CN111082111A - Intermediate-temperature solid oxide fuel cell composite cathode material and preparation method and application thereof - Google Patents

Intermediate-temperature solid oxide fuel cell composite cathode material and preparation method and application thereof Download PDF

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CN111082111A
CN111082111A CN201911412275.5A CN201911412275A CN111082111A CN 111082111 A CN111082111 A CN 111082111A CN 201911412275 A CN201911412275 A CN 201911412275A CN 111082111 A CN111082111 A CN 111082111A
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fuel cell
solid oxide
powder
cathode material
oxide fuel
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孙丽萍
李娜
赵辉
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Heilongjiang University
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Heilongjiang University
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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
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/0071—Oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • H01M2300/0091—Composites in the form of mixtures
    • 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

Abstract

The invention belongs to the technical field of fuel cell materials, and particularly relates to a medium-temperature solid oxide fuel cell composite cathode material, and a preparation method and application thereof. The invention provides a medium-temperature solid oxide fuel cell composite cathode material, which has the chemical formula of x [ La ] La0.85Sr0.15MnO3‑δ]·(1‑x)[Bi2CuO4]And x is 40 wt.% to 70 wt.%. The results of the examples show that the polarization resistance R of the symmetrical cell prepared by using the composite cathode material of the intermediate-temperature solid oxide fuel cell provided by the invention as the cathode material is 700 DEG CPIs only 0.13. omega. cm2(ii) a The prepared anode-supported single cell has the maximum output power of 661mW/cm at 700 DEG C2And the electrochemical performance is excellent under the condition of medium temperature.

Description

Intermediate-temperature solid oxide fuel cell composite cathode material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of fuel cell materials, and particularly relates to a medium-temperature solid oxide fuel cell composite cathode material, and a preparation method and application thereof.
Background
A Solid Oxide Fuel Cell (SOFC) is a power generation device that directly converts chemical energy of fuel into electrical energy, and has the advantages of high energy conversion efficiency, wide fuel application range, low pollutant emission, and the like. In recent years, it is widely believed that reducing the operating temperature is the key to commercialize the SOFC, and reducing the operating temperature of the cell not only can effectively reduce the aging rate of each component, improve the stability of the SOFC, and prolong the service life, but also can use a cheap stainless steel metal material as a connecting material, thereby greatly reducing the cost. Therefore, lowering the operating temperature (<800 ℃) has become one of the main research directions for SOFCs.
The cathode is one of the important components of the SOFC, and provides an electrochemical reaction site for the reduction of oxygen, and the performance of the cathode directly affects the performance of the whole cell. Traditional SOFC cathode material- -lanthanum strontium manganate (La, Sr) MnO3High temperature(s) still are the most commonly used at present due to their high structural chemical stability and high electronic conductivity>800 ℃) SOFC cathode material. However, the negligible ionic conductivity and the high activation energy of the oxygen reduction reaction lead the catalytic capability of the cathode material to the oxygen reduction reaction to be sharply reduced along with the reduction of the temperature, the cathode impedance is rapidly increased, and the cathode material cannot adapt to medium and low temperatures: (<800 deg.c) and provides excellent electrochemical performance.
One commonly used method for increasing (La, Sr) MnO3The electrochemical performance of the cathode is determined in the presence of (La, Sr) MnO3Adding a certain amount of ion conductor material. The addition of the ionic conduction phase improves the oxygen ion conductivity of the cathode material, expands the three-phase interface reaction region in the cathode, but the electrochemical performance still cannot meet the use requirement of the solid oxide fuel cell under the medium-low temperature condition.
Disclosure of Invention
In view of the above, the present invention aims to provide a composite cathode material for an intermediate-temperature solid oxide fuel cell, which exhibits excellent electrochemical performance under the intermediate-temperature condition; the invention also provides a preparation method and application of the intermediate-temperature solid oxide fuel cell composite cathode material.
In order to achieve the purpose of the invention, the invention provides the following technical scheme:
the invention provides a medium-temperature solid oxide fuel cell composite cathode material, and the chemical composition of the medium-temperature solid oxide fuel cell composite cathode materialIs of the formula x [ La ]0.85Sr0.15MnO3-δ]·(1-x)[Bi2CuO4]，x＝40wt.％～70wt.％。
Preferably, La in the intermediate-temperature solid oxide fuel cell composite cathode material0.85Sr0.15MnO3-δHas a perovskite structure; bi in the composite cathode material of the intermediate-temperature solid oxide fuel cell2CuO4Has a spinel structure.
The invention also provides a preparation method of the composite cathode material of the intermediate-temperature solid oxide fuel cell in the technical scheme, which comprises the following steps:
providing Bi2CuO4Powder;
la0.85Sr0.15MnO3-δPowder and Bi2CuO4Mixing and ball-milling the powder to obtain a ball grinding material;
and drying the ball milling material to obtain the intermediate-temperature solid oxide fuel cell composite cathode material.
Preferably, the La0.85Sr0.15MnO3-δPowder and Bi2CuO4The mass ratio of the powder is 4: 6-7: 3.
preferably, the La0.85Sr0.15MnO3-δThe particle size of the powder is 100-150 nm; the Bi2CuO4The particle size of the powder is 1-2 μm.
Preferably, the grinding balls for ball milling are agate balls; the diameter of the grinding ball is 5-7 mm; the La0.85Sr0.15MnO3-δPowder and Bi2CuO4The ratio of the total mass of the powder to the grinding balls is 5 g: (25-40).
Preferably, the liquid medium for ball milling is absolute ethyl alcohol; the La0.85Sr0.15MnO3-δPowder and Bi2CuO4The ratio of the total mass of the powder to the liquid medium is 5 g: (20-30) mL.
Preferably, the rotation speed of the ball mill is 200-300 rpm, and the time is 5-10 h.
Preferably, the drying temperature is 80-120 ℃, and the drying time is 2-6 h.
The invention also provides the application of the intermediate-temperature solid oxide fuel cell composite cathode material in the technical scheme or the intermediate-temperature solid oxide fuel cell composite cathode material prepared by the preparation method in the technical scheme in a fuel cell.
The invention provides a medium-temperature solid oxide fuel cell composite cathode material, which has the chemical formula of x [ La ] La0.85Sr0.15MnO3-δ]·(1-x)[Bi2CuO4]And x is 40 wt.% to 70 wt.%. In the present invention, La0.85Sr0.15MnO3-δ(LSM) is a purely electronic conductor, and Bi2CuO4(BCO) exhibits mixed ion-electron conductivity at 700 ℃, so the addition of BCO can extend the oxygen reduction reaction active region from the cathode/electrolyte interface into the cathode interior; in addition, the oxygen transport performance of BCO is superior to that of LSM, namely the oxygen diffusion and surface exchange performance of BCO are higher than that of LSM, so that the addition of BCO also improves the conductivity of oxygen in the composite cathode and accelerates the migration rate of oxygen in the composite cathode and at the interface of the cathode/electrolyte; compared with pure LSM cathode, the x [ La ] provided by the invention0.85Sr0.15MnO3-δ]·(1-x)[Bi2CuO4]The (LSM-BCO) composite cathode shows excellent electrochemical performance; in addition, compared with a pure LSM cathode material, the required sintering temperature for preparing the cathode layer is remarkably reduced, the sintering temperature for preparing the cathode layer can be reduced to 700-850 ℃ from 1100 ℃ of the traditional LSM cathode material, the sintering temperature is lower, the reduction of the sintering temperature not only effectively avoids the occurrence of adverse chemical reaction between the cathode and an electrolyte, but also avoids the growth of cathode particles and the coarsening of the microscopic morphology of the cathode, and is beneficial to ensuring and improving the electrochemical performance of a solid oxide fuel cell under the condition of medium temperature.
The results of the examples show that the composite cathode material of the intermediate-temperature solid oxide fuel cell provided by the invention is prepared by taking the composite cathode material as the cathode materialSymmetrical cell, polarization resistance R at 700 DEG CPIs only 0.13. omega. cm2Is 60 wt.% La0.85Sr0.15MnO3-δ·40wt.％Gd0.1Ce0.9O1.95(optimum proportion) polarization resistance value (0.38 omega cm) of composite cathode under the same condition2) 34% of (A), only pure La0.85Sr0.15MnO3-δPolarization resistance value (2.18 omega cm) of cathode under the same condition2) 6% of; the anode-supported single cell prepared by using the intermediate-temperature solid oxide fuel cell composite cathode material provided by the invention as a cathode material has the maximum output power of 661mW/cm at 700 DEG C2And the electrochemical performance is excellent under the condition of medium temperature.
Drawings
FIG. 1 is an XRD test pattern of example 1 of the present invention and comparative examples 1 to 2;
FIG. 2 is an impedance test chart of a symmetrical battery composed of examples 1 to 4 of the present invention and comparative example 1;
FIG. 3 is the I-V and I-P curves at 550 deg.C to 700 deg.C for a cell made according to example 3 of the present invention.
Detailed Description
The invention provides a medium-temperature solid oxide fuel cell composite cathode material, which has the chemical formula of x [ La ] La0.85Sr0.15MnO3-δ]·(1-x)[Bi2CuO4]，x＝40wt.％～70wt.％。
In the invention, the lower corner mark delta in the chemical formula of the intermediate-temperature solid oxide fuel cell composite cathode material is a numerical value for ensuring the electrical neutrality of a substance.
In the invention, La in the intermediate-temperature solid oxide fuel cell composite cathode material0.85Sr0.15MnO3-δHas a perovskite structure; bi in the composite cathode material of the intermediate-temperature solid oxide fuel cell2CuO4Has a spinel structure.
The invention also provides a preparation method of the composite cathode material of the intermediate-temperature solid oxide fuel cell in the technical scheme, which comprises the following steps:
providing Bi2CuO4Powder;
la0.85Sr0.15MnO3-δPowder and Bi2CuO4Mixing and ball-milling the powder to obtain a ball grinding material;
and drying the ball milling material to obtain the intermediate-temperature solid oxide fuel cell composite cathode material.
The present invention provides Bi2CuO4And (3) powder. In the present invention, the Bi2CuO4The particle size of the powder is preferably 1 to 2 μm, more preferably 1.2 to 1.8 μm, and still more preferably 1.4 to 1.6 μm. In the present invention, the Bi2CuO4The powder is preferably prepared according to the following steps:
adding Bi2O3Mixing powder and CuO powder, and then performing ball milling, drying and calcining in sequence to obtain Bi2CuO4And (3) powder. The invention is directed to the Bi2O3The sources of the powder and the CuO powder are not particularly limited, and those known to those skilled in the art may be used, specifically, those commercially available. In the present invention, the Bi2O3The mass ratio of the powder to the CuO powder is preferably 4.271: 0.729. in the invention, the grinding balls for ball milling are preferably agate balls; the diameter of the grinding ball is preferably 5-7 mm, and more preferably 6.3 mm; the Bi2O3The ratio of the total mass of the powder and CuO powder to the grinding balls is preferably 5 g: (25-40), more preferably 5 g: 30 pieces. In the present invention, the liquid medium for ball milling is preferably absolute ethanol; the Bi2O3The ratio of the total mass of the powder and CuO powder to the liquid medium is preferably 5 g: (20-30) mL, more preferably 5 g: 25 mL. In the invention, the rotation speed of the ball mill is preferably 200-300 rpm, more preferably 220-280 rpm; the time is preferably 5 to 10 hours, and more preferably 6 to 9 hours. In the invention, the drying temperature is preferably 80-120 ℃, and more preferably 90-110 ℃; the time is preferably 2 to 6 hours, and more preferably 3 to 5 hours. In the present invention, the drying means is preferably an air-blast drying oven. In the present inventionThe calcination temperature is preferably 750-800 ℃, and the calcination time is preferably 24-36 h.
To obtain Bi2CuO4After the powder is prepared, the invention mixes La0.85Sr0.15MnO3-δPowder and Bi2CuO4And mixing and ball-milling the powder to obtain the ball grinding material.
In the present invention, the La0.85Sr0.15MnO3-δPowder and Bi2CuO4The mass ratio of the powder is preferably 4: 6-7: 3, more preferably 4.5: 5.5-6.5: 3.5. in the present invention, the La0.85Sr0.15MnO3-δThe particle size of the powder is preferably 100 to 150nm, more preferably 110 to 140nm, and still more preferably 120 to 130 nm. The invention is to the La0.85Sr0.15MnO3-δThe source of the powder is not particularly limited, and La known to those skilled in the art is used0.85Sr0.15MnO3-δThe powder can be obtained from any source, such as commercially available sources.
In the invention, the grinding balls for ball milling are preferably agate balls; the diameter of the grinding ball is preferably 5-7 mm, and more preferably 6.3 mm; the La0.85Sr0.15MnO3-δPowder and Bi2CuO4The ratio of the total mass of the powder to the grinding balls is preferably 5 g: (25-40), more preferably 5 g: 30 pieces. In the present invention, the liquid medium for ball milling is preferably absolute ethanol; the La0.85Sr0.15MnO3-δPowder and Bi2CuO4The ratio of the total mass of the powder to the liquid medium is preferably 5 g: (20-30) mL, more preferably 5 g: 25 mL. In the invention, the rotation speed of the ball mill is preferably 200-300 rpm, more preferably 220-280 rpm; the time is preferably 5 to 10 hours, and more preferably 6 to 9 hours.
After the ball grinding material is obtained, the ball grinding material is dried to obtain the intermediate-temperature solid oxide fuel cell composite cathode material.
In the invention, the drying temperature is preferably 80-120 ℃, and more preferably 90-110 ℃; the time is preferably 2 to 6 hours, and more preferably 3 to 5 hours.
The invention also provides the application of the intermediate-temperature solid oxide fuel cell composite cathode material in the technical scheme or the intermediate-temperature solid oxide fuel cell composite cathode material prepared by the preparation method in the technical scheme in a fuel cell.
In the invention, the application is preferably to prepare the solid oxide fuel cell by taking the intermediate-temperature solid oxide fuel cell composite cathode material as a cathode material of the solid oxide fuel cell; the applicable temperature of the solid oxide fuel cell is preferably 550-800 ℃.
In order to further illustrate the present invention, the following examples are provided to describe the composite cathode material for intermediate-temperature solid oxide fuel cell and the preparation method and application thereof in detail, but they should not be construed as limiting the scope of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
4.271g of Bi2O3Pouring the powder and 0.729g of CuO powder into a 100mL ball milling tank, adding 30 agate balls with the diameter of 6.3mm as a grinding medium, pouring 25mL of absolute ethyl alcohol, then ball milling for 8h at the rotating speed of 220rpm, then placing the mixture into a forced air drying oven to dry for 4h at 100 ℃, placing the dried mixture into a crucible to calcine for 30h at 780 ℃ to obtain Bi2CuO4Powder;
la0.85Sr0.15MnO3-δPowder and Bi obtained by preparation2CuO4The powder is prepared according to the following steps of 5: 5 (the total mass is 5g), pouring into a 100mL ball milling tank, adding 30 agate balls with the diameter of 6.3mm as a grinding medium, pouring 25mL absolute ethyl alcohol, and then carrying out ball milling for 8 hours at the rotating speed of 220rpm to obtain a ball grinding material;
drying the obtained ball-milled material in a forced air drying oven at 100 ℃ for 4h to obtain the intermediate-temperature solid oxide fuel cell composite cathode material (50 wt.% of La)0.85Sr0.15MnO3-δ·50wt.％Bi2CuO4I.e., LSM-50 BCO).
Example 2
La0.85Sr0.15MnO3-δPowder and Bi obtained by preparation2CuO4The powder mass ratio is 4: the other operations are the same as example 1 to obtain the intermediate-temperature solid oxide fuel cell composite cathode material (40 wt.% La)0.85Sr0.15MnO3-δ·60wt.％Bi2CuO4I.e., LSM-60 BCO).
Example 3
La0.85Sr0.15MnO3-δPowder and Bi obtained by preparation2CuO4The powder mass ratio is 6: the other operations are the same as example 1 to obtain the intermediate-temperature solid oxide fuel cell composite cathode material (60 wt.% La)0.85Sr0.15MnO3-δ·40wt.％Bi2CuO4I.e., LSM-40 BCO).
Example 4
La0.85Sr0.15MnO3-δPowder and Bi obtained by preparation2CuO4The powder mass ratio is 7: the other operations are the same as example 1, and the intermediate-temperature solid oxide fuel cell composite cathode material (70 wt.% La) is obtained0.85Sr0.15MnO3-δ·30wt.％Bi2CuO4I.e., LSM-30 BCO).
Comparative example 1
With La in example 10.85Sr0.15MnO3-δPowder (pure LSM) is the comparative example 1 material.
Comparative example 2
Bi obtained in example 12CuO4The powder was the material of comparative example 2.
Comparative example 3
La0.85Sr0.15MnO3-δPowder and Gd0.1Ce0.9O1.95The powder is prepared according to the following steps of 6: 4 (total mass is 5g), poured into a 100mL ball mill pot, and added with 30 agate balls with diameter of 6.3mmPouring 25mL of absolute ethyl alcohol as a grinding medium, and then carrying out ball milling for 8h at the rotating speed of 220rpm to obtain a ball grinding material;
the resulting ball milled material was dried in a forced air drying oven at 100 ℃ for 4h to give 60 wt.% La0.85Sr0.15MnO3-δ·40wt.％Gd0.1Ce0.9O1.95(LSM-GDC) composite cathode material.
Test example 1
The materials of example 1 and comparative examples 1-2 were treated as follows:
pressing a material to be tested into a circular blank, calcining for 10h at 800 ℃, then grinding into powder, respectively carrying out XRD (X-ray diffraction) test on the obtained powder material, wherein the test conditions comprise that an X' PertPROX ray diffractometer is adopted to detect the phase of a sample, the scanning range is 20-80 degrees, the angle step is 0.02 degree, a Cu target is adopted, the X ray is Cu K α ray, the wavelength is 0.15418nm, and the test result is shown in figure 1.
As can be seen from fig. 1, after the mixed powder of LSM and BCO is calcined at 800 ℃ for 10 hours, their respective structures are still maintained, and no other impurity peaks appear, and the spectrogram is only the respective characteristic peaks of LSM and BCO, which indicates that no detectable phase reaction occurs between LSM and BCO at 800 ℃ or below; this also indicates good chemical compatibility between LSM and BCO at the cathode preparation sintering temperature required for the solid oxide fuel cell cathode material and the operating temperature range of intermediate temperature solid oxide fuel cells.
Test example 2
The intermediate-temperature solid oxide fuel cell composite cathode materials obtained in the embodiments 1 to 4 are respectively processed as follows:
mixing a cathode material to be tested and an organic binder (3 wt.% ethyl cellulose +97 wt.% terpineol) according to a mass ratio of 3: 2, mixing to obtain cathode slurry;
pressing Gd by dry pressing0.1Ce0.9O1.95(GDC) electrolyte support, which is then calcined at 1400 ℃ for 24h to form a dense GDC electrolyte sheet;
symmetrically coating the cathode slurry on two sides of a compact GDC electrolyte sheet, and drying the GDC electrolyte sheet coated with the cathode slurry at 100 ℃;
and then placing the battery in a high-temperature furnace, and sintering the battery for 2 hours at 800 ℃ to obtain the symmetrical battery.
Measuring the impedance of the cathode by adopting a symmetrical electrode method: the Autolab electrochemical workstation is used for testing the alternating-current impedance spectrum of the symmetrical battery, and the testing frequency range is 0.1-106Hz, the applied alternating voltage is 10 mV; the test results are shown in FIG. 2.
After the GDC electrolyte sheet coated with the pure LSM material provided in comparative example 1 was calcined at 1100 c for 2h, the resistance test was performed according to the resistance test method described above, and the test results are shown in fig. 2.
After the GDC electrolyte sheet coated with the LSM-GDC composite cathode material provided in comparative example 3 was calcined at 1100 c for 2 hours, the resistance test was performed according to the resistance test method described above, and the test results are shown in fig. 2.
As can be seen from FIG. 2, the composite cathode material component of the intermediate-temperature solid oxide fuel cell provided in the embodiment 3 of the present invention is 60 wt.% La0.85Sr0.15MnO3-δ·40wt.％Bi2CuO4(i.e., LSM-40BCO) composite cathodes have the lowest polarization resistance and the highest electrochemical activity, the polarization resistance R of which is at 700 deg.CPIs only 0.13. omega. cm2Is 60 wt.% La0.85Sr0.15MnO3-δ·40wt.％Gd0.1Ce0.9O1.95(LSM-GDC, the best mass ratio) the polarization resistance value of the composite cathode under the same condition (0.38 omega cm)2) 34% of the total electrode, only the polarization resistance value (2.18. omega. cm) of a pure LSM cathode under the same conditions2) 6% of the total. Therefore, the electrochemical performance of the intermediate-temperature solid oxide fuel cell composite cathode material provided by the invention under the intermediate-temperature condition is far superior to that of the traditional cathode material.
Test example 3
Output performance tests were performed on an anode-supported single cell using NiO-YSZ as the anode, YSZ as the electrolyte, GDC as the separator, and the intermediate-temperature solid oxide fuel cell composite cathode material provided in example 3 as the cathode. The preparation of the cathode layer in the single cell was the same as the preparation of the cathode layer in the symmetric cell in test example 2. The output performance of the monocell is tested by adopting a four-electrode method, and during the test of the cell, humidified hydrogen is taken as fuel gas, surrounding air is taken as an oxidant, and silver paste is uniformly coated on the two sides of a cathode and an anode respectively to be taken as current collecting layers. Testing the volt-ampere characteristic curve (i.e., I-V curve) of the cells using the german Zahner electrochemical workstation; then, calculating output power density according to the measured current and voltage values to obtain an I-P curve; the results of the I-V and I-P curve tests at 550-700 ℃ for the single cell using the composite cathode material of the intermediate-temperature solid oxide fuel cell provided in example 3 as the cathode are shown in FIG. 3.
As is clear from FIG. 3, the maximum output power of the single cell was 148mW/cm at 550 ℃, 600 ℃, 650 ℃ and 700 ℃ respectively2、283mW/cm2、481mW/cm2、661mW/cm2The intermediate-temperature solid oxide fuel cell composite cathode material provided by the invention has good intermediate-temperature electrochemical performance.
The test results show that the polarization resistance R of the symmetrical battery prepared by taking the intermediate-temperature solid oxide fuel cell composite cathode material provided by the invention as the cathode material is 700 DEG CPIs only 0.13. omega. cm2Is 60 wt.% La0.85Sr0.15MnO3-δ·40wt.％Gd0.1Ce0.9O1.95(optimum proportion) polarization resistance value (0.38 omega cm) of composite cathode under the same condition2) 34% of (A), only pure La0.85Sr0.15MnO3-δPolarization resistance value (2.18 omega cm) of cathode under the same condition2) 6% of; the anode-supported single cell prepared by using the intermediate-temperature solid oxide fuel cell composite cathode material provided by the invention as a cathode material has the maximum output power of 661mW/cm at 700 DEG C2The composite cathode material of the intermediate-temperature solid oxide fuel cell provided by the invention has excellent application potential in the intermediate-temperature solid oxide fuel cell; the preparation method provided by the invention is simple in process, suitable for industrial production and has great economic value.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. The intermediate-temperature solid oxide fuel cell composite cathode material is characterized in that the chemical formula of the intermediate-temperature solid oxide fuel cell composite cathode material is x [ La ] La0.85Sr0.15MnO3-δ]·(1-x)[Bi2CuO4]，x＝40wt.％～70wt.％。
2. An intermediate-temperature solid oxide fuel cell composite cathode material according to claim 1, characterized in that La in the intermediate-temperature solid oxide fuel cell composite cathode material0.85Sr0.15MnO3-δHas a perovskite structure; bi in the composite cathode material of the intermediate-temperature solid oxide fuel cell2CuO4Has a spinel structure.
3. A method for preparing a composite cathode material of an intermediate-temperature solid oxide fuel cell according to claim 1 or 2, characterized by comprising the following steps:
providing Bi2CuO4Powder;
la0.85Sr0.15MnO3-δPowder and Bi2CuO4Mixing and ball-milling the powder to obtain a ball grinding material;
and drying the ball milling material to obtain the intermediate-temperature solid oxide fuel cell composite cathode material.
4. The method according to claim 3, wherein the La is0.85Sr0.15MnO3-δPowder and Bi2CuO4The mass ratio of the powder is 4: (6-7): 3.
5. the method according to claim 4, wherein the La is0.85Sr0.15MnO3-δThe particle size of the powder is 100-150 nm; the Bi2CuO4The particle size of the powder is 1-2 μm.
6. The preparation method according to claim 3, wherein the milling balls for ball milling are agate balls; the diameter of the grinding ball is 5-7 mm; the La0.85Sr0.15MnO3-δPowder and Bi2CuO4The ratio of the total mass of the powder to the grinding balls is 5 g: (25-40).
7. The method according to claim 3, wherein the liquid medium for ball milling is absolute ethanol; the La0.85Sr0.15MnO3-δPowder and Bi2CuO4The ratio of the total mass of the powder to the liquid medium is 5 g: (20-30) mL.
8. The preparation method of claim 3, wherein the rotation speed of the ball mill is 200-300 rpm and the time is 5-10 h.
9. The preparation method according to claim 3, wherein the drying temperature is 80-120 ℃ and the drying time is 2-6 h.
10. An intermediate-temperature solid oxide fuel cell composite cathode material as defined in any one of claims 1 to 2 or an intermediate-temperature solid oxide fuel cell composite cathode material prepared by the preparation method as defined in any one of claims 3 to 9, for use in a fuel cell.
CN201911412275.5A 2019-12-31 2019-12-31 Intermediate-temperature solid oxide fuel cell composite cathode material and preparation method and application thereof Pending CN111082111A (en)

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