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    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H01M4/8828—Coating with slurry or ink
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
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    • H01M8/00—Fuel cells; Manufacture thereof
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    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/1213—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/1231—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte with both reactants being gaseous or vaporised
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
    • H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
    • H01M8/1253—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides the electrolyte containing zirconium oxide
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Abstract

The invention discloses a nano composite cathode for a high-temperature solid oxide electrolytic cell, and a preparation method and application thereof. The nano composite cathode is structurally characterized in that a YSZ framework with micropores is prepared by adopting PMMA as a pore-forming agent, an LSFM-GDC (M is Mn, Fe and Ni) composite nano electrode catalyst is prepared by adopting a co-impregnation method, and the nano composite cathode for the high-temperature solid oxide electrolytic cell is prepared after roasting. The high-temperature solid oxide nano composite cathode prepared by the invention is suitable for high-temperature CO2Electrolysis and CO2‑H2Co-electrolysis of O for high temperature CO2Electrolysis and CO2‑H2The O co-electrolysis has good electrochemical performance, can obviously improve the performance and the operation stability of the solid oxide electrolytic cell, and has good development prospect. The invention is suitable for the fields of high-temperature carbon dioxide reduction, clean carbon fuel preparation and energy and fuel cell technologies.

Description

Nano composite cathode and preparation and application thereof
Technical Field
The invention relates to the technical field of energy and fuel cells, in particular to a nano composite cathode and a preparation method and application thereof.
Background
The demand of conventional fossil energy such as coal, oil and natural gas in our country is increasing and the reserves thereof are restricted, so that the national energy safety situation becomes more severe. In addition, the consumption of traditional fossil energy is related to CO2Emission-related problems resulting in climate change are also an important issue in the international society of today. A Solid Oxide Electrolysis Cell (SOEC) is an electrochemical device that converts electrical and thermal energy to chemical energy in fuels in an efficient and environmentally friendly manner at medium and high temperatures. Solid oxide electrolytic cells) are operated at a temperature in the range of 600-. The solid oxide electrolytic cell technology can produce H by electrolyzing water2CO-electrolysis of water and CO2The synthesis gas production has attracted much attention in recent years. The high operating temperature of the SOEC can reduce the electrical energy requirements of the electrolysis process, thereby reducing hydrogen production andthe cost of the synthesis gas also improves the dynamic performance of the electrode and reduces the electrolyte resistance of the SOEC, thereby reducing the performance loss of the battery. SOEC will exhibit greater efficiency in producing hydrogen and syngas than low temperature electrolytic cells if the waste heat of a power plant or other industrial process can be used to maintain the operation of the electrolytic cells. Thermodynamically, high temperature electrolysis can reduce the power consumption in the electrolysis process and can utilize the waste heat of power stations or other industrial processes; in terms of dynamics, high-temperature electrolysis can reduce the internal resistance of the battery and improve the current density, thereby improving the electrolysis efficiency. The high working temperature can accelerate the electrode reaction rate, obviously reduce the electrode polarization voltage, effectively reduce the irreversible energy loss in the electrolysis process, and simultaneously reduce the energy required by electrolysis and the electrolysis voltage along with the rise of the temperature, thereby further reducing the loss of electric energy. Thus, SOEC has higher electrolysis efficiency and energy conversion than low temperature electrolysis technology, and is considered to be currently CO2One of the most feasible and promising technological routes to fuel conversion.
In solid oxide electrolyzers, the conventional fuel electrode is usually a porous electrode of a composite of metallic Ni and YSZ, but it is CO-operated at high temperature2Electrolysis and CO-electrolysis of water and CO2There are still some unsolved problems with the application of (1): if the oxygen reduction stability is poor, a reducing gas with a certain concentration is needed to prevent Ni of the electrode from being oxidized into NiO, Ni particles are agglomerated at high temperature and volatilized at high temperature, the performance of the battery is reduced due to the influence of various impurity elements, and the problems of carbon deposition and the like exist at the same time.
Therefore, the development of new high-performance and high-stability fuel electrode materials is one of the important approaches for advancing the commercialization process of high-temperature solid oxide electrolytic cells.
Disclosure of Invention
At present, CO is at high temperature2And CO2And H2In O-CO-electrolysis cells, the conventional fuel electrode is usually a porous electrode of a composite of metallic Ni and YSZ, which is CO-electrolyzed at high temperature2Electrolysis and CO2And H2The use in O co-electrolysis still presents some unsolved problems such as stability problems and carbon deposition problems. To overcome the disadvantages ofBulk oxide CO2The present invention is directed to a nanocomposite electrode for high temperature solid oxide having excellent high temperature CO and a method for preparing the same2Electrolysis and CO2And H2O-co-electrolysis performance and anti-carbon deposition performance.
A nanometer composite cathode for a high-temperature solid oxide electrolytic cell is characterized in that a YSZ framework which is prepared by adopting PMMA as a pore-forming agent and has micron pores is covered on an electrolyte layer of a semi-electrolytic cell sheet, LSFM-GDC (M is Mn, Cu and Ni) composite nanoparticles are prepared by adopting a co-immersion method and cover the YSZ framework to form the novel nanometer composite cathode for the high-temperature solid oxide electrolytic cell; wherein the LSFM-GDC composite nano-particles are electrode catalysts of the SOEC composite nano-cathode.
Wherein: SOEC is solid oxide electrolytic cell; PMMA is polymethyl methacrylate; LSFM is Sr and M (M ═ Mn, Cu and Ni) doped LaFeO3Of composition LaxSr1-xFeyM1-yO3(wherein x is more than or equal to 0 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 1); LSFM-GDC is LSFM and Gd doped CeO2The GDC is GdxCe1-xO2X is more than or equal to 0 and less than or equal to 1; YSZ is yttria stabilized zirconia (8 YSZ).
The electrolytic cell prepared by the invention is an electrolyte-supported solid oxide electrolytic cell, and the nano composite cathode has the characteristics of stable structure, high oxidation-reduction property, high mixed conductivity, high catalytic activity, high three-phase interface and the like, and can be used for treating high-temperature CO2The electrolysis has good electrochemical performance and good development prospect.
The active electrode catalyst of the SOEC nano composite cathode is LSFM-GDC composite nano particles, wherein M is Mn, Fe, Ni and the like), the material has a perovskite phase-fluorite phase composite structure, and a large number of oxygen vacancies are formed on the surface of the material, so that the interaction between gas molecules and the surface of the electrode under a high-temperature condition is favorably strengthened, and the CO is improved2Electrolysis and CO2、H2O-common electrolysis efficiency; meanwhile, the active catalyst layer can also provide a large number of oxygen ion conduction channels, which is beneficial to oxygen ion conductionThereby improving the electrochemical performance of the electrolytic cell.
The invention adopts a screen printing method, a slurry coating method or a spin coating method to prepare a YSZ framework, then adopts a co-soaking method to uniformly deposit LSFM-GDC nano composite active catalyst on the surface and in micropores of the YSZ framework to prepare a nano composite cathode active catalyst layer, and prepares a nano composite cathode for a high-temperature solid oxide electrolytic cell after high-temperature sintering, and the specific preparation steps are as follows:
the method comprises the following steps: preparation of LSFM-GDC precursor solution
(1) La according to the formula LSFM-GDCxSr1-xFeyM1-yO3-GdzCe1-zO2(M is Mn, Cu and Ni, wherein the mass ratio of LSFM to GDC is 50:50, x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, and z is more than or equal to 0 and less than or equal to 1) to prepare a nitrate mixed solution, and accurately weighing La according to the metal ion proportion in the chemical formula3+、Sr2+、Fe3+、Mn+、Gd3+And Ce4+Adding a proper amount of deionized water into the nitrate in a beaker, and stirring for 30-60 min until the nitrate is completely dissolved to obtain mixed La3+、Sr2+、Fe3+、Mn+、Gd3+And Ce4+A nitrate solution.
(2) In mixed La3+、Sr2+、Fe3+、Mn+、Gd3+And Ce4+Adding ammonium citrate into the nitrate solution, wherein the ratio of the adding amount of the ammonium citrate to the total mole number of the metal ions is 1.5: 1;
(3) adjusting the pH value of the solution obtained in the step (2) to 1-2 by using nitric acid with the molar concentration of 2mol/L to prepare an LSFM-GDC precursor solution; and heating the precursor solution at a constant temperature of 60-80 ℃, continuously stirring, and putting the precursor solution into a volumetric flask for constant volume to obtain the LSFM-GDC precursor solution with a certain metal ion concentration.
Step two: preparation of YSZ skeleton
(1) Weighing a certain amount of YSZ powder and PMMA, wherein the mass ratio of the YSZ powder to the PMMA is 50:50wt%, then adding a proper amount of n-butyl alcohol as a solvent, fish oil as a dispersing agent, PVB as a binder and DOP as a plasticizer, uniformly mixing, putting the mixture into an ultrasonic device, carrying out ultrasonic treatment for 8 hours until the powder inside is uniformly dispersed, then putting the mixture under a baking lamp for baking, adding a proper amount of organic binder, and uniformly stirring to obtain white viscous YSZ slurry for later use;
(2) and (2) uniformly coating the YSZ slurry obtained in the step (1) on two sides of the YSZ electrolyte support body by adopting a screen printing method, a slurry coating method or a spin-coating method, and roasting for 2-8h at the temperature of 1000-1300 ℃ in an air atmosphere to obtain the YSZ framework with the microporous structure on the YSZ electrolyte support body.
Step three: preparing LSFM-GDC nano composite cathode on YSZ framework with microporous structure by adopting impregnation method
(1) Dipping the LSFM-GDC precursor solution obtained in the step one into the surface and the micropores of the YSZ framework with the micropore structure obtained in the step two by using a vacuum dipping method to obtain an electrolytic cell sheet deposited with the LSFM-GDC precursor;
(2) sintering the electrolytic cell sheet of the LSFM-GDC precursor for 1-2 h at the temperature of 600-800 ℃ in the air atmosphere to obtain the LSFM-GDC composite nano active catalyst layer covering the surface and the micropores of the YSZ framework, namely preparing the LSFM-GDC nano composite cathode on the YSZ framework with the microporous structure.
The electrolyte supporting semi-electrolytic cell sheet material is YSZ, the thickness is 100-1000 microns, a compact electrolyte layer can be provided for an electrolytic cell, the comprehensive electrochemical performance of the electrolytic cell is improved, and meanwhile, sufficient mechanical strength can be provided for the electrolytic cell.
The solid oxide electrolytic cell is a symmetrical cell, and both a cathode and an anode are LSFM-GDC nano composite electrodes, and the thickness of the solid oxide electrolytic cell is 20-100 micrometers.
The YSZ framework thickness of the nano composite cathode is 20-100 micrometers, and in the most suitable electrode thickness range, the nano composite cathode can provide enough mechanical strength for an electrode, and provides a pore channel required by gas diffusion and an ion channel required by ion diffusion; the thickness of the LSFM-GDC catalytic layer is 5-20 microns, a large number of reaction active sites and three-phase interfaces can be provided for electrode reaction, and the improvement of the battery performance is facilitated.
The LSFM-GDC nano composite electrode material of the solid oxide electrolytic cell is LSFM-GDC, wherein M can be one or more of Mn, Cu and Ni, and can provide good electronic conductivity and oxygen ion conductivity for the electrode, thereby being beneficial to improving the comprehensive electrochemical performance of the electrolytic cell.
According to the invention, the YSZ framework slurry obtained by adopting a screen printing method, a slurry coating method or a spin coating method is coated on the electrolyte layer of the semi-electrolytic cell plate, and is calcined for 2-8 hours at 1000-1300 ℃ in an air atmosphere, so that the YSZ framework with a microporous structure on the YSZ electrolyte support body can be simply and effectively obtained.
The LSFM-GDC precursor solution is soaked on a YSZ framework of an electrolytic cell sheet by adopting a soaking method, and is sintered for 1-2 hours at the temperature of 600-800 ℃ in an air atmosphere to obtain an LSFM-GDC composite nano active catalyst layer covering the surface and the inner part of a micropore of the YSZ framework, namely an LSFM-GDC nano composite cathode is prepared on the YSZ framework with a micropore structure.
The high-temperature solid oxide nano composite cathode prepared by the invention is suitable for high-temperature CO2Electrolysis and CO2-H2Co-electrolysis of O for high temperature CO2Electrolysis and CO2-H2The O co-electrolysis has good electrochemical performance, can obviously improve the performance and the operation stability of the solid oxide electrolytic cell, and has good development prospect. The invention is suitable for the fields of high-temperature carbon dioxide reduction, clean carbon fuel preparation and energy and fuel cell technologies.
Detailed Description
The invention is further illustrated by the following examples:
example 1:
(1) la according to the formula LSFM-GDC0.6Sr0.4Fe0.8Mn0.2O3-Gd0.2Ce0.8O2LSFMn: the mass ratio of GDC is 50:50 wt%) to prepare nitrate mixed solution, and accurately weighing La according to the metal ion proportion in the chemical formula3+、Sr2+、Fe3+、Mn4 +、Gd3+And Ce4+Adding a proper amount of deionized water into the nitrate in a beaker, and stirring for 30-60 min until the nitrate is completely dissolved to obtain mixed La3+、Sr2+、Fe3+、Mn4+、Gd3+And Ce4+A nitrate solution.
(2) In mixed La3+、Sr2+、Fe3+、Mn4+、Gd3+And Ce4+Adding ammonium citrate into the nitrate solution, wherein the ratio of the adding amount of the ammonium citrate to the total mole number of the metal ions is 1.5: 1;
(3) regulating the pH value of the solution obtained in the step (2) to 1-2 by using nitric acid with the molar concentration of 2mol/L to prepare an LSFMn-GDC precursor solution; and heating the precursor solution at a constant temperature of 80 ℃, continuously stirring, and putting the precursor solution into a volumetric flask for constant volume to obtain the LSFMn-GDC precursor solution with the metal ion concentration of 2 mol/L.
(4) Weighing 50g of YSZ powder and PMMA, wherein the mass ratio of the YSZ powder to the PMMA is 50:50wt%, then adding 100g of n-butyl alcohol as a solvent, 1g of fish oil as a dispersing agent, 6g of PVB as a binder and 6g of DOP as a plasticizer, uniformly mixing, putting the mixture in an ultrasonic device, carrying out ultrasonic treatment for 8 hours until the powder inside is uniformly dispersed, then putting the mixture under a baking lamp for baking, adding 10g of organic binder, and uniformly stirring to obtain white viscous YSZ slurry for later use;
(5) and (3) uniformly coating the YSZ slurry obtained in the step (4) on two sides of a YSZ electrolyte support body by adopting a screen printing method, and roasting for 5 hours at 1300 ℃ in an air atmosphere to obtain a YSZ framework with a microporous structure on the YSZ electrolyte support body.
(6) Dipping the LSFMn-GDC precursor solution obtained in the step (3) into the surface and micropores of the YSZ framework with the micropore structure obtained in the step (5) by using a vacuum dipping method to obtain an electrolytic cell sheet deposited with the LSFMn-GDC precursor;
(7) sintering the electrolytic cell sheet of the LSFMn-GDC precursor for 2h at 800 ℃ in an air atmosphere to obtain the LSFMn-GDC composite nano active catalyst layer covering the surface and the micropores of the YSZ framework, namely preparing the LSFMn-GDC nano composite cathode on the YSZ framework with the microporous structure.
(8) The electrolytic cell obtained by the invention has pure CO at the cathode atmosphere of 800 DEG C2The anode atmosphere is air, the charging is carried out at 1.5V, and the electrolytic current density can reach 0.85A cm-2CO yield 5.57mL min-1cm-2。
Example 2:
(1) la according to the formula LSFM-GDC0.6Sr0.4Fe0.8Mn0.2O3-Gd0.2Ce0.8O2LSFNi: the mass ratio of GDC is 50:50 wt%) to prepare nitrate mixed solution, and accurately weighing La according to the metal ion proportion in the chemical formula3+、Sr2+、Fe3+、Ni2 +、Gd3+And Ce4+Adding a proper amount of deionized water into the nitrate in a beaker, and stirring for 60min until the nitrate is completely dissolved to obtain mixed La3 +、Sr2+、Fe3+、Ni2+、Gd3+And Ce4+A nitrate solution.
(2) In mixed La3+、Sr2+、Fe3+、Ni2+、Gd3+And Ce4+Adding ammonium citrate into the nitrate solution, wherein the ratio of the adding amount of the ammonium citrate to the total mole number of the metal ions is 1.5: 1;
(3) adjusting the pH value of the solution obtained in the step (2) to 1-2 by using nitric acid with the molar concentration of 2mol/L to prepare an LSFNi-GDC precursor solution; and heating the precursor solution at a constant temperature of 70 ℃, continuously stirring, and putting the precursor solution into a volumetric flask for constant volume to obtain the LSFNi-GDC precursor solution with the metal ion concentration of 2 mol/L.
(4) Weighing 50g of YSZ powder and PMMA, wherein the mass ratio of the YSZ powder to the PMMA is 50:50wt%, then adding 80g of n-butyl alcohol as a solvent, 1g of fish oil as a dispersing agent, 4g of PVB as a binder and 4g of DOP as a plasticizer, uniformly mixing, putting the mixture in an ultrasonic device, carrying out ultrasonic treatment for 8 hours until the powder inside is uniformly dispersed, then putting the mixture under a baking lamp for baking, adding 15g of organic binder, and uniformly stirring to obtain white viscous YSZ slurry for later use;
(5) and (3) uniformly coating the YSZ slurry obtained in the step (4) on two sides of a YSZ electrolyte support body by adopting a screen printing method, and roasting for 7 hours at 1250 ℃ in an air atmosphere to obtain a YSZ framework with a microporous structure on the YSZ electrolyte support body.
(6) Dipping the LSFNi-GDC precursor solution obtained in the step (3) into the surface and the micropores of the YSZ framework with the micropore structure obtained in the step (5) by a vacuum dipping method to obtain an electrolytic cell sheet deposited with the LSFNi-GDC precursor;
(7) sintering the electrolytic cell sheet of the LSFNi-GDC precursor for 2h at 750 ℃ in air atmosphere to obtain the LSFNi-GDC composite nano active catalyst layer covered on the surface and in the micropores of the YSZ framework, namely preparing the LSFNi-GDC nano composite cathode on the YSZ framework with the micropore structure.
(8) The electrolytic cell obtained by the invention has a cathode atmosphere of 50% CO at 800 DEG C2-50％H2O, the anode atmosphere is air, 1.5V is charged, and the electrolytic current density can reach 1.26A cm-2。
Example 3:
(1) la according to the formula LSFM-GDC0.6Sr0.4Fe0.8Mn0.2O3-Gd0.2Ce0.8O2LSFCu: the mass ratio of GDC is 50:50 wt%) to prepare nitrate mixed solution, and accurately weighing La according to the metal ion proportion in the chemical formula3+、Sr2+、Fe3+、Cu2 +、Gd3+And Ce4+Adding a proper amount of deionized water into the nitrate in a beaker, and stirring for 60min until the nitrate is completely dissolved to obtain mixed La3 +、Sr2+、Fe3+、Cu2+、Gd3+And Ce4+A nitrate solution.
(2) In mixed La3+、Sr2+、Fe3+、Cu2+、Gd3+And Ce4+Adding ammonium citrate into the nitrate solution, wherein the ratio of the adding amount of the ammonium citrate to the total mole number of the metal ions is 1.5: 1;
(3) adjusting the pH value of the solution obtained in the step (2) to 1-2 by using nitric acid with the molar concentration of 2mol/L to obtain an LSFCu-GDC precursor solution; and heating the precursor solution at a constant temperature of 70 ℃, continuously stirring, and putting the precursor solution into a volumetric flask for constant volume to obtain the LSFCu-GDC precursor solution with the metal ion concentration of 2 mol/L.
(4) Weighing 50g of YSZ powder and PMMA, wherein the mass ratio of the YSZ powder to the PMMA is 50:50wt%, then adding 120g of n-butyl alcohol as a solvent, 1g of fish oil as a dispersing agent, 4g of PVB as a binder and 4g of DOP as a plasticizer, uniformly mixing, putting the mixture in an ultrasonic device, carrying out ultrasonic treatment for 8 hours until the powder inside is uniformly dispersed, then putting the mixture under a baking lamp for baking, adding 20g of organic binder, and uniformly stirring to obtain white viscous YSZ slurry for later use;
(5) and (3) uniformly coating the YSZ slurry obtained in the step (4) on two sides of a YSZ electrolyte support body by adopting a screen printing method, and roasting for 7 hours at 1280 ℃ in an air atmosphere to obtain a YSZ framework with a microporous structure on the YSZ electrolyte support body.
(6) Dipping the LSFCu-GDC precursor solution obtained in the step (3) into the surface and micropores of the YSZ framework with the micropore structure obtained in the step (5) by using a vacuum dipping method to obtain an electrolytic cell sheet deposited with the LSFCu-GDC precursor;
(7) sintering the electrolytic cell sheet of the LSFCu-GDC precursor for 2 hours at the temperature of 750 ℃ in an air atmosphere to obtain the LSFCu-GDC composite nano active catalyst layer covered on the surface and in the micropores of the YSZ framework, namely preparing the LSFCu-GDC nano composite cathode on the YSZ framework with the microporous structure.
(8) The electrolytic cell obtained by the invention has pure CO at the cathode atmosphere of 800 DEG C2The anode atmosphere is air, the charging is carried out at 1.5V, and the electrolytic current density can reach 0.56A cm-2CO yield 3.79mL min-1cm-2。

Claims (9)

1. A preparation method of a nano composite cathode for a high-temperature solid oxide electrolytic cell is characterized in that a YSZ framework which is prepared by adopting PMMA as a pore-forming agent and has micropores is covered on an electrolyte layer of a semi-electrolytic cell plate, and LSFM-GDC composite nano particles are prepared by adopting a co-immersion method to cover the YSZ framework to form the nano composite cathode for the high-temperature solid oxide electrolytic cell; wherein the LSFM-GDC composite nano particles are electrode catalysts of the SOEC composite nano cathode;
wherein: SOEC is solid oxide electrolytic cell; PMMA is polymethyl methacrylate; LSFM is LaFeO3Or Sr, M doped LaFeO3Of composition LaxSr1-xFeyM1-yO3Wherein x is more than or equal to 0 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 1; LSFM-GDC is LSFM and CeO2Or Gd doped with CeO2The GDC is GdxCe1-xO2X is more than or equal to 0 and less than or equal to 1; YSZ is yttria stabilized zirconia 8 YSZ;
the preparation method of the nano composite cathode comprises the following steps: preparing a YSZ framework by adopting a screen printing method, a slurry coating method or a spin-coating method, then uniformly depositing an LSFM-GDC nano composite active catalyst on the surface and in micropores of the YSZ framework by adopting a co-immersion method to prepare a nano composite cathode active catalyst layer, and preparing a nano composite cathode for a high-temperature solid oxide electrolytic cell by high-temperature sintering, wherein the specific preparation steps are as follows:
the method comprises the following steps: preparation of LSFM-GDC precursor solution
(1) La according to the formula LSFM-GDCxSr1-xFeyM1-yO3-GdzCe1-zO2Preparing a nitrate mixed solution, wherein M = one or more of Mn, Cu and Ni, and LSFM: the mass ratio of GDC is 50:50, x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, and z is more than or equal to 0 and less than or equal to 1; accurately weighing La according to the proportion of metal ions in the chemical formula3+、Sr2+、Fe3+、Mn+、Gd3+And Ce4+Adding a proper amount of deionized water into the nitrate in a beaker, and stirring for 30-60 min until the nitrate is completely dissolved to obtain mixed La3+、Sr2+、Fe3+、Mn+、Gd3+And Ce4+A nitrate solution;
(2) in mixed La3+、Sr2+、Fe3+、Mn+、Gd3+And Ce4+Adding ammonium citrate into the nitrate solution, wherein the ratio of the adding amount of the ammonium citrate to the total mole number of the metal ions is 1.5: 1;
(3) with a molar concentration of 2mol/LAdjusting the pH value of the solution obtained in the step (2) to 1-2 by nitric acid to prepare an LSFM-GDC precursor solution; the precursor solution is added at 60-80%oHeating at constant temperature under C, stirring continuously, and placing in a volumetric flask to constant volume to obtain LSFM-GDC precursor solution with certain metal ion concentration;
step two: preparation of YSZ skeleton
(1) Weighing a certain amount of YSZ powder and PMMA, wherein the mass ratio of the YSZ powder to the PMMA is 50:50wt%, then adding a proper amount of n-butyl alcohol as a solvent, fish oil as a dispersing agent, PVB as a binder and DOP as a plasticizer, uniformly mixing, putting the mixture into an ultrasonic device, carrying out ultrasonic treatment for 8 hours until the powder inside is uniformly dispersed, then putting the mixture under a baking lamp for baking, adding a proper amount of organic binder, and uniformly stirring to obtain white viscous YSZ slurry for later use;
(2) uniformly coating the YSZ slurry obtained in the step (1) on two sides of a YSZ electrolyte support body by adopting a screen printing method, a slurry coating method or a spin coating method, and performing screen printing on the YSZ electrolyte support body at a temperature of 1000-oC, roasting for 2-8h in an air atmosphere to obtain a YSZ framework with a microporous structure on the YSZ electrolyte support body;
step three: preparing LSFM-GDC nano composite cathode on YSZ framework with microporous structure by adopting impregnation method
(1) Dipping the LSFM-GDC precursor solution obtained in the step one into the surface and the micropores of the YSZ framework with the micropore structure obtained in the step two by using a vacuum dipping method to obtain an electrolytic cell sheet deposited with the LSFM-GDC precursor;
(2) the electrolytic cell piece of the LSFM-GDC precursor is subjected to temperature of 600-800 DEG CoAnd C, sintering for 1-2 h in an air atmosphere to obtain an LSFM-GDC composite nano active catalyst layer covering the surface and the micropores of the YSZ framework, namely preparing the LSFM-GDC nano composite cathode on the YSZ framework with the micropore structure.
2. A method according to claim 1, wherein said half-cell plate is an electrolyte-supporting half-cell plate.
3. The preparation method of claim 2, wherein the electrolyte-supporting half-cell sheet is made of YSZ and prepared by a tape casting method, and the thickness of the YSZ is 100-1000 microns.
4. The method as claimed in claim 1, wherein the solid oxide electrolytic cell is a symmetrical cell, and the cathode and the anode are both LSFM-GDC nanocomposite electrodes with a thickness of 20-100 μm.
5. The preparation method of claim 1, wherein the SOEC nano composite cathode has a LSFM-GDC nano catalytic layer with a thickness of 20-100 nm.
6. The preparation method of claim 1, wherein the LSFM-GDC composite nanopowder has a particle size of 10-100 nm.
7. The method of claim 1, wherein the LSFM-GDC precursor solution has a total metal ion molar concentration of 1-2 mol/L.
8. The method of claim 1, wherein the organic binder is prepared by dissolving ethyl cellulose in terpineol, wherein the ethyl cellulose accounts for 6wt% and the terpineol accounts for 94%.
9. Use of a nanocomposite cathode for a high temperature solid oxide electrolytic cell prepared by the preparation method according to any one of claims 1 to 8 in a high temperature solid oxide electrolytic cell.
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