CN114883580A - Perovskite type high-entropy cathode material and preparation method and application thereof - Google Patents
Perovskite type high-entropy cathode material and preparation method and application thereof Download PDFInfo
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8684—Negative electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The invention relates to a perovskite type high-entropy cathode material and a preparation method and application thereof, wherein the high-entropy cathode material has a chemical general formula as follows: (La) 0.3 Ca 0.3 Nd 0.2 Sm 0.1 Gd 0.1 )MnO 3 Prepared by a sol-gel method. Compared with the prior art, the high-entropy cathode material has extremely high chemical stability, and the chemical stability of the high-entropy cathode material and electrolyte 8YSZ can reach 1400 ℃. When the cathode material is adopted to prepare the fuel cell, a barrier layer does not need to be additionally arranged between the cathode and the electrolyte, so that the preparation process of the cell is greatly simplified, the cell structure is simplified, and the production cost is reduced.
Description
Technical Field
The invention belongs to the technical field of fuel cells and ceramic materials, and relates to a perovskite type high-entropy cathode material, a preparation method thereof and application thereof in solid oxide fuel cells.
Background
Solid Oxide Fuel Cells (SOFCs) are a type of fuel cell that can efficiently convert chemical energy in hydrocarbon fuels directly into electrical energyA solid-state power generation device is mainly composed of a cathode, an anode, an electrolyte, a connection layer and the like. In general, the polarization loss of SOFC is mainly the polarization loss of the oxygen reduction reaction on the cathode due to its higher activation energy. The cathode material of an SOFC strongly affects the final performance of the cell. At present, the common cathode material of SOFC is mainly La 0.8 Sr 0.2 MnO 3 、La 0.6 Sr 0.4 CoO 3 、La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3 And the like. However, during the preparation process of the SOFC cathode material and the electrolyte material, high-resistivity mixed phases such as lanthanum zirconate can be generated during sintering at about 1100-1200 ℃, and the final performance of the battery is greatly reduced. For example, La 0.8 Sr 0.2 MnO 3 Has the characteristics of higher conductivity, excellent electrochemical catalytic activity and the like, and the thermal expansion coefficient of the catalyst is close to 8 YSZ. However, La 0.8 Sr 0.2 MnO 3 Readily react with 8YSZ at high temperatures to form highly insulating phases, e.g. La 2 Zr 2 O 7 Or SrZrO 3 . Therefore, the chemical stability of the common SOFC cathode material needs to be improved.
In order to further improve the chemical stability of SOFCs, workers in the field have conducted a number of investigations and studies. Currently, in addition to adding a barrier layer between a cathode and an electrolyte, high-entropy ceramic formation of SOFC cathode materials is more studied. The high-entropy ceramic refers to a multi-principal-element solid solution formed by five or more ceramic components, and the absolute value of the mixed entropy of the high-entropy ceramic is more than 1.5R (0.0124kJ mol) –1 K –1 And R is a gaseous constant). The high-entropy ceramics show excellent performances such as high hardness, high modulus, low thermal conductivity, high stability, high corrosion resistance and the like due to unique high-entropy effect, delayed diffusion effect, lattice distortion effect and cocktail effect. Among the high-entropy ceramics that have been found, perovskite-type high-entropy oxides are particularly spotlighted by many researchers because of their unique crystal structures and properties. For example, the document A novel surface strand to documents Sr segreglation for high-entry stabilized La 0.8 Sr 0.2 MnO 3-δ cathode reports aChemical composition of La 0.2 Pr 0.2 Nd 0.2 Sm 0.2 Sr 0.2 MnO 3-δ The high-entropy perovskite cathode material of (2) can be used, but the barrier layer material (GDC material) is also required to be used in the preparation of the battery, which undoubtedly increases the preparation cost and the process flow of the battery; furthermore, the document New aproach to enhance Sr-free catalyst performance by high-entry multi-component transition metal coupling reports a composition La (Mn) 0.2 Fe 0.2 Co 0.2 Ni 0.2 Cu 0.2 )O 3-δ The multi-component high-entropy cathode material has the chemical stability of only 900 ℃ with 8YSZ, so that the cathode is easy to chemically react with 8YSZ in the co-sintering process of battery preparation.
Disclosure of Invention
The invention aims to provide a perovskite type high-entropy cathode material and a preparation method and application thereof. The crystal structure of the high-entropy cathode material is perovskite type, and the chemical general formula is (La) 0.3 Ca 0.3 Nd 0.2 Sm 0.1 Gd 0.1 )MnO 3 . The high-entropy cathode is prepared by a sol-gel method, has extremely high chemical stability, and can reach 1400 ℃ with the chemical stability of electrolyte 8 YSZ. When the cathode material is adopted to prepare the fuel cell, a barrier layer does not need to be additionally arranged between the cathode and the electrolyte, so that the preparation process of the cell is greatly simplified, the cell structure is simplified, and the production cost is reduced.
The purpose of the invention can be realized by the following technical scheme:
a perovskite type high-entropy cathode material has a perovskite (ABO) crystal structure 3 Type), the chemical formula is: (La) 0.3 Ca 0.3 Nd 0.2 Sm 0.1 Gd 0.1 )MnO 3 。
According to the definition of the high-entropy ceramics, the mixed entropy (Delta S) of the high-entropy ceramics mix ) The absolute value of (A) needs to be higher than 1.5R (R is a gas constant), i.e. more than 0.0124kJ mol –1 K –1 . Perovskite type (ABO) of the present invention 3 Type) the calculation formula of the mixed entropy of the high-entropy cathode material is as follows:
wherein x is a 、x b And x c A, B and the mole fraction of ions at the O position, respectively.
In addition, the ion size difference calculation formula of the A site element of the perovskite type high-entropy cathode material is as follows:
wherein,
is the radius of the i-th ion in position A, c i The corresponding mole fraction of the ith ion.
Thus, the absolute value of the mixed entropy of the high-entropy cathode material in the present invention is 1.505R (R is a gas constant) and the difference in ion size of the a-site element is 3.37%.
A preparation method of a perovskite type high-entropy cathode material comprises the following steps:
1) preparing a lanthanum source, a calcium source, a neodymium source, a samarium source, a gadolinium source and a manganese source into a raw material solution according to the chemical general formula;
2) mixing the raw material solution with EDTA-NH 4 Mixing the OH solution and citric acid, adjusting the pH of the mixed solution to be alkaline to obtain sol, and sequentially performing gelation, drying and grinding to obtain precursor powder;
3) and calcining the precursor powder to obtain the high-entropy cathode material.
Further, in step 1), the lanthanum source comprises La (NO) 3 ) 3 Said calcium source comprises Ca (NO) 3 ) 2 Said neodymium source comprises Nd (NO) 3 ) 3 Said samarium source comprises Sm (NO) 3 ) 3 Said source of gadolinium comprising Gd (NO) 3 ) 3 Said manganese source comprises Mn (NO) 3 ) 2 。
Further, in step 2), the total metal ions in the mixed solution: EDTA: the molar ratio of citric acid is 1: 1: 1.5.
further, in step 2), the EDTA-NH is added 4 In the OH solution, the mass fraction of the EDTA is 45-55%, and the balance is ammonia water with the concentration of 25-28%.
Further, in the step 2), adding ammonia water to adjust the pH value of the mixed solution to 8-9.
Further, in the step 2), the gelation process comprises stirring the sol at 80-90 ℃ for 12-36 h.
Further, in the step 3), the calcining temperature is 1100-1300 ℃, and the calcining time is 1-4 h.
The application of the perovskite high-entropy cathode material comprises the step of applying the high-entropy cathode material to a cathode material of a solid fuel cell.
Furthermore, in the solid fuel cell, the electrolyte is 8YSZ, and the chemical stability between the high-entropy cathode material and the electrolyte can reach 1400 ℃, so that no additional barrier layer material is needed to be arranged during cell preparation.
Compared with the prior art, the invention has the following characteristics:
1) the perovskite high-entropy cathode material is prepared by a sol-gel method, and has simple process and strong repeatability;
2) the perovskite type high-entropy cathode material has extremely high chemical stability, and the chemical stability of the perovskite type high-entropy cathode material and electrolyte 8YSZ can reach 1400 ℃;
3) when the perovskite high-entropy cathode material is adopted to prepare the fuel cell, a barrier layer does not need to be additionally arranged between the cathode and the electrolyte, the structure is simple, the preparation process of the cell is greatly simplified, and the cell structure is simplified and the production cost is reduced.
Drawings
FIG. 1 shows a perovskite-type high-entropy cathode material (La) prepared in example 1 0.3 Ca 0.3 Nd 0.2 Sm 0.1 Gd 0.1 )MnO 3 And the XRD pattern of electrolyte 8YSZ after being calcined for 5h at 1400 ℃;
FIG. 2 shows high entropy of perovskite type (La) described in example 1 0.3 Ca 0.3 Nd 0.2 Sm 0.1 Gd 0.1 )MnO 3 Cross-sectional SEM images (SEM samples were prepared from resin inlays) of anode-supported fuel cells as cathode materials.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
A perovskite type high-entropy cathode material has a perovskite (ABO) crystal structure 3 Type), the chemical formula is: (La) 0.3 Ca 0.3 Nd 0.2 Sm 0.1 Gd 0.1 )MnO 3 . The preparation method can be prepared by a sol-gel method, and specifically comprises the following steps:
1) solution preparation: adding a lanthanum source, a calcium source, a neodymium source, a samarium source, a gadolinium source and a manganese source into deionized water according to the chemical general formula, and stirring and dissolving uniformly at normal temperature to obtain a raw material solution;
mixing hexanediamine tetrahexanoic acid with ammonia water to obtain EDTA-NH 4 OH solution;
wherein the lanthanum source comprises La (NO) 3 ) 3 The calcium source comprises Ca (NO) 3 ) 2 The neodymium source includes Nd (NO) 3 ) 3 The samarium source comprises Sm (NO) 3 ) 3 The source of gadolinium comprises Gd (NO) 3 ) 3 The manganese source comprises Mn (NO) 3 ) 2 ；
2) Preparing sol: mixing the raw material solution with EDTA-NH 4 Mixing the OH solutions, adding citric acid, stirring at normal temperature for 5-10 min to obtain a mixed solution, and then adding ammonia water to adjust the pH of the mixed solution to 8-9 to obtain sol;
wherein, the total metal ions in the mixed solution are as follows: EDTA: the molar ratio of citric acid is 1: 1: 1.5; EDTA-NH 4 In the OH solution, the mass fraction of EDTA is 45-55%, and the balance is ammonia water with the concentration of 25-28%.
3) And (3) gelation: stirring and evaporating the sol at 80-90 ℃ for 12-36 h to obtain gel;
4) drying: drying the gel at 200-300 ℃ for 4-8 h (preferably 200 ℃) to obtain dry gel, and grinding the dry gel into powder to obtain precursor powder;
5) calcining and post-treating: calcining the precursor powder at 1100-1300 ℃ for 1-4 h, grinding into powder, and sieving by a 170-270-mesh sieve to obtain the high-entropy cathode material.
The application of the perovskite type high-entropy cathode material comprises the step of using the high-entropy cathode material as a cathode material of a solid fuel cell. And preferably, the electrolyte used in the solid fuel cell is 8 YSZ.
The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
Example 1:
a perovskite type high-entropy cathode material is prepared by the following steps:
1) solution preparation: adding La (NO) 3 ) 3 、Ca(NO 3 ) 2 、Nd(NO 3 ) 3 、Sm(NO 3 ) 3 、Gd(NO 3 ) 3 、Mn(NO 3 ) 2 According to the general chemical formula: (La) 0.3 Ca 0.3 Nd 0.2 Sm 0.1 Gd 0.1 )MnO 3 Adding the mixture into deionized water, and magnetically stirring and dissolving the mixture uniformly at normal temperature to obtain a nitrate aqueous solution; simultaneously mixing hexanediamine tetrahexanoic acid (EDTA) with 25% ammonia water in a mass ratio of 1:1, and stirring to obtain EDTA-NH 4 And (4) OH solution.
2) Sol preparation: mixing aqueous nitrate solution with EDTA-NH 4 And (3) mixing the OH solutions, adding citric acid, stirring at normal temperature for 10min, and then adding ammonia water to adjust the pH value of the mixed solution to 8 to obtain sol. Wherein, the total metal ions in the mixed solution are as follows: EDTA: the molar ratio of citric acid is 1: 1: 1.5.
3) and (3) gelation: placing the sol in a conical flask and transferring the sol into an oil bath pan, mechanically stirring the sol at 90 ℃, and carrying out open evaporation for 12 hours to obtain gel;
4) drying: drying the gel at 200 ℃ for 8h to obtain dry gel, and grinding the dry gel into powder to obtain precursor powder;
5) calcining and post-treating: and (3) putting the precursor powder into a crucible, transferring the crucible into a box-type furnace, calcining for 4 hours at 1100 ℃, grinding into powder, and sieving by a 200-mesh sieve to obtain the high-entropy cathode material.
Through testing, the absolute value of the mixing entropy of the high-entropy cathode material to be prepared in the embodiment is 1.505R (R is a gas constant) and the ion size difference of the A-bit element is 3.37%.
In this example, the mass ratio of the prepared high-entropy cathode material to an electrolyte 8YSZ (yb-stabilized zirconia nano-powder, beijing delke island gold technologies ltd) was 1:1, and calcining at 1400 ℃ for 5 hours, wherein the XRD pattern of the obtained product is shown in figure 1, and the high-entropy cathode material (La) can be seen from the figure 0.3 Ca 0.3 Nd 0.2 Sm 0.1 Gd 0.1 )MnO 3 And 8YSZ have no obvious chemical change, so that the high-entropy cathode material prepared by the embodiment has excellent high-temperature-resistant chemical stability with the electrolyte 8YSZ, and can reach 1400 ℃.
In addition, the embodiment also comprises the step of preparing an anode-supported fuel cell without additionally arranging a barrier layer between a cathode and an electrolyte 8YSZ by using the high-entropy cathode material, wherein the preparation method is a conventional screen printing method.
Example 2:
compared with the embodiment 1, the preparation method of the perovskite type high-entropy cathode material is only different from that of the embodiment 1 in that: the chemical general formula is (La) 0.3 Ca 0.3 Nd 0.2 Sm 0.1 Y 0.1 )MnO 3 Using Y (NO) 3 ) 3 Substituting Gd (NO) 3 ) 3 The absolute value of the entropy of the mixture of the resulting material was 1.505R (R is a gas constant) and the difference in the ion size of the A-bit element was 6.46%, as in example 1, for the remainder.
The chemical stability of the perovskite type high-entropy cathode material and the 8YSZ electrolyte is only 1000 ℃ through testing. When the cathode is used for preparing an anode-supported fuel cell, a barrier layer is additionally arranged between the cathode and an electrolyte.
Example 3:
perovskite type high-entropy cathodeThe material, the preparation method of which differs from example 1 only in that: the chemical general formula is (La) 0.2 Ca 0.2 Nd 0.2 Sm 0.2 Gd 0.2 )MnO 3 The absolute value of the entropy of the mixture of the obtained material was 1.609R (R is a gas constant) and the difference in the ion size of the A-bit element was 3.54%, as in example 1.
The chemical stability of the perovskite type high-entropy cathode material and the 8YSZ electrolyte is only 1200 ℃ through testing. When the cathode is used for preparing an anode-supported fuel cell, a barrier layer is additionally arranged between the cathode and an electrolyte.
Example 4:
compared with the embodiment 1, the preparation method of the perovskite type high-entropy cathode material is only different from that of the embodiment 1 in that: the chemical general formula is (La) 0.3 Sr 0.3 Nd 0.2 Sm 0.1 Gd 0.1 )MnO 3 Using Sr (NO) 3 ) 2 Substitution of Ca (NO) 3 ) 2 The absolute value of the entropy of the mixture of the resulting material was 1.505R (R is a gas constant) and the difference in the ion size of the A-bit element was 5.55%, as in example 1, except for the remainder.
The chemical stability of the perovskite type high-entropy cathode material and the 8YSZ electrolyte is only 1100 ℃ through testing. When the cathode is used for preparing an anode-supported fuel cell, a barrier layer is additionally arranged between the cathode and an electrolyte.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A perovskite type high-entropy cathode material is characterized in that the chemical general formula of the high-entropy cathode material is as follows: (La) 0.3 Ca 0.3 Nd 0.2 Sm 0.1 Gd 0.1 )MnO 3 。
2. The method for preparing a perovskite-type high-entropy cathode material as claimed in claim 1, which comprises the steps of:
1) preparing a lanthanum source, a calcium source, a neodymium source, a samarium source, a gadolinium source and a manganese source into a raw material solution according to the chemical general formula;
2) mixing the raw material solution with EDTA-NH 4 Mixing the OH solution and citric acid, adjusting the pH of the mixed solution to be alkaline to obtain sol, and sequentially performing gelation, drying and grinding to obtain precursor powder;
3) and calcining the precursor powder to obtain the high-entropy cathode material.
3. The method for preparing a perovskite-type high-entropy cathode material as claimed in claim 2, wherein in the step 1), the lanthanum source comprises La (NO) 3 ) 3 Said calcium source comprises Ca (NO) 3 ) 2 Said neodymium source comprises Nd (NO) 3 ) 3 The samarium source comprises Sm (NO) 3 ) 3 Said source of gadolinium comprising Gd (NO) 3 ) 3 Said manganese source comprises Mn (NO) 3 ) 2 。
4. A method for preparing a perovskite-type high entropy cathode material according to claim 2, wherein in step 2), the total metal ions in the mixed solution: EDTA: the molar ratio of citric acid is 1: 1: 1.5.
5. the method for preparing a perovskite-type high-entropy cathode material as claimed in claim 2, wherein in the step 2), EDTA-NH is added 4 In the OH solution, the mass fraction of the EDTA is 45-55%, and the balance is ammonia water with the concentration of 25-28%.
6. The preparation method of the perovskite high-entropy cathode material as claimed in claim 2, wherein in the step 2), ammonia water is added to adjust the pH value of the mixed solution to 8-9.
7. The preparation method of the perovskite high-entropy cathode material as claimed in claim 2, wherein in the step 2), the gelation process comprises stirring the sol at 80-90 ℃ for 12-36 h.
8. The preparation method of the perovskite high-entropy cathode material as claimed in claim 2, wherein in the step 3), the calcination temperature is 1100-1300 ℃ and the calcination time is 1-4 h.
9. Use of a perovskite-type high entropy cathode material as claimed in claim 1, wherein the high entropy cathode material is used as a cathode material for a solid fuel cell.
10. Use of a perovskite high entropy cathode material as claimed in claim 9, wherein the electrolyte used in the solid fuel cell is 8 YSZ.
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