CN111092233A - 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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CN111092233A
CN111092233A CN201911412234.6A CN201911412234A CN111092233A CN 111092233 A CN111092233 A CN 111092233A CN 201911412234 A CN201911412234 A CN 201911412234A CN 111092233 A CN111092233 A CN 111092233A
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fuel cell
solid oxide
oxide fuel
powder
cathode material
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李娜
孙丽萍
赵辉
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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
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • 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
    • 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
    • H01M4/90—Selection of catalytic material
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • H01M4/9025—Oxides specially used in fuel cell operating at high temperature, e.g. SOFC
    • 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 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 chemical composition of the intermediate-temperature solid oxide fuel cell composite cathode material provided by the invention is that the chemical formula of the intermediate-temperature solid oxide fuel cell composite cathode material is xBi2CuO4]·(1‑x)[Gd0.1Ce0.9O1.95]And x is 40-70 wt.%. The results of the examples show that the polarization resistance 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 only 0.40 omega cm at 700 DEG C2And a polarization resistance at 550 ℃ of 5.45. omega. cm2(ii) a The maximum output power of the prepared anode-supported single cell at 700 ℃ is up to 326mW/cm2And 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. Some of the currently common intermediate-temperature SOFC cathode materials are La0.6Sr0.4Co0.2Fe0.8O3-δ、Ba0.5Sr0.5Co0.8Fe0.2O3-δAnd PrBaCo2O5+δEtc. although having good catalytic activity for oxygen reduction reaction, these materials contain rare earth elements and alkaline earth elements, so there are some critical problems directly affecting SOFC performance, such as: poor chemical and structural stability at high temperature, easy to have adverse chemical reaction with the traditional electrolyte material and CO resistance2The poisoning ability is poor. In response to these problems, a cathode material having a spinel structure, which does not contain rare earth and alkaline earth elements, has attracted attention.
SOFC cathode materials with spinel structure are currently mainly composed of transition metal elements (Co, Mn)3O4、(Cu,Mn)3O4Or (Cu, Co)3O4The oxides do not contain rare earth or alkaline earth elements, so the chemical compatibility between the oxides and other component materials in contact with the SOFC is better; in addition, the catalytic activity of the material on oxygen reduction reaction is generally higher than that of the traditional cathode material (La, Sr) MnO3. However, since these materials are mainly composed of transition metal elements, they have strong metal-oxygen bond energy; meanwhile, oxygen is densely stacked in the structure of the material, so that the oxygen is difficult to conduct in the material, the materials basically belong to pure electronic conductors, and the electrochemical performance cannot meet the medium-low temperature conditionThe use requirements of SOFCs.
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 does not contain rare earth or alkaline earth elements, has electron conductivity and excellent oxygen reduction catalytic activity, and exhibits excellent electrochemical performance under an 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 composite cathode material of an intermediate-temperature solid oxide fuel cell, which has the chemical formula of xBi2CuO4]·(1-x)[Gd0.1Ce0.9O1.95]，x＝40wt.％～70wt.％。
Preferably, Bi in the intermediate-temperature solid oxide fuel cell composite cathode material2CuO4Has a spinel structure; gd in the composite cathode material of the intermediate-temperature solid oxide fuel cell0.1Ce0.9O1.95Has a fluorite 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;
adding Bi2CuO4Powder and Gd0.1Ce0.9O1.95Mixing 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, said Bi2CuO4Powder and Gd0.1Ce0.9O1.95The mass ratio of the powder is 4: 6-7: 3.
preferably, said Bi2CuO4The particle size of the powder is 1-2 μm; the Gd0.1Ce0.9O1.95The particle size of the powder is 60-90 nm.
Preferably, the grinding balls for ball milling are agate balls; the diameter of the grinding ball is 5-7 mm; the Bi2CuO4Powder and Gd0.1Ce0.9O1.95The 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 Bi2CuO4Powder and Gd0.1Ce0.9O1.95The 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 composite cathode material of an intermediate-temperature solid oxide fuel cell, which has the chemical formula of xBi2CuO4]·(1-x)[Gd0.1Ce0.9O1.95]And x is 40 wt.% to 70 wt.%. In the present invention, Bi2CuO4Due to the specific 6s orbital lone pair electrons of the middle Bi, the distribution height of electron clouds around bismuth ions is uneven, so that the arrangement of oxygen ions coordinated with the bismuth ions presents high relaxation deformation, the rapid migration of oxygen is facilitated, the oxygen diffusion coefficient and the oxygen surface exchange coefficient of the material are increased, and the composite cathode material has good oxygen transport performance; at the same time, Bi2CuO4The material exhibits mixed oxygen ion-electron conductivity at 700 ℃ or higher, but below 700 ℃, Bi2CuO4Is a pure electronic conductor, and is mixed with a proper amount of oxygen ion conductor material Gd0.1Ce0.9O1.95Mixed to prepare the composite cathode materialThe addition of the oxygen ion conductor phase can not only increase the oxygen ion conductivity in the cathode, but also effectively enlarge the active area of the oxygen reduction reaction in the cathode, thereby being beneficial to improving the catalytic activity of the composite cathode on the oxygen reduction reaction.
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 0.40 omega cm2Is the polarization resistance (0.59 omega cm) of a pure BCO cathode under the same conditions2) 67.8% of; the polarization resistance of a symmetrical battery prepared by taking the intermediate-temperature solid oxide fuel cell composite cathode material as a cathode material at 550 ℃ is 5.45 omega-cm2Is the polarization resistance (14.88 omega cm) of a pure BCO cathode under the same conditions2) 36.6% of; the anode-supported single cell (the configuration is Ni-YSZ/YSZ/GDC/cathode) prepared by taking the intermediate-temperature solid oxide fuel cell composite cathode material provided by the invention as a cathode material has the maximum output power of 326mW/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 a graph showing the impedance test of a symmetrical cell composed of example 3 of the present invention and comparative example 2;
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 composite cathode material of an intermediate-temperature solid oxide fuel cell, which has the chemical formula of xBi2CuO4]·(1-x)[Gd0.1Ce0.9O1.95]，x＝40wt.％～70wt.％。
In the invention, the Bi in the intermediate-temperature solid oxide fuel cell composite cathode material2CuO4Has a spinel structure; the intermediate-temperature solid oxide fuel cell composite cathode materialGd in the material0.1Ce0.9O1.95Has a fluorite 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;
adding Bi2CuO4Powder and Gd0.1Ce0.9O1.95Mixing 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. Bi of the present invention2CuO4The 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 present invention, the drying isThe 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 invention, the calcining temperature is preferably 750-800 ℃, and the time is preferably 24-36 h.
To obtain Bi2CuO4After the powder is prepared, Bi is mixed in the invention2CuO4Powder and Gd0.1Ce0.9O1.95And mixing and ball-milling the powder to obtain the ball grinding material.
In the present invention, the Bi2CuO4Powder and Gd0.1Ce0.9O1.95The 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 Gd0.1Ce0.9O1.95The particle size of the powder is preferably 60 to 90nm, more preferably 65 to 85nm, and still more preferably 70 to 80 nm. The invention is directed to the Gd0.1Ce0.9O1.95The source of the powder is not particularly limited, and Gd, which is well known to those skilled in the art, is used0.1Ce0.9O1.95The 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 Bi2CuO4Powder and Gd0.1Ce0.9O1.95The 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 Bi2CuO4Powder and Gd0.1Ce0.9O1.95The 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. When the intermediate-temperature solid oxide fuel cell composite cathode material is used as a cathode material of a solid oxide fuel cell, the application temperature of the obtained 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;
bi with the grain diameter of 1-2 mu m obtained by the preparation method2CuO4Powder and Gd with the particle diameter of 60-90 nm0.1Ce0.9O1.95The powder is prepared according to the following steps of 5: 5 (total mass: 5g), poured into a 100mL ball mill pot, and addedPouring 25mL of absolute ethyl alcohol into 30 agate balls with the diameter of 6.3mm as grinding media, and then carrying out ball milling for 8h 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.% Bi)2CuO4·50wt.％Gd0.1Ce0.9O1.95I.e., BCO-50 GDC).
Example 2
Bi obtained by preparation2CuO4Powder and Gd0.1Ce0.9O1.95The mass ratio of the powder 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.% Bi)2CuO4·60wt.％Gd0.1Ce0.9O1.95I.e., BCO-60 GDC).
Example 3
Bi obtained by preparation2CuO4Powder and Gd0.1Ce0.9O1.95The mass ratio of the powder 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.% Bi)2CuO4·40wt.％Gd0.1Ce0.9O1.95I.e., BCO-40 GDC).
Example 4
Bi obtained by preparation2CuO4Powder and Gd0.1Ce0.9O1.95The mass ratio of the powder is 7: the other operations are the same as example 1, and the intermediate-temperature solid oxide fuel cell composite cathode material (70 wt.% Bi) is obtained2CuO4·30wt.％Gd0.1Ce0.9O1.95I.e., BCO-30 GDC).
Comparative example 1
With pure Gd from example 10.1Ce0.9O1.95Powder (GDC) is the comparative example 1 material.
Comparative example 2
Bi obtained in example 12CuO4Powder (BCO) is the comparative example 2 material.
Test example 1
The materials of example 1 and comparative examples 1-2 were treated as follows:
the material obtained in example 1 was pressed into a round green body, calcined at 800 ℃ for 10 hours, and then ground into powder, and XRD tests were performed on the obtained powder materials, respectively, under the test conditions that an X' Pert PRO X-ray diffractometer was used to detect the phase of a sample, the scanning range was 20 to 80 °, the angle step was 0.02 °, the Cu target, the X-ray was Cu K α ray, the wavelength was 0.15418nm, and the test results are shown in fig. 1.
As can be seen from FIG. 1, the BCO provided in comparative example 2 forms a tetragonal spinel structure and no hetero-phase is generated, and has space group P4/ncc; bi2CuO4Powder and Gd0.1Ce0.9O1.95After the powder is mixed and calcined for 10 hours at 800 ℃, the respective structure is still maintained, other impurity peaks do not appear, and only Bi appears in a spectrogram2CuO4And Gd0.1Ce0.9O1.95The results of the respective characteristic peaks show that Bi is at 800 ℃ or below2CuO4With Gd0.1Ce0.9O1.95There is no detectable phase reaction between the two, which also indicates good chemical compatibility between the two at the cathode preparation temperature and the operating temperature range of the medium temperature SOFC.
Test example 2
Pressing Gd by dry pressing0.1Ce0.9O1.95(GDC) electrolyte support, in particular: gd is added0.1Ce0.9O1.95Pressing the powder under 200MPa to obtain a wafer with the diameter of 15mm, and then calcining the wafer at 1400 ℃ for 24h to obtain a compact GDC electrolyte sheet;
the intermediate-temperature solid oxide fuel cell composite cathode material BCO-40GDC obtained in example 3 and the pure BCO material of comparative example 2 are respectively processed as follows:
mixing a 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;
symmetrically coating cathode slurry obtained by BCO-40GDC obtained in example 3 on two sides of a compact GDC electrolyte sheet, drying the GDC electrolyte sheet coated with the cathode slurry at 100 ℃, then placing the GDC electrolyte sheet in a high-temperature furnace, and sintering the GDC electrolyte sheet for 2 hours at 800 ℃ to obtain a symmetrical battery;
and symmetrically coating the cathode slurry obtained from the pure BCO material of the comparative example 2 on two sides of the compact GDC electrolyte sheet, drying the GDC electrolyte sheet coated with the cathode slurry at 100 ℃, then placing the GDC electrolyte sheet in a high-temperature furnace, and sintering the GDC electrolyte sheet for 2 hours at 700 ℃ to obtain the symmetrical battery.
Measuring the impedance of the cathode by adopting a symmetrical electrode method: testing the alternating current impedance spectrum of the obtained symmetrical battery by using an Autolab electrochemical workstation, wherein the testing frequency range is 106-0.1Hz and an alternating voltage of 10 mV; 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 example 3 of the present invention is 60 wt.% Bi2CuO4·40wt.％Gd0.1Ce0.9O1.95The polarization resistance of the composite cathode (namely BCO-40GDC) is less than that of a pure BCO cathode in the test temperature range of 550-700 ℃, and the polarization resistance R of the composite cathode at 700 DEG CPIs 0.40 omega cm2Is the polarization resistance (0.59 omega cm) of a pure BCO cathode under the same conditions2) 67.8% of; the polarization resistance at 550 ℃ is 5.45 omega cm2Is the polarization resistance (14.88 omega cm) of a pure BCO cathode under the same conditions2) 36.6% of. The results show that Bi is comparable to pure Bi2CuO4The cathode and the composite cathode show higher catalytic activity to oxygen reduction reaction, Gd0.1Ce0.9O1.95The proper amount of the composite cathode improves the electrochemical performance of the composite cathode, and the lower the test temperature is, the more remarkable the effect of improving the electrochemical performance is.
Test example 3
The output performance test was performed on the anode-supported single cell using Ni-YSZ as the anode, YSZ as the electrolyte, GDC as the separator, and the composite cathode material of the intermediate-temperature solid oxide fuel cell 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 of example 3 in test example 2. The output performance of the single cell is tested by adopting a four-electrode method, when the cell is tested, humidified hydrogen is introduced to one side of an anode to serve as fuel gas, a cathode is exposed to ambient air, namely air serves as an oxidant, the test temperature range is 550-750 ℃, and silver colloid is coated on the two sides of the cathode and the anode respectively to serve 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 550-750 ℃ for a 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 density of the single cell was 507mW/cm at 750 ℃, 700 ℃, 650 ℃, 600 ℃ and 550 ℃ respectively2，326mW/cm2，192mW/cm2，110mW/cm2，56mW/cm2The test results show that Bi provided by the present invention2CuO4And Gd0.1Ce0.9O1.95The formed composite cathode material shows good catalytic performance of oxygen reduction reaction under the practical application condition of the SOFC.
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 0.40 omega cm2Is the polarization resistance (0.59 omega cm) of a pure BCO cathode under the same conditions2) 67.8% of; the polarization resistance at 550 ℃ is 5.45 omega cm2Is the polarization resistance (14.88 omega cm) of a pure BCO cathode under the same conditions2) 36.6% of; 60 wt.% Bi in a test temperature range of 550 to 700 DEG C2CuO4·40wt.％Gd0.1Ce0.9O1.95The polarization resistance of the composite cathode is less than that of pure Bi2CuO4The polarization resistance of (1); the anode supporting single cell prepared by taking the intermediate-temperature solid oxide fuel cell composite cathode material provided by the invention as a cathode material has the maximum output power of 507mW/cm at 750 DEG C2Maximum of 700 ℃ CThe output power is up to 326mW/cm2The 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; in addition, the sintering temperature required by the cathode layer in the preparation process of the composite cathode material of the intermediate-temperature solid oxide fuel cell is low, so that the occurrence of adverse chemical reaction between the cathode and an electrolyte is effectively avoided, the growth of cathode particles and the coarsening of the microscopic morphology of the cathode can be avoided, and the guarantee and the improvement of the performance of the solid oxide fuel cell are facilitated; 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 xBi2CuO4]·(1-x)[Gd0.1Ce0.9O1.95]，x＝40wt.％～70wt.％。
2. An intermediate-temperature solid oxide fuel cell composite cathode material according to claim 1, characterized in that Bi in the intermediate-temperature solid oxide fuel cell composite cathode material2CuO4Has a spinel structure; gd in the composite cathode material of the intermediate-temperature solid oxide fuel cell0.1Ce0.9O1.95Has a fluorite 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;
adding Bi2CuO4Powder and Gd0.1Ce0.9O1.95Mixing 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 said Bi2CuO4Powder and Gd0.1Ce0.9O1.95The mass ratio of the powder is 4: 6-7: 3.
5. the method according to claim 3 or 4, wherein the Bi is2CuO4The particle size of the powder is 1-2 μm; the Gd0.1Ce0.9O1.95The particle size of the powder is 60-90 nm.
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 Bi2CuO4Powder and Gd0.1Ce0.9O1.95The 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 Bi2CuO4Powder and Gd0.1Ce0.9O1.95The 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.
CN201911412234.6A 2019-12-31 2019-12-31 Intermediate-temperature solid oxide fuel cell composite cathode material and preparation method and application thereof Pending CN111092233A (en)

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