CN114182288A - Solid oxide electrolytic cell oxygen electrode and preparation method thereof - Google Patents
Solid oxide electrolytic cell oxygen electrode and preparation method thereof Download PDFInfo
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- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses an oxygen electrode of a solid oxide electrolytic cell and a preparation method thereof, wherein the oxygen electrode consists of an oxygen ion-electron mixed conductor framework and a nano composite catalyst uniformly covering the surface of the oxygen ion-electron mixed conductor framework, the particle size of the oxygen ion-electron mixed conductor framework is 200-2000 nm, the porosity of the framework is 40-70%, the particle size of the nano composite catalyst is 1-100 nm, and the electrode has rich oxygen evolution active sites, and shows excellent electrochemical performance and good stability.
Description
Technical Field
The invention relates to the field of fuel cells and electrolytic cells, in particular to a solid oxide electrolytic cell oxygen electrode with good stability and performance and a preparation method thereof.
Background
A Solid Oxide Electrolysis Cell (SOEC) can electrolyze water vapor into hydrogen and oxygen at high temperature, the electrical efficiency can reach 100%, and the Solid Oxide electrolysis Cell is considered to be the most efficient hydrogen production technology.
The performance and stability are key to the practical application of the SOEC technology. The core component of the SOEC is the membrane electrode, which has a sandwich structure and is dense in the middleThe electrolyte layer of (2) has porous hydrogen and oxygen electrodes on both sides. With the decrease in operating temperature, the slower kinetics of the Oxygen Evolution Reaction (OER) at the oxygen electrode is a major factor that limits membrane electrode performance compared to the rapid water dissociation process at the hydrogen electrode. The oxygen precipitation reaction relates to the processes of oxygen molecule diffusion in electrode pore channels, oxygen molecule absorption and desorption, oxygen intermediate species surface diffusion, charge transfer reaction, oxygen ion-electron transfer and the like. The above reaction process requires that the electrode material should have high electronic conductivity, high oxygen ion conductivity, excellent catalytic oxygen surface reaction activity and reasonable pore structure, however, the electrode material with single phase composition or structure is difficult to meet the above requirements, and it is difficult to achieve high performance output and stable operation at the same time. For example, (La, Sr) MnO3The oxygen electrode has good structural stability, but its low OER activity results in very low hydrogen production performance by electrolysis, and the oxygen electrode/electrolyte interface is easily delaminated in the electrolysis mode. (Ba, Sr) (Co, Fe) O3The oxygen electrode has extremely high oxygen ion conductivity and oxygen surface exchange coefficient, but has the problem of poor structural stability. The invention provides an oxygen electrode of a solid oxide electrolytic cell, which strengthens the gas-ion-electron transmission and electrochemical reaction process and improves the hydrogen production performance of SOEC.
Disclosure of Invention
The invention aims to provide a solid oxide electrolytic cell oxygen electrode with good stability and performance. The technical scheme of the invention is as follows:
an oxygen electrode of a solid oxide electrolytic cell, which consists of an oxygen ion-electron mixed conductor framework and a nano composite catalyst uniformly covering the surface of the oxygen electrode; the mass ratio of the nano composite catalyst to the oxygen ion-electron mixed conductor is 1: 99-20: 80;
the oxygen ion-electron mixed conductor is composed of perovskite oxide A1A2BO3-δA1 is one or more of La, Pr, Sm, Gd, Ce, Er, Yb and Y, A2 is one or more of Ca, Sr, Ba and Mg, B is one or more of Mn, Fe, Co, Ni and Cu, and 0 is more than or equal to 6 and less than 0.5;
the size of the oxygen ion-electron mixed conductor framework particles is 200-2000 nm, and the framework porosity is 40-70%;
the nano composite catalyst is fluorite oxide NxCe1-xO2And spinel oxide K1K22O4The compound is formed, N is one or more of La, Pr, Sm, Gd, Er, Yb and Y, K1 is one of Mn, Fe, Co, Ni, Cu and Zn, K2 is one of Mn, Fe, Co, Ni, Cu and Zn, and x is more than 0 and less than or equal to 0.5; the particle size of the nano composite catalyst is 1-100 nm;
fluorite oxide N in nano composite catalystxCe1-xO2And spinel oxide K1K22O4The mass ratio of (A) to (B) is 20: 80-50: 50.
Further, in the above technical solution, the oxygen ion-electron mixed conductor A1A2BO in the oxygen electrode3-δThe A1 is preferably one or more of La, Pr and Sm, the A2 is preferably one or more of Ba, Sr and Ca, and the B is preferably one or more of Fe, Co, Ni and Mn.
Further, in the above technical solution, the nano composite catalyst in the oxygen electrode is fluorite oxide NxCe1-xO2And spinel oxide K1K22O4In the composite, N is preferably one or more of La, Pr, Sm and Gd.
Further, in the technical scheme, the oxygen ion-electron mixed conductor in the oxygen electrode preferably has a framework particle size of 500-1500 nm, a framework porosity of 50-60%, and a particle size of the nano composite catalyst is preferably 2-50 nm.
Further, in the above technical solution, fluorite oxide N in the nanocomposite catalyst in the oxygen electrodexCe1-xO2And spinel oxide K1K22O4The mass ratio of the nano composite catalyst to the oxygen ion-electron mixed conductor is preferably 25: 75-40: 60, and the mass ratio of the nano composite catalyst to the oxygen ion-electron mixed conductor is preferably 2: 98-10: 90.
The invention provides a preparation method of the oxygen electrode, which comprises the following steps: (1) synthesizing initial powder of the oxygen ion-electron mixed framework material by adopting a solid phase method or a combustion method, and pre-sintering the initial powder at the high temperature of 300-600 ℃ for 1-10 h preferentially; (2) preparing corresponding nitrate mixed liquor according to the molar ratio of elements in the nano composite catalyst, adding a complexing agent, wherein the molar ratio of the complexing agent to metal ions is 1: 1-4: 1, and the concentration of the metal ions is 0.5-3M; (3) adding the framework material powder obtained in the step 1 into the solution obtained in the step 2, then continuously heating and stirring the solution until a combustion reaction occurs, and roasting the initial oxygen electrode powder after combustion at a high temperature of 600-1000 ℃ to obtain the oxygen electrode.
Further, in the above technical solution, after synthesizing the initial powder of the oxygen ion-electron mixed skeleton material by a solid phase method or a combustion method, it is preferable to pre-sinter the initial powder at a high temperature of 400 to 500 ℃.
Further, in the technical scheme, the corresponding nitrate mixed solution is prepared according to the mole ratio of each element in the nano composite catalyst, a complexing agent is added, the ratio of the complexing agent to metal ions is preferably 1.5: 1-2: 1, and the concentration of the metal ions is preferably 0.5-2M.
Further, in the above technical solution, the complexing agent is selected from one or more of glycine, citric acid, and ethylenediaminetetraacetic acid.
The invention has the advantages that:
(1) the invention adopts perovskite oxide A1A2BO with oxygen ion-electron mixed conductive performance3-δThe oxygen electrode is a framework, the oxygen ion and electron transmission performance of the oxygen electrode is improved, and the oxygen evolution reaction active site extends to the surface of the oxygen ion-electron mixed conductor from the oxygen electrode/electrolyte interface, so that the reaction active site is increased;
(2) the invention adds a nano composite catalyst on the surface of a framework, which is fluorite oxide NxCe1-xO2And spinel oxide K1K22O4The composite of the components, the former increases the electrocatalytic activity, the latter increases the surface electron transmission, and the composite of the former and the latter strengthens the oxygen precipitation surface reaction and improves the oxygen precipitation reaction activity;
(3) the nano-composite interphase interaction stabilizes the interface composition and structure, and finally forms the high-efficiency and high-stability SOEC oxygen electrode.
Detailed Description
The invention is further illustrated by the following examples.
Comparative example 1
Preparing a hydrogen electrode supporting button membrane electrode, taking Ni-YSZ (mass ratio of 1: 1) as a hydrogen electrode, gamma SZ as an electrolyte and GDC as an interlayer. Oxygen electrode made of La0.6Sr0.4Co0.2Fe0.8O2.9The oxygen electrode is prepared by a combustion method, is roasted at the high temperature of 900 ℃ for 2 hours, and has the particle size of 500-1500 nm and the framework porosity of 55 percent.
The membrane electrode is used for testing the performance of the electrolyzed water vapor, and the current density of the electrolyzed water reaches-0.98 Acm under the conditions that the absolute humidity of the membrane electrode is 70 percent, the temperature is 800 ℃ and the voltage is 1.3V-2。
Comparative example 2
Preparing a hydrogen electrode supporting button membrane electrode, taking Ni-YSZ (mass ratio of 1: 1) as a hydrogen electrode, YSZ as an electrolyte and GDC as an interlayer. Oxygen electrode made of La0.6Sr0.4Co0.2Fe0.8O2.9@La0.45Ce0.55O2Composition of, wherein, La0.6Sr0.4Co0.2Fe0.8O2.9Is an oxygen ion-electron mixed conductor framework, the particle size is 500-1000 nm, the porosity of the framework is 55%, and La on the surface of the framework0.45Ce0.55O2The particle size is 30-50 nm, the total mass of the oxygen electrode is 0.01g, wherein, La0.6Sr0.4Co0.2Fe0.8O2.90.0095g, La0.45Ce0.55O2The mass was 0.0005 g.
The membrane electrode is used for testing the performance of the electrolyzed water vapor, and the current density of the membrane electrode reaches-1.15 Acm under the conditions that the absolute humidity is 70 percent, the temperature is 800 ℃ and the voltage is 1.3V-2。
Comparative example 3
Preparing a hydrogen electrode supporting button membrane electrode, taking Ni-YSZ (mass ratio of 1: 1) as a hydrogen electrode, YSZ as an electrolyte and GDC as an interlayer. Oxygen electrode made of La0.6Sr0.4Co0.2Fe0.8O2.9@MnCo2O4Composition of, wherein, La0.6Sr0.4Co0.2Fe0.8O2.9Is an oxygen ion-electron mixed conductor framework, the particle size is 500-1000 nm, the porosity of the framework is 55 percent, and the MnCo on the surface of the framework2O4The particle size is 50-100 nm, the total mass of the oxygen electrode is 0.01g, wherein, La0.6Sr0.4Co0.2Fe0.8O2.90.0095g, MnCo2O4The mass was 0.0005 g.
The membrane electrode is used for testing the performance of the electrolyzed water vapor, and the current density of the membrane electrode reaches-1.05 Acm under the conditions that the absolute humidity is 70 percent, the temperature is 800 ℃ and the voltage is 1.3V-2。
Comparative example 4
Preparing a hydrogen electrode supporting button membrane electrode, taking Ni-YSZ (mass ratio of 1: 1) as a hydrogen electrode, gamma SZ as an electrolyte and GDC as an interlayer. Oxygen electrode made of Pr0.8Sr0.2CoO2.85@Pr0.4Ce0.6O2-CoFe2O4Composition of, wherein, Pr0.8Sr0.2CoO2.85The catalyst is an oxygen ion-electron mixed conductor framework, the particle size is 300-1000 nm, the porosity of the framework is 60%, and the particle size of the nano composite catalyst is 10-30 nm. The total mass of the oxygen electrode is 0.01g, wherein Pr0.8Sr0.2CoO2.850.0090g, Pr0.4Ce0.6O2-CoFe2O4Is 0.0010g, wherein Pr0.4Ce0.6O2With CoFe2O4The mass ratio is 30: 70.
The oxygen electrode was prepared as follows: the oxygen electrode is prepared by the following steps: (1) (1) with Pr (NO)3)3.6H2O，sr(NO3)2，Co(NO3)2.6H2Dissolving O in deionized water, adding ammonium citrate, complexing for 5h, continuously heating to form sol, transferring to an electric furnace, and continuously heating until the sol is burnt, wherein the generated powder is pre-sintered for 10h at the high temperature of 1000 ℃ preferentially; (2) preparing corresponding nitrate mixed liquor according to the molar ratio of each element in the nano composite catalyst, and adding an ammonium citrate complexing agent, wherein the ratio of ammonium citrate to metal ions is 1: 1, metalRegulating and controlling the ion concentration to be 0.5M; (3) and (3) adding the powder obtained in the step (1) into the solution obtained in the step (2), then continuously heating and stirring the solution until a combustion reaction occurs, and roasting the powder after combustion at the high temperature of 1000 ℃ for 2 hours to obtain the oxygen electrode.
The membrane electrode is used for testing the performance of the electrolyzed water vapor, and the current density of the electrolyzed water reaches-1.25 Acm under the conditions that the absolute humidity of the membrane electrode is 70 percent, the temperature is 800 ℃ and the voltage is 1.3V-2。
Example 1
Preparing a hydrogen electrode supporting button membrane electrode, taking Ni-YSZ (mass ratio of 1: 1) as a hydrogen electrode, YSZ as an electrolyte and GDC as an interlayer. Oxygen electrode made of La0.6Sr0.4Co0.2Fe0.8O2.9@La0.45Ce0.55O2-MnCo2O4Composition of, wherein, La0.6Sr0.4Co0.2Fe0.8O2.9Is an oxygen ion-electron mixed conductor framework, the particle size is 500-1000 nm, the framework porosity is 55%, the particle size of the nano composite catalyst is 10-50 nm, the total mass of the oxygen electrode is 0.01g, wherein, La0.6Sr0.4Co0.2Fe0.8O2.90.0095g, La0.45Ce0.55O2With MnCo2O4Has a total mass of 0.0005g, wherein La0.45Ce0.55O2With MnCo2O4The mass ratio is 25: 75.
the oxygen electrode was prepared as follows: (1) preparation of La by combustion method0.6Sr0.4Co0.2Fe0.8O2.9Powder of La (NO)3)3.6H2O，Sr(NO3)2，Co(NO3)2.6H2O，Fe(NO3)3.9H2Dissolving O in deionized water, adding ammonium citrate, complexing for 5h, continuously heating to form sol, transferring to an electric furnace, and continuously heating until the sol is burnt, wherein the generated powder is pre-sintered for 5h at the high temperature of 600 ℃; (2) preparing corresponding nitrate mixed liquor according to the mole ratio of each element in the nano composite catalyst, adding ammonium citrate complexing agent, and separating ammonium citrate from metal ionsThe seed ratio is 1.5: 1, and the concentration of metal ions is regulated to be 0.5M; (3) and (3) adding the powder obtained in the step (1) into the solution obtained in the step (2), then continuously heating and stirring the solution until a combustion reaction occurs, and roasting the powder after combustion at the high temperature of 900 ℃ for 2 hours to obtain the oxygen electrode.
The membrane electrode is used for testing the performance of the electrolyzed water vapor, and the current density of the membrane electrode reaches-1.5 Acm under the conditions that the absolute humidity is 70 percent, the temperature is 800 ℃ and the voltage is 1.3V-2。
Example 2
Preparing a hydrogen electrode supporting button membrane electrode, taking Ni-YSZ (mass ratio of 1: 1) as a hydrogen electrode, gamma SZ as an electrolyte and GDC as an interlayer. Oxygen electrode is formed by Sm0.5Sr0.5CoO2.75@Sm0.5Ce0.5O2-MnCu2O4Composition of, wherein Sm0.5Sr0.5CoO2.75The catalyst is an oxygen ion-electron mixed conductor framework, the particle size is 500-1500 nm, the porosity of the framework is 60%, and the particle size of the nano composite catalyst is 10-30 nm. The total mass of the oxygen electrode is 0.01g, wherein Sm0.5Sr0.5CoO2.750.0085g, Sm0.5Ce0.5O2-MnCu2O4Is 0.0015g, wherein Sm is0.5Ce0.5O2With MnCu2O4The mass ratio is 30: 70.
the oxygen electrode was prepared as follows: the oxygen electrode is prepared by the following steps: (1) sm is prepared by adopting combustion method0.5Sr0.5CoO2.75Powder of Sm (NO)3)3.6H2O，sr(NO3)2，Co(NO3)2.6H2Dissolving O in deionized water, adding ammonium citrate, complexing for 5h, continuously heating to form sol, transferring to an electric furnace, and continuously heating until the sol is burnt, wherein the generated powder is pre-sintered for 5h at the high temperature of 600 ℃; (2) preparing corresponding nitrate mixed liquor according to the molar ratio of each element in the nano composite catalyst, and adding an ammonium citrate complexing agent, wherein the ratio of ammonium citrate to metal ions is 2.5: 1, and the concentration of the metal ions is regulated and controlled to be 1M; (3) adding the powder obtained in the step 1 into the solution obtained in the step 2, and thenAnd continuously heating and stirring the solution until a combustion reaction occurs, and roasting the burnt powder for 2 hours at the high temperature of 850 ℃ to obtain the oxygen electrode.
The membrane electrode is used for testing the performance of the electrolyzed water vapor, and the current density of the electrolyzed water reaches-2.0 Acm under the conditions that the absolute humidity of the membrane electrode is 70 percent, the temperature is 800 ℃ and the voltage is 1.3V-2。
Example 3
Preparing a hydrogen electrode supporting button membrane electrode, taking Ni-YSZ (mass ratio of 1: 1) as a hydrogen electrode, gamma SZ as an electrolyte and GDC as an interlayer. Oxygen electrode made of Pr0.8Sr0.2CoO2.85@Pr0.4Ce0.6O2-CoFe2O4Composition of, wherein, Pr0.8Sr0.2CoO2.85The catalyst is an oxygen ion-electron mixed conductor framework, the particle size is 300-1000 nm, the porosity of the framework is 60%, and the particle size of the nano composite catalyst is 10-30 nm. The total mass of the oxygen electrode is 0.01g, wherein Pr0.8Sr0.2CoO2.850.0090g, Pr0.4Ce0.6O2-CoFe2O4Is 0.0010g, wherein Pr0.4Ce0.6O2With CoFe2O4The mass ratio is 30: 70.
The oxygen electrode was prepared as follows: the oxygen electrode is prepared by the following steps: (1) with Pr (NO)3)3.6H2O，sr(NO3)2，Co(NO3)2.6H2Dissolving O in deionized water, adding ammonium citrate, complexing for 5h, continuously heating to form sol, transferring to an electric furnace, and continuously heating until the sol is burnt, wherein the generated powder is pre-sintered for 10h at the high temperature of 500 ℃ preferentially; (2) preparing corresponding nitrate mixed liquor according to the molar ratio of each element in the nano composite catalyst, adding an ammonium citrate complexing agent, wherein the ratio of ammonium citrate to metal ions is 1: 1, and regulating and controlling the concentration of the metal ions to be 0.5M; (3) and (3) adding the powder obtained in the step (1) into the solution obtained in the step (2), then continuously heating and stirring the solution until a combustion reaction occurs, and roasting the powder after combustion at the high temperature of 1000 ℃ for 2 hours to obtain the oxygen electrode.
The membrane electrode is used for testing the performance of the electrolyzed water vaporThe current density of the electrolyzed water reaches-1.45 Acm under the conditions that the absolute humidity of the membrane electrode is 70 percent, the temperature is 800 ℃ and the voltage is 1.3V-2。
Claims (9)
1. A solid oxide electrolytic cell oxygen electrode characterized by:
the oxygen electrode consists of an oxygen ion-electron mixed conductor framework and a nano composite catalyst uniformly covering the surface of the oxygen electrode, and the mass ratio of the nano composite catalyst to the oxygen ion-electron mixed conductor is 1: 99-20: 80;
the oxygen ion-electron mixed conductor is perovskite oxide A1A2BO3-δA1 is one or more of La, Pr, Sm, Gd, Ce, Er, Yb and Y, A2 is one or more of Ca, Sr, Ba and Mg, B is one or more of Mn, Fe, Co, Ni and Cu, and delta is more than or equal to 0 and less than 0.5;
the size of the oxygen ion-electron mixed conductor framework particles is 200-2000 nm, and the framework porosity is 40-70%;
the nano composite catalyst is fluorite oxide NxCe1-xO2And spinel oxide K1K22O4The compound is composed of N which is one or more than two of La, Pr, Sm, Gd, Er, Yb and Y, and K1 and K2 which are Mn, Fe and C independentlyoX is more than 0 and less than or equal to 0.5;
the particle size of the nano composite catalyst is 1-100 nm;
fluorite oxide N in nano composite catalystxCe1-xO2-γAnd spinel oxide K1K22O4The mass ratio of (A) to (B) is 20: 80-50: 50.
2. A solid oxide electrolysis cell oxygen electrode according to claim 1 wherein: oxygen ion-electron mixed conductor A1A2BO in the oxygen electrode3-δWherein A1 is selected from one or more of La, Pr and Sm, A2 is selected from one or more of Ba, Sr and Ca, and B is selected from one or more of Fe, Co, Ni and Mn.
3. A solid oxide electrolytic cell as defined in claim 1An oxygen electrode, characterized in that: the nano composite catalyst in the oxygen electrode is fluorite oxide NxCe1-xO2-γAnd spinel oxide K1K22O4The N is one or more of La, Pr, Sm and Gd.
4. A solid oxide electrolysis cell oxygen electrode according to claim 1 wherein: the oxygen ion-electron mixed conductor in the oxygen electrode has the skeleton particle size of 500-1500 nm, the skeleton porosity of 50-60% and the particle size of 2-50 nm.
5. A solid oxide electrolysis cell oxygen electrode according to claim 1 wherein: fluorite oxide N in nano composite catalyst in oxygen electrodexCe1-xO2And spinel oxide K1K22O4The mass ratio of the nano composite catalyst to the oxygen ion-electron mixed conductor is 25: 75-40: 60, and the mass ratio of the nano composite catalyst to the oxygen ion-electron mixed conductor is 2: 98-10: 90.
6. A method of manufacturing a solid oxide electrolysis cell oxygen electrode according to any of claims 1 to 5, characterized in that: the oxygen electrode is prepared by the following steps:
(1) synthesizing initial powder of the oxygen ion-electron mixed framework material by adopting a solid phase method or a combustion method, and pre-sintering the initial powder at the high temperature of 300-600 ℃ for 1-10 h preferentially;
(2) preparing corresponding nitrate mixed liquor according to the molar ratio of elements in the nano composite catalyst, adding a complexing agent, wherein the molar ratio of the complexing agent to metal ions is 1: 1-4: 1, and the concentration of the metal ions is 0.5-3M;
(3) adding the framework material powder obtained in the step 1 into the solution obtained in the step 2, then continuously heating and stirring the solution until a combustion reaction occurs, and roasting the oxygen electrode initial powder after combustion at a high temperature of 600-1000 ℃ to obtain the oxygen electrode.
7. A method of making a solid oxide electrolysis cell oxygen electrode according to claim 6, wherein: synthesizing initial powder of the oxygen ion-electron mixed framework material by adopting a solid phase method or a combustion method, and then presintering at the high temperature of 400-500 ℃.
8. A method of making a solid oxide electrolysis cell oxygen electrode according to claim 6, wherein: preparing corresponding nitrate mixed liquor according to the molar ratio of elements in the nano composite catalyst, and adding a complexing agent, wherein the molar ratio of the complexing agent to metal ions is 1.5: 1-2: 1, and the concentration of the metal ions is 0.5-2M.
9. A method of making a solid oxide electrolysis cell oxygen electrode according to claim 6, wherein: the complexing agent is selected from one or more of glycine, citric acid and ethylene diamine tetraacetic acid.
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